New! View global litigation for patent families

US3163606A - Textile bleaching composition - Google Patents

Textile bleaching composition Download PDF

Info

Publication number
US3163606A
US3163606A US3339760A US3163606A US 3163606 A US3163606 A US 3163606A US 3339760 A US3339760 A US 3339760A US 3163606 A US3163606 A US 3163606A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
lightness
oxygen
active
sodium
parts
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 - Lifetime
Application number
Inventor
Wilhelmus J C Viveen
Cornelis U Kloosterman
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.)
Konink Ind Mij Vorheen Noury &
Original Assignee
Konink Ind Mij Vorheen Noury &
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
Grant date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators; Bleach catalysts
    • C11D3/3907Organic compounds
    • C11D3/3917Nitrogen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06Inorganic compounds
    • C11D9/08Water-soluble compounds
    • C11D9/10Salts

Description

3,163,606 TEXTILE BLEACHING COMPOSITION Wilheimus J. C. Viveen and Corneiis U. Kloosterman,

Deventer, Netheriands, assignors to Koninklijke Industrieele Maatschappy vorheen Notary 8: van der Lande N.V., Deventer, Netherlands, a corporatien of the Netherlands No Drawing. Filed June 2, 1969, Ser. No. 33,3?7 Claims priority, application Great Britain, June 19, 1959, 21,220/59; July 29, 1959, 26,061/59; Oct. 13, E59, 34,695/59; Netherlands, June '6, 1959, 239,952.

Claims. (Cl. 252-98) 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.

It is an object of this invention to provide washing and bleaching compositions containing active oxygen releasing compounds and activators for such compounds.

It is a further object of this invention to provide certain novel compounds and mixtures of said compounds for use as activators for active oxygen releasing compounds in washing and bleaching compositions.

It is a further object of this invention to provide a process for producing said novel activator compounds.

It is a further object of this invention to provide said activator compounds in a coated form to enhance the activity and stability of said compounds.

Further objects and attendant advantages of this invention will become apparent from the following more detailed description.

The term textiles as used throughout the specification is intended to include natural and synthetic fibres as well as products manufactured therefrom or therewith.

It is well-known that on Washing and/or bleaching textiles use is made of agents containing active oxygen releasing compounds having a bleaching elfect on the textiles to be treated. As the active oxygen releasing compounds, inorganic persalts such as perborates, percarbonates, perphosphates, persilicates, persulphates and, moreover, hydrogen peroxide and sodium peroxide are used.

However, 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.

It has already been proposed to enhance theeifect of a washing and/or bleaching agent containing an active oxygen releasing compound by adding thereto particular substances, so-called activators. Definite quantities of organic acid anhydrides, for instance, have been added to washing and bleaching agents containing active oxygen nited States Patent 0 ice ' is hightly eflicient for the washing and/ or bleaching treatment of textiles at a temperature below boiling temperature.

Consequently, 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. Moreover, 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. Apart from this, the compositions according to the invention are particularly effective for washing cotton goods,

as this material even if washed several times keeps a high degree oflightness and does not easily become yellow. 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.

As activators for oxygen releasing compounds accordingto this invention there are included: 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. However, in practice, this measure a does not yield the desired result, as the reactivity of most acid anhydrides appears to be insuificient in this respect.

It has also been proposed to add formamide and retire-- sentatives of the nitrile group to washing agents containing active oxygen releasing compounds. However, 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.

Now it has been found that if a compound containing one or more nitrogen atoms having at least two acyl groups attached to the same nitrogen atom or a mixture of such compounds is added to a washng and/oibleaching agent of the usual composition containing an active oxygen releasing compound, a composition is obtained which thanes, e.g., N,N-diacetylethylurethane, N-acetyLN-propionylethylurethane; N-diacetylated hydrazines, e.g., tri. acetylhydrazine, tetra-acetylhydrazine, tripfopionylhydrazine, N,N-diacetyl-N-benzoylhydrazine and N,Ndiacetyl- N'-isopropylidenehydrazine; N-diacylated alkylenediamines, e.g., triacetylmethylenediamine,- tetra-acetylmethylenediamine, hexamethylenediamine and tetra-acetylphenylenediamine,

bazide and dicyanodiamide. :f I

The favourable properties mentioned above of the washing and/or bleaching agents according to the invention the 'N-diacyl compounds of semicarbazide, thiosemicar:

may surprisingly still be improved to a large extent, if the activator according to the invention iscovered with a solid material soluble in the washing and/ or bleaching liquid. j As such, 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 Furthermore condensation products of ethyleneoxide and propyleneoxide may be used. More partetra-acetylethylenediamine, tetra-'acetyh' ticularly those compounds having a useful function in the suds, such as, e.g., polyvinylalcohol, carboxymethylcellulose, cetylalcohol and fatty acid alkanolamides, are especially suitable. Moreover, by this means the shelf life, especially of the finished powders, is enhanced.

It is recommended to granulate the activator before covering.

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. As to 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.

However, it is also possible to execute this treatment with a washing or bleaching liquid to which one or more activators have been added, just prior to the treatment or during the same.

In any case very good results are obtained with a treatment temperature below boiling temperature, preferably however with a temperature between 15 and 85 C.

As activators for the active oxygen releasing compound in a washing and/or bleaching agent there have been found especially effective the hitherto unknown compounds with the general formula CH3C O C C113 in which R represents a hydrogen-atom or a COCH group.

These new compounds according to the invention, or mixtures thereof, may be obtained by either of the following two methods.

Thus it is possible to prepare 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.

According to the invention, 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.

If during the reaction between diacetylmethylenediamine and acetic acid anhydride, the acetic acid liberated is not eliminated from the reaction mixture, mainly N,N,N-triacetylmethylenediamine is formed.

When only part of the quantity of acetic acid that theoretically could be formed during the acetylation is eliminated from the reaction mixture, mixtures are obtained that appearto contain triacetylmethylenediamine and tetra-acetylmethylenediamine with the quantity of the former increasing as less acetic acid is eliminated.

The following examples are presented to further illustrate the invention, and should not be considered as limiting thereof.

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

Parts of the pieces of material were washed for 15 minutes at 60 in suds of the following composition:

G./l. Sodium salt of dodecyl benzene sulphonic acid 0.85 Lauryl isopropanolamide 0.10 Tetrasodium pyrophosphate 0.75 Pentasodium tripolyphosphate 0.60 Alkaline water-glass (Na O/SiO =l/2) 0.20 Na CMC (sodium carboxymethylcellulose) 0.04 Sodium sulphate 0.80 Sodium perborate-tetrahydrate (10.2% active oxygen) 0.50

The percentage of lightness of the washed pieces of material amounted to 64 (lightness of magnesium oxide=100 units), which is 13 units higher than the percentage of lightness of the pieces of material after thorough rinsing with water, which was 51.

Other parts of the material were Washed in three samples of suds of the same composition, to which respectively 0.1, 0.4 and 0.5 g./l. of tetra-acetyl hydrazine was added. These suds contained per atom of active oxygen from the perborate 0.63, 2.50 and 3.14 acetyl groups as tetra-acetyl hydrazine, respectively.

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%.

EXAMPLE II Pieces of the same kind of fabric, soiled with black currant juice, as used in Example I, were washed for 15 minutes at 60 C. in suds of the following composition:

G./l. Sodium soap 3.1T Sodium carbonate 1.00 Neutral water-glass (Na O/SiO =1/3.3) 0.17 Sodium perborate-tetrahydrate (9.9% of active oxygen) 0.68

The percentage of lightness of the material was increased to 62% by washing (lightness of magnesium oxide=100 unit); this is 11 units higher than the lightness obtained by only rinsing the material thoroughly with water.

If 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%. In this case, the number of acetyl groups added to the suds as tetra-acetyl hydrazine was 2.0 per atom of active oxygen from the perborate.

EXAMPLE III A detergent in powder form had the following composition:

100 parts by weight of this powder were mixed with 8 parts by weight of sodium perborate-tetrahydrate and 6.25 parts by weight of tetra-acetyl hydrazine (STAH mixture).

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.

With this test, a similar test was carried out with a mixture of 100 parts by weight of the afore-mentioned powder and 8 parts by weight of sodium perboratetetrahydrate without tetra-acetyl hydrazine (mixture SO). 5.4 grams per litre solution were used of this mixture.

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).

In the case of the SO mixture, this difference in lightness was 12 units (lightness of magnesium oxide=100 units).

So by using a quantity of tetra-acetyl hydrazine such as to correspond to 2.5 bound acetyl groups per atom of active oxygen, 21 relative improvement of 125% was obtained.

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).

A solution was prepared containing 5.75 g. per litre of this STrAH mixture and the same washing test was carried out with it as described in Example III.

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.

So the relative improvement in this case, where 2.5 bound acetyl groups per atom of active oxygen were used, was 83%.

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).

A solution was prepared, containing 5.95 g. per litre of this STrPrH mixture and a similar washing test was carried out with it as described in Example III, except that in this case the experiment Was carried out at 50 C.

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.

So the relative improvement in this case, where 3.3 bound propionyl groups per atom of active oxygen were used, was 92%.

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. a

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.

So the relative improvement in this case, where 2.5

bound acetyl groups per atom of active oxygen were used, was 77% 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).

A solution was prepared, containing 5.72 g. per litre of this SDAA mixture and a similar washing testwas carried out with it as described in Example VI.

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.

So the relative improvement in this case, where 2.5 bound acetyl groups per atom of active oxygen were used, was 69%. 1

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).

A solution was prepared containing 5.70 g. per litre of this STrAA mixture and a similar washing test Was I carried out with it as described in Example VI.

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.

So the relative improvement in this case, where 2.5 bound acetyl groups per atom of active oxygen were used, was 131%.

EXAMPLE D A detergent in powder form had the following composition:

of sodium soap of sodium carbonate of neutral water-glass of water With this test, a similar test was carried outwith a mixture of 100 parts by weight of the afore-mentioned powder and 7.5 parts by weight of sodium perbroratetetrahydrate without diacetyl propylarnine (ZO mixture). 8.60 grams per litre of this mixture were used.

' The lightness of thematerial washed with the ZDAPrA mixture was 19 units higher than the lightness of material thoroughly rinsed with water only (51 units).

In the case of the Z0 mixture, this diiierence in lightness was 12 units (lightness of magnesium oxide=100 units). 7'

So by using a quantity of diacetyl propylamine such as to correspond to 2.0 bound acetyl groups per atom of active oxygen, a relative improvement of 58% was obtained. V a

' EXAMPLE X 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).

A solution was prepared containing 9.30 g. per litre of 7 this ZDAAL mixture and a similar washing test was carried out with it as described in Example IX.

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.

So the relative improvement in this case, where 2.0 bound acetyl groups per atom of active oxygen were used, was 92% EXAMPLE XI A similar washing test, as described in Example I, was carried out using suds containing 513 mg. N-ethyldiacetamide per litre instead of tetra-acetyl hydrazine.

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%.

EXAMPLE XII A similar washing test as described in Example II was carried out using suds containing 724 mg. N,N-diacetyl urethane per litre instead of tetra-acetyl hydrazine.

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 XIII A similar washing test as described in Example I was carried out using suds containing 753 mg. N-acetyl phthalimide per litre instead of tetra-acetyl hydrazine.

The relative improvement, as to the lightness of the washed material, Was in the case, where 1.25 bound acetyl groups per atom of active oxygen were used, 136%.

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.

Seven lots of these pieces of material were washed for minutes at 60 C. in seven diiferent suds.

All these suds contained:

Sodium salt of dodecyl benzene sulphonic acid 0.85 Lauryl isopropanolamide 0.10 Tetrasodium pyrophosphate 0.75 Pentasodium tripolyphosphate 0.60 Alkaline water-glass (Na O/SiO /2) 0.20

NaCMC (100%) (sodium carboxymethylcellulose) 0.040

Sodium sulphate 0.80

All concentrations refer to the anhydrous substances.

Further components of the different suds were as follows.

Suds 1: Sodium perborate (10.0% active oxygen) 0.52 Suds 2:

Sodium perborate 0.50 N,N tetra acetylmethylene diamine (hereinafter referred to as TAMD) 0.40

bound acetyl groups 2 4 Ratio atoms active oxygen Suds 3:

Sodium perborate 0.40 TAMD 0.40

Ratio bound acetyl groups 30 atoms active oxygen Suds 4:

Sodium perborate 0.40 TAMD 0.30

bound acetyl groups 25 Ratio atoms active oxygen bound aeetyl groups Ratio atoms active oxygen After washing, rinsing and drying, the lightness of the pieces of material was measured.

The results were:

Suds N0 1 2 3 4 5 6 7 Lightuess (percent of MgO) 62 81 79 79 76 76 71.5 Difference with the washing-test without TAMD 0 19 17 17 14 14 9. 5 Relative improvement,

percent 0 210 190 190 155 155 105 V The relative improvement is expressed as percentages of the diflFerence in lightness between the pieces of material washed with 0.52 g./l. perborate without TAMD, and the pieces of material only rinsed with water (lightness 53).

In spite of the very considerable decrease in perborate content of some of the suds, great improvements in bleaching effect were obtained when TAMD was addedto the suds.

EXAMPLE XV A detergent in powder form was made up having the following composition:

of sodium soap,

of sodium carbonate, of neutral water-glass, of water.

Subsequently five mixtures were prepared, namely:

Mixture 1:

parts by weight of above-mentioned detergent 10 parts by weight of sodium perborate (9.7% active oxygen) Mixture 2:

85.9 parts by weight of above mentioned detergent 8.6 parts by weight of sodium perborate 5.5 parts by weight of TAMD Ratio bound acyl groups :20

atoms active oxygen Mixture 3:

87.1 parts by weight of above-mentioned detergent 8.7 parts by weight of sodium perborate 4.2 parts by weight of TAMD bound acyl groups Ratio atoms active oxygen Mixture 4:

88.5 parts .by weight of above-mentioned detergent 5.8 parts by weight of sodium perborate 5.7 parts by weight of TAMD bound acyl groups Ram) atoms active oxygen 9 Mixture V 91.0 parts by weight of above-mentioned detergent 4.6 parts by weight of sodium perborate 4.4 parts by weight of TAMD A detergent was made up having the following composition: Percent Sodium salt of dodecyl benzene sulphonic acid 22.4

5 Lauryl isopropanolamide 2.6 Tetrasodium pyrophosphate 20.0 Ratio bound acyl groups Pentasodiurn tripolyphosphate 15.8 ato a ti e xygen Alkaline water-glass (Na O/SiO /2) 5.1 Sodium carboxymethylcellulose (NaCMC) (100%) 1.0 0 Sodium sulphate 2l.O These mixtures were used in concentrations of 6.9; Water 12.1 7.2; 7.1; 7.0 and 6.8 g./l. respectively.

In this way, the following concentrations were obtained quently four mixtures Were prepared, namely: (in g./l.). Mixture l:

85.5 parts by weight of above-mentioned detergent 14.5 parts by weight of sodium pyrophosphate perhydrate (8.05% active oxygen)- Mixture No 1 2 3 i 4 5 Mixture 2: v sodium Soap 31 31 3.1 3-1 3.1 p 77.9 parts by welght of above-mentioned detergent Sodium carbonate..- 1.0 1.0 1.0 1.0 1.0 Parts y Welght 0f sodlllm py p p e pera-a 8- s-a 8'1; 81 hydrate Tidt15 i ffff:::::::::3:: 0' 0:40 0136 0:40 0:30 parts y weight of TAMD Mixture 3:

91.2 parts by weight of above-mentioned detergent 8.8 parts by Weight of sodium percarbonate 14.6% Five lots of pieces of cotton material, soiled with the active Oxygen) same black currant juice as in Example XIV, were washed Mixture 4; these Suds r 10 mlnptes at After Washms, 82.7 parts by weight of above-mentioned detergent rinsing and drying, the lightness of the pieces of mate- 7.8 parts by weight of sodium percarbonate rial was measured, which gave the following results: 95 parts by Weight f A These mixtures were used in concentrations of 4.45, 4.88, 4.16 and 4.59 g./l. respectively. To each of the suds, a quantity of oxygen bleaching agent was added Mlxture N0 1 2 3 4 5 which corresponded to 52 mg./l. of active oxygen. t f1\ I 0) 62 5 75 6 5 7 655 q .conta'lned the components the orlglnal Difierence wgh the washing-testwith- 0 4 7 5 3 0 detergent 1n the same concentrations.

t'rAw 12.5 .0 g movements, percent 0 208 67 125 J Walior the TAMD containing mlxtures 2 and 4, the ratio Bound acyl groups The relative improvement 1s expressed as percentages {F oxygen of the difierence 1n lightness between the pieces of material washed with 0.69 g./l. of perborate without TAMD (mixture 1) and the pieces of material only rinsed with After Washing, rinsing and drying, the lightness of the water (lightness 56.5 V pieces of material was measured.

In spite of the very considerable decrease in perhorate The results were: 1

Mixture No .1 2 3 g 4 Oxygen releasing substance. Pyrophosphate Pyrophosphate Percarbon- Percarbonperhydrate. perhydrate. 7 ate. ate. Addition TAMD TAMD. Lilg/litgess (percent of '62 80 V g 61 79. Difie l'enee with the ,wash- 0 12 n 18.

ing-test without TAMD. Relative improvement--. 0 190 0 212%.

content of some of the suds, great improvements in bleaching eliect were obtained when TAMD was added to the suds.

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

7 EXAMPLE XvrI g g 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:

Mixture 1:

88 parts by weight of above-mentioned detergent 12 parts by weight of sodium pyrophosphate perhydrate (8.1% active oxygen) Mixture 2:

82.6 parts by weight of above-mentioned detergent 11.3 parts by weight of sodium pyrophosphate perhydrate 6.1 parts by weight of TAMD Mixture 3:

93 parts by weight of above-mentioned detergent 7 parts by Weight of sodium percarbonate (14.6%

active oxygen) Mixture 4:

87 parts by weight of above-mentioned detergent 6.6 parts by weight of sodium percarbonate 6.4 parts by Weight of TAMD For the TAMD-containing mixtures 2 and 4, the ratio was:

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.

All suds contained the components of the original detergent in the same concentrations.

Four lots of pieces of cotton material stained with the same black currant juice as described in Example I were washed in these suds for 10 minutes at 60 C. After washing, rinsing and drying, the lightness of the pieces of material was measured, which gave the follow- The coating amounted to 25% of the weight of the tetra-acetyl methylenediamine and consisted of a technical eutectic mixture of stearic and palmitic acid (M.P. 5355 C.). The experiments. were performed at 50 C.

The relative improvements as to the lightness of the washed material, were in these cases, where 2.0 bound acetyl groups per atom of active oxygen were used respectively 86% and 103%.

When applying a covered tetra-acetyl methylene diamine, an increase in lightness of about 20% as compared with the non-covered compound was obtained.

When applying 275 mg. of tetra-acetyl hydrazine covered with 18% of carboxy-methylcellulose or 428 mg. of tetra-acetylethylenediamine covered with 9% of cetylalcohol an increase in lightness of respectively 29% and 25% as compared with the corresponding non-covered compounds was found. Also in these cases the ratio Bound acetyl groups Atom of active oxygen EXAMPLE XX EXAMPLE XXI was 2.0

Each of four different detergent compositions A, B, C and D contained:

lug results: 12% non 1omc detergent (1sononylphenolpolyglycol- Mixture No 1 2 3 4 Oxygenreleasingsubstanee. Pyrophosphnte Pyrophosphate Percarbon- Percarbonperhydrate. perhydrate. ate. a Addition TAMD TAMD. Lightness (percent of 627 78 60.5 73.

MgO Difiference with the wash- 0 16 0 12.

ing-test without TAMD. Relativeimprovement 0 200% 0 192%.

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 In order to illustrate the beneficial effect of covering an activator according to the invention with a solid material soluble in the washing and/ or bleaching liquid, 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.

ether, containing about 8 ethylene oxide groups in each molecule) 36% sodium tripolyphosphate 8% sodium silicate, SiO /Na O ratio=2/ l 2% commercial CMC, containing 50% sodium salt. of

carboxymethyl-cellulose 6.6% sodium perborate Further these four compositions contained respectively:

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:

Total meq. combined acyl groups Mg. at. active oxygen was equal to 2.021.

All four compositions were used in a concentration of 5.00 g./l. for washing pieces of a cotton fabric, which had been soiled uniformly with black currant juice. After thoroughly rinsing with water, and ironing, the lightness (or apparent luminosity) of the fabric was 49.4 (lightness of magnesium oxide=).

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.

Lightness of fabric pieces, washed and bleached in composition 14 to the bleaching liquid. At 20 the pH of this solution was 10.0.

After the bleaching process, the pieces of cotton fabric were rinsed with softened water and dried.

Temperature of treatment 5 Measuring with the photo-electric remission meter gave A B O D the following remission-values:

g i tBlezitching Temp" Tristimulus leIIllSSlOll values Yrellggv 66.3 67. 68.3 mem G B A In the following table, the improvements in the light- 60 79.5 67.8 82.5 18.3 ness, caused by the above-mentioned activators are ex- 2%: 2 ggressed as percentages of the difference between the lightness of the fabric after rinsing with water only and the lightness of the material after treatment with detergent While by bleaching with hydrogen peroxide without composition D at 50 C., as compared with the lightness TAMD the yellowness calculated according to the formula of the latter. from Hunter had hardly altered or even had somewhat 2 increased, by bleaching in the presence of TAMD it de- Percentage improvement of lightness. 0 creased consifierably- Temperature of treatment Treatment compomwn- Expressed in percentages of the diiference between the remission values of the piece of fabric bleached accord- A B C D ing to treatment (a) and those of the unbleached sample M, the improvements of the remission values of the 3% treated materials, as compared with those of the fabric 90 79 96 bleached according to treatment (a) were: 54 65 72 Percentage Improvements The same results are obtained, if the detergent compon sitions contain fluorescent brighteners, dyestuffs and/or Tristimulus-lemission Values perfumes. Essentially the same results are obtained with Bleachmg treatment if? other kinds of fabrics, like wool, linen, silk, viscose rayon, G B A acetate rayon, polyamide, polyester, polynitrile, polyvinyl and other natural and synthetic fibres. The same applies 0 0 0 82 19 59 16 to the use of other non ionic surface active agents and 133 487 173 other builders.

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. Asample of the treated fabric was dried (sample M) and the light remissions (difiuse reflections) were measured with the aid of a photo-electric remission-meter. 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 yellowness, J, was 17.1 according to the formula from R. S. Hunter (Photoelectric Tristimulus Colorim etry With Three Filters, Circular of the National Bureau of Standards C 429, US. Government Printing Office, Washington, 1942, p. 22):

The pieces of cotton fabric boiled with sodium hydroxide and rinsed with softened water were bleached for 15 minutes in the following ways:

(a) At 60 with a solution containing 3.0 g. of anhydrous soda and 2.0 g. of sodium bicarbonate per litre and a quantity of hydrogen peroxide equivalent to an active oxygen content of 1.18 g. per litre of solution. At 20 the pH of the solution was 10.0;

(b) At 82 with a bleaching liquid of the'same composition as that mentioned under (a). At 20 the pH of this solution was 10.0;

(0) At 60 with a bleaching liquid of the same composition as described under (a) and (b) but containing in addition 7.9 g. of TAMD (tetra-acetyhnethylenediamine) and 2.62 g. of sodium hydroxide per litre. Thus a quantity of TAMD equivalent to 2 meq. acyl groups of TAMD per mg. at. active oxygen was added Consequently the improvements by adding TAMD at 60 were 8 to 10 times as great as the improvements by increasing the temperature from 60 to 82 without TAMD.

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.

I Various parts of. the piece of cotton fabric boiled with peratures'and the results of the measurements are indi cated in the following table.

,a l o l 6 Composition of the bleaching liquid Tristimulus-remission-values Percentage improvements of the Temp, End pH Yellow- Neutral ness J 30% H201, water, NaOH, TAMD, G B A Light- YellowmL/l. g./l. g./l. g./l. ness G ness .1

0 0 50 8.0 82.2 75. 4 83. 4 9.6 0 0 0 0. 53 3 78 50 5. 1 85. 9 80. 7 8G. 0 6. 1 132 875 2. 14 0 0 50 9. 8 84. 0 76. 7 84. 2 8.8 64 200 2. 14 3. 18 3. 78 50 9. 6 86. 7 82. 3 86. 6 4. 9 161 1, 175 0 0 0 82 7.6 86. 8 82. 0 8G. 9 5.6 164 1,000 0 0. 98 3, 78 82 5. 0 88. 0 84. 88. 0 3. 9 207 1, 425 2. 14 0 0 82 9. 7 86. 6 81. 6 86. 8 6. 0 157 900 2. 14 3. 1O 3. 78 82 9. 0 88. 2 84. 7 87. 9 3. 6 214 1, 500

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.

The improvements due to the presence of TAMD in the bleaching liquid were most significant both at 82 and at 50 without and with waterglass. All pieces of cotton fabric bleached in the presence of TAMD do not contain any seedrests, in contrast to the cotton pieces bleached without TAMD.

In these tests, a quantity of TAMD equivalent to 0.75 meq. acyl groups of TAMD per mg. at. of active oxygen was present in the bleaching liquid. The concentrations of active oxygen and TAMD may be chosen both higher and lower whereby it is not necessary to stick to the value 0.75 for the above-mentioned ratio.

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.

The 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.

Instead of hydrogen peroxide in the Examples XXII- XXIV other compounds releasing active oxygen may be used, such as perborate, percarbonate, pyrophosphate-perhydrate. Instead of TAMD, also other activating agents according to the invention may be used. The duration of the bleaching treatment may be chosen dependent on the bleaching and the activating agent concentrations, the temperature, the pH of the bleaching liquid and the improvement required. If desired a surface active substance may be added so as to accelerate wetting the fabric.

EXAMPLE )OCV Pieces of cotton fabric, soiled with the juice of black currants as described in Example I, were treated according to one of the following three processes.

A. Washing for 10 minutes at 50 C. in suds containing:

Sodium soap 1.00 Sodium CMC 0.10 Sodium carbonate anhydrous 3.86 Neutral waterglass (100%) 0.36

After washing, the material was rinsed twice with water, first for 10 minutes at 50 C., subsequently for 3 minutes at 20 C.

B. Washing and bleaching for 10 minutes at different temperatures in suds of the same composition as described under A, but containing in addition:

G./l. Sodium perborate (10.2% active oxygen) 0.500 Tetra-acetylmethylenediamine 0.335

G./l. Sodium perborate (10.2% active oxygen 0.500 Tetra-acetylmethylenediamine 0.335

After this treatment the material was rinsed for 3 minutes at 20 C.

The lightness of the treated material is disclosed in the following table.

Process U A 13 0 Temperature of test in C 50 35 50 60 35 50 60 Lightness of treated material in units 58 65 70 68 66 73 75 Lightness of magncsiu1noxide=100 units.

Of the above described acylated activator compounds,

a preferred group are those compounds having the formula:

000E; X-N

COOH:

1 7 wherein 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

group in which 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.

EXAMPLE XXVI The tetraand tri-acetyl methylenediamine or mixtures of these compounds used in the experiments as described in the Examples XIV-XIX and XXI-XXV were prepared as follows:

Preparation of 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.

B. 325 g. (2.5 mols) 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.

By distillation under reduced pressure all the acetic acid anhydride still present in the reaction mixture is removed yielding 523 g. crude product (theor. 535 g.).

After recrystallization from 523 cc. isopropyl alcohol 480 g. (=2.25 mols) pure tetra-acetylmethylenediamine, M.P. 9596 C., is obtained.

Preparation of 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.

Preparation of a Mixture of T riand T etra-A cetylmethylenediamine 325 g. (2.5 mols) diacetylmethylenediamine (M.P. 200-200.5 C.) is dissolved by heating in 1530 g. (15 mols) acetic acid anhydride 98%.

With the aid of a fractionating column 160 g. of acetic 18 acid is distilled off during the reaction at a bottom temperature of -145 C. in 4 hours.

From the reaction mixture the solvents are distilled off under reduced pressure yielding 490 g. crude product containing besides tri-acetylmethylenediamine also tetraacetylmethylenediamine.

By fractional distillation under reduced pressure 148 g. tri-acetylmethylenediamine, BP. 129-131 C. at 2 mm. Hg and 301 g. tetra-acetylmethylenediamine, BR 138- 140 C. at 2 mm. Hg could be isolated from the crude product.

The invention is not limited by the above-mentioned examples, as within the scope of the invention various modifications will be possible. 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.

What is claimed is:

l. 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.

2. A composition according to claim 1 wherein said active oxygen releasing compound is sodium perborate.

3. A composition according to claim 1 wherein said activator compound is N,N,N'N-tetra-acetyl hydrazine.

4. A composition according to claim 1 wherein said activator compound is N,N,N'N'-tetra-acetylmethylenediarnine.

5. A composition according to claim 1 wherein said activator is in finely divided form covered with 130% of its weight by a material selected from the group consisting of stearic acid, a solid polyethylene glycol having an average molecular weight of 3000-3700, a solid polyethylene glycol having an average molecular weight of 60007500, carboxymethylcellulose and cetyl alcohol.

References Cited by the Examiner UNITED STATES PATENTS 1,950,956 3/34 Wilhelm 252--187 2,267,685 12/41 Kyrides 260561 XR 2,445,319 7/48 Engelbrecht 260 --561 XR 2,742,501 4/56 Kleine et a1. 260562 2,838,459 6/58 Sprout 252186 2,898,181 8/59 Dithmar et a1. 25299 XR 2,923,738 2/60 Williams et al 260-561 2,927,082 3/60 Young 252186 2,932,667 4/ 60 Welcher 260561 3,061,550 10/62 Baevsky 25299 OTHER REFERENCES Beilsteins Handbuch der Organischen Chemie, vol. IV (4th Ed), First Supplement, page 416 (1929).

JULIUS GREENWALD, Primary Examiner.

IRVING MARCUS, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3, 163 ,606 December 29, 1964 Wilhelmus J. C. Viveen et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 9, line 39, the second table, under the column heading "5", line 3 thereof, insert 5O column 12, line 12, for "275" read 375 columns 15 and 16, the first table, under the column heading "B", line 6 thereof, for "84.5" read 84.6 same column 15, EXAMPLE XXIV, in the table, under the column heading "Bleaching treatment b", line 2 thereof, for "9.440" read 9.44

Signed and sealed this 22nd day of June 1965.

(SEAL) Attest:

Commissioner of Patents I UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 163 ,606 December 29, 1964 wilhelmus J. c. Viveen et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 9, line 39, the second table, under the column heading "5'', line 3 thereof, insert 50 column 12, line 12, for "275" read 375 columns 15 and 16, the first table, under the column heading "B", line 6 thereof, for

"84.5" read 84.6 same column 15, EXAMPLE XXIV, in the table, under the column heading "Bleaching treatment b", line 2 thereof, for "9.440" read 9.44

Signed and sealed this 22nd day of June 1965.

(SEAL) Attest:

ERNEST W. SWIDER' EDWARD J. BRENNER Attesting Officer Commissioner of Patents

Claims (1)

1. A TEXTILE TREATING COMPOSITIN 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,N,N''N''-TETRA-ACETYL HYDRAZINE AND N,N, N''N''-TETRA-ACETYLMETHYLENEDIAMINE, THE SAID ACTIVATOR COMPOUND BEING PRESENT IN SUCH A QUANTITY AS CORRESPONDS TO 0.5-4.0 NITROGEN BOUND ACETYL GRUPS PER ATOM OF ACTIVE OXYGEN IN THE ACTIVE OXYGEN RELEASING COMPOUND.
US3163606A 1959-06-19 1960-06-02 Textile bleaching composition Expired - Lifetime US3163606A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
GB2122059A 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

Publications (1)

Publication Number Publication Date
US3163606A true US3163606A (en) 1964-12-29

Family

ID=27257993

Family Applications (1)

Application Number Title Priority Date Filing Date
US3163606A Expired - Lifetime US3163606A (en) 1959-06-19 1960-06-02 Textile bleaching composition

Country Status (7)

Country Link
US (1) US3163606A (en)
BE (1) BE591624A (en)
CA (2) CA678942A (en)
DE (2) DE1149349B (en)
FI (1) FI42698B (en)
GB (3) GB907356A (en)
NL (3) NL239952A (en)

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3338839A (en) * 1964-12-28 1967-08-29 Fmc Corp Activating of peroxygen compounds
US3349035A (en) * 1964-05-12 1967-10-24 Degussa Activated bleaching composition
US3425786A (en) * 1965-06-09 1969-02-04 Degussa Inorganic peroxidic bleaches activated with n,n'-diacyl-methylene-diformamide
US3532634A (en) * 1966-03-01 1970-10-06 United States Borax Chem Bleaching compositions and methods
US3637339A (en) * 1968-03-07 1972-01-25 Frederick William Gray Stain removal
US3741903A (en) * 1968-12-12 1973-06-26 Lever Brothers Ltd Detergent compositions
US3901819A (en) * 1972-09-14 1975-08-26 Kao Corp Compositions for activating an inorganic peroxide bleaching agent
US3925234A (en) * 1972-07-31 1975-12-09 Henkel & Cie Gmbh Coated bleach activator
US3969257A (en) * 1971-07-23 1976-07-13 Colgate-Palmolive Company Washing and bleaching composition containing bleach, activator and a nitrilotricarboxylic acid compound
US3975153A (en) * 1975-08-25 1976-08-17 Fmc Corporation Activation of peroxygen bleaches using isophorone enol acetates and isophorone oximinoacetate
US3982891A (en) * 1967-10-24 1976-09-28 Colgate-Palmolive Company Bleaching and detergent compositions having imide activator and peroxygen bleach
US4003841A (en) * 1974-08-14 1977-01-18 Henkel & Cie G.M.B.H. Coated stabilized bleach activators, process and washing compositions
DE2650429A1 (en) * 1975-11-03 1977-05-05 Unilever Nv Bleaching auxiliaries and process for their manufacture
US4087369A (en) * 1976-11-08 1978-05-02 The Procter & Gamble Company Peroxybleach activated detergent composition
US4166794A (en) * 1978-05-25 1979-09-04 Colgate-Palmolive Company Liquid bleach-softener compositions
US4199466A (en) * 1978-08-21 1980-04-22 Shell Oil Company Activated bleaching process and compositions therefor
US4207199A (en) * 1977-07-27 1980-06-10 Basf Aktiengesellschaft Solid cold bleach activators for detergents and cleaning agents containing an active oxygen donor
US4273661A (en) * 1978-05-25 1981-06-16 Colgate-Palmolive Company Article for dispensing liquid bleach softener composition
EP0053859A1 (en) * 1980-12-09 1982-06-16 Unilever N.V. Bleach activator granules
US4372868A (en) * 1980-03-28 1983-02-08 Henkel Kommanditgesellschaft Auf Aktien Process for the preparation of a stable, readily soluble granulate with a content of bleach activators
US4421668A (en) * 1981-07-07 1983-12-20 Lever Brothers Company Bleach composition
US4457858A (en) * 1981-07-17 1984-07-03 Henkel Kommanditgesellschaft Auf Aktien Method of making coated granular bleach activators by spray drying
US4681695A (en) * 1984-09-01 1987-07-21 The Procter & Gamble Company Bleach compositions
US4859800A (en) * 1986-11-06 1989-08-22 The Clorox Company Phenoxyacetate peracid precursors
US4956117A (en) * 1986-11-06 1990-09-11 The Clorox Company Phenoxyacetate peracid precursors and perhydrolysis systems therewith
US4957647A (en) * 1986-11-06 1990-09-18 The Clorox Company Acyloxynitrogen peracid precursors
US4964870A (en) * 1984-12-14 1990-10-23 The Clorox Company Bleaching with phenylene diester peracid precursors
US5049305A (en) * 1986-11-06 1991-09-17 Zielske Alfred G Phenoxyacetate peracid precursors and perhydrolysis systems therewith
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
US5328634A (en) * 1986-11-06 1994-07-12 The Clorox Company Acyloxynitrogen peracid precursors
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
US20080113036A1 (en) * 2004-09-08 2008-05-15 Clariant Produkte (Deutschland) Gmbh Bleach Activator Mixtures

Families Citing this family (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1046487A (en) * 1962-08-20 1966-10-26 British Celanese Polyacetyl methylene diamines
GB2078716B (en) * 1980-06-27 1985-04-24 Warwick Chem Ltd Production of amines
DE3218889A1 (en) * 1982-05-19 1983-11-24 Hoechst Ag cellulose fibers method for the simultaneous desizing and bleaching textile material from
DE3304848A1 (en) * 1983-02-12 1984-08-16 Henkel Kgaa Organic cyanamide as activators for inorganic per
EP0253772A3 (en) * 1986-07-15 1989-07-19 Warner-Lambert Company Denture cleansing and/or washing compositions containing a bleach activator
GB8619152D0 (en) * 1986-08-06 1986-09-17 Unilever Plc Conditioning fabrics
GB8619153D0 (en) * 1986-08-06 1986-09-17 Unilever Plc Fabric conditioning composition
DE68908439D1 (en) * 1988-03-01 1993-09-23 Unilever Nv Quatenaere-ammonium compounds for use in bleach-systems.
DE3842008A1 (en) * 1988-12-14 1990-06-21 Hoechst Ag Using triacylated ehtanolaminen as Liquid, water-Peroxide
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
CA2087308C (en) * 1992-01-17 1997-10-14 Andrew P. Chapple Detergent compositions
JPH0680988A (en) * 1992-01-17 1994-03-22 Unilever Nv Detergent composition
US5372740A (en) * 1993-09-03 1994-12-13 Lever Brothers Company, Division Of Conopco, Inc. Homogeneous liquid automatic dishwashing detergent composition based on sodium potassium tripolyphosphate
US5468410A (en) * 1993-10-14 1995-11-21 Angevaare; Petrus A. Purine class compounds in detergent compositions
US5480576A (en) * 1993-10-14 1996-01-02 Lever Brothers Company, Division Of Conopco, Inc. 1,3-N azole containing detergent compositions
GB9413729D0 (en) 1994-07-07 1994-08-24 Procter & Gamble Detergent compositions
EP0693549A1 (en) 1994-07-19 1996-01-24 THE PROCTER & GAMBLE COMPANY Solid bleach activator compositions
US5856282A (en) * 1994-12-22 1999-01-05 The Procter & Gamble Company Silicone compositions
DE19530786A1 (en) 1995-08-22 1997-02-27 Hoechst Ag A bleaching composition comprising polyoxometalates as bleach catalyst
US5750483A (en) 1995-12-06 1998-05-12 Basf Corporation Non-phosphate machine dishwashing compositions containing polycarboxylate polymers and nonionic graft copolymers of vinyl acetate and polyalkylene oxide
EP0778340A3 (en) 1995-12-06 1999-10-27 Basf Corporation Improved non-phosphate machine dishwashing compositions containing copolymers of alkylene oxide adducts of allyl alcohol and acrylic acid
DE19600159A1 (en) 1996-01-04 1997-07-10 Hoechst Ag Bleach systems comprising bis and tris (mu-oxo) -di manganese complex salts
DE19605526A1 (en) 1996-02-15 1997-08-21 Hoechst Ag Ammonionitriles and their use as bleach activators
DE19606343A1 (en) 1996-02-21 1997-08-28 Hoechst Ag bleach
US5850086A (en) * 1996-06-21 1998-12-15 Regents Of The University Of Minnesota Iron complexes for bleach activation and stereospecific oxidation
DE19635070A1 (en) * 1996-08-30 1998-03-05 Clariant Gmbh Liquid bleach suspension
DE19801049A1 (en) * 1998-01-14 1999-07-15 Clariant Gmbh Use of formamidinium salts as bleach activators
GB0011527D0 (en) 2000-05-12 2000-06-28 Unilever Plc Bleach catalyst and composition and method for bleaching a substrate
WO2002072746A1 (en) 2001-03-14 2002-09-19 Unilever Plc Bleaching catalysts with unsaturated surfactant and antioxidants
GB0106285D0 (en) 2001-03-14 2001-05-02 Unilever Plc Air bleaching catalysts with moderating agent
DE102004040212B4 (en) * 2004-08-19 2007-07-05 Icfs Gmbh New acylation and formylating agent, to processes for their preparation and new manufacturing method for aromatic and heterocyclic aldehydes
US8969283B2 (en) * 2009-02-05 2015-03-03 American Sterilizer Company Low odor, hard surface sporicides and chemical decontaminants
GB0918914D0 (en) 2009-10-28 2009-12-16 Revolymer Ltd Composite
CA2801513A1 (en) 2010-06-28 2012-01-05 Basf Se Metal free bleaching composition
US9051285B2 (en) 2010-12-13 2015-06-09 Basf Se Bleach catalysts
GB201106409D0 (en) 2011-04-15 2011-06-01 Revolymer Ltd Novel composite
WO2014202954A1 (en) 2013-06-20 2014-12-24 Chemsenti Limited Bleach and oxidation catalyst
WO2017076771A1 (en) 2015-11-03 2017-05-11 Basf Se Bleach catalysts
EP3176157A1 (en) 2015-12-01 2017-06-07 Basf Se Bleach catalysts
WO2017182295A1 (en) 2016-04-18 2017-10-26 Basf Se Liquid cleaning compositions
WO2017186480A1 (en) 2016-04-26 2017-11-02 Basf Se Metal free bleaching composition

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1950956A (en) * 1931-10-19 1934-03-13 Marshall Field & Company Method of coating chloramine and product thereof
US2267685A (en) * 1938-07-05 1941-12-23 Monsanto Chemicals Nu,nu'-lower aliphatic diacyl-nu, nu'-dicyclohexyl alkylene diamines
US2445319A (en) * 1939-04-22 1948-07-20 American Hyalsol Corp Method for the manufacture of quaternary nitrogen compounds
US2742501A (en) * 1951-06-11 1956-04-17 Glanzstoff Ag Method of producing alkylidene bis-amides
US2838459A (en) * 1955-02-01 1958-06-10 Pennsalt Chemicals Corp Stabilization of solutions containing peroxygen compounds
US2898181A (en) * 1953-05-20 1959-08-04 Degussa Process for washing and bleaching compositions therefor
US2923738A (en) * 1958-05-08 1960-02-02 Gen Aniline & Film Corp Addition products of n-alkyl-gamma-hydroxycarboxylic acid amides and alkanolamines
US2927082A (en) * 1956-01-19 1960-03-01 Du Pont Peroxide bleaching compositions and their use
US2932667A (en) * 1956-10-18 1960-04-12 American Cyanamid Co Preparation of monothiooxamides
US3061550A (en) * 1959-05-11 1962-10-30 Du Pont Textile bleaching composition

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1093773B (en) * 1953-11-21 1960-12-01 Degussa A process for washing fibrous materials or textiles
NL208181A (en) * 1955-07-08

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1950956A (en) * 1931-10-19 1934-03-13 Marshall Field & Company Method of coating chloramine and product thereof
US2267685A (en) * 1938-07-05 1941-12-23 Monsanto Chemicals Nu,nu'-lower aliphatic diacyl-nu, nu'-dicyclohexyl alkylene diamines
US2445319A (en) * 1939-04-22 1948-07-20 American Hyalsol Corp Method for the manufacture of quaternary nitrogen compounds
US2742501A (en) * 1951-06-11 1956-04-17 Glanzstoff Ag Method of producing alkylidene bis-amides
US2898181A (en) * 1953-05-20 1959-08-04 Degussa Process for washing and bleaching compositions therefor
US2838459A (en) * 1955-02-01 1958-06-10 Pennsalt Chemicals Corp Stabilization of solutions containing peroxygen compounds
US2927082A (en) * 1956-01-19 1960-03-01 Du Pont Peroxide bleaching compositions and their use
US2932667A (en) * 1956-10-18 1960-04-12 American Cyanamid Co Preparation of monothiooxamides
US2923738A (en) * 1958-05-08 1960-02-02 Gen Aniline & Film Corp Addition products of n-alkyl-gamma-hydroxycarboxylic acid amides and alkanolamines
US3061550A (en) * 1959-05-11 1962-10-30 Du Pont Textile bleaching composition

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3349035A (en) * 1964-05-12 1967-10-24 Degussa Activated bleaching composition
US3338839A (en) * 1964-12-28 1967-08-29 Fmc Corp Activating of peroxygen compounds
US3425786A (en) * 1965-06-09 1969-02-04 Degussa Inorganic peroxidic bleaches activated with n,n'-diacyl-methylene-diformamide
US3532634A (en) * 1966-03-01 1970-10-06 United States Borax Chem Bleaching compositions and methods
US3982891A (en) * 1967-10-24 1976-09-28 Colgate-Palmolive Company Bleaching and detergent compositions having imide activator and peroxygen bleach
US3637339A (en) * 1968-03-07 1972-01-25 Frederick William Gray Stain removal
US3714050A (en) * 1968-03-07 1973-01-30 Colgate Palmolive Co Stain removal
US3741903A (en) * 1968-12-12 1973-06-26 Lever Brothers Ltd Detergent compositions
US3969257A (en) * 1971-07-23 1976-07-13 Colgate-Palmolive Company Washing and bleaching composition containing bleach, activator and a nitrilotricarboxylic acid compound
US3925234A (en) * 1972-07-31 1975-12-09 Henkel & Cie Gmbh Coated bleach activator
US3901819A (en) * 1972-09-14 1975-08-26 Kao Corp Compositions for activating an inorganic peroxide bleaching agent
US4003841A (en) * 1974-08-14 1977-01-18 Henkel & Cie G.M.B.H. Coated stabilized bleach activators, process and washing compositions
US3975153A (en) * 1975-08-25 1976-08-17 Fmc Corporation Activation of peroxygen bleaches using isophorone enol acetates and isophorone oximinoacetate
DE2650429A1 (en) * 1975-11-03 1977-05-05 Unilever Nv Bleaching auxiliaries and process for their manufacture
US4111826A (en) * 1975-11-03 1978-09-05 Lever Brothers Company Bleaching assistants
US4087369A (en) * 1976-11-08 1978-05-02 The Procter & Gamble Company Peroxybleach activated detergent composition
US4207199A (en) * 1977-07-27 1980-06-10 Basf Aktiengesellschaft Solid cold bleach activators for detergents and cleaning agents containing an active oxygen donor
US4166794A (en) * 1978-05-25 1979-09-04 Colgate-Palmolive Company Liquid bleach-softener compositions
US4273661A (en) * 1978-05-25 1981-06-16 Colgate-Palmolive Company Article for dispensing liquid bleach softener composition
US4199466A (en) * 1978-08-21 1980-04-22 Shell Oil Company Activated bleaching process and compositions therefor
US4372868A (en) * 1980-03-28 1983-02-08 Henkel Kommanditgesellschaft Auf Aktien Process for the preparation of a stable, readily soluble granulate with a content of bleach activators
US4422950A (en) * 1980-12-09 1983-12-27 Lever Brothers Company Bleach activator granules and preparation thereof
EP0053859A1 (en) * 1980-12-09 1982-06-16 Unilever N.V. Bleach activator granules
US4421668A (en) * 1981-07-07 1983-12-20 Lever Brothers Company Bleach composition
US4457858A (en) * 1981-07-17 1984-07-03 Henkel Kommanditgesellschaft Auf Aktien Method of making coated granular bleach activators by spray drying
US4681695A (en) * 1984-09-01 1987-07-21 The Procter & Gamble Company Bleach compositions
US4964870A (en) * 1984-12-14 1990-10-23 The Clorox Company Bleaching with phenylene diester peracid precursors
US5380457A (en) * 1986-11-06 1995-01-10 The Clorox Company Acyloxynitrogen peracid precursors
US4859800A (en) * 1986-11-06 1989-08-22 The Clorox Company Phenoxyacetate peracid precursors
US4956117A (en) * 1986-11-06 1990-09-11 The Clorox Company Phenoxyacetate peracid precursors and perhydrolysis systems therewith
US4957647A (en) * 1986-11-06 1990-09-18 The Clorox Company Acyloxynitrogen peracid precursors
US5049305A (en) * 1986-11-06 1991-09-17 Zielske Alfred G Phenoxyacetate peracid precursors and perhydrolysis systems therewith
US5328634A (en) * 1986-11-06 1994-07-12 The Clorox Company Acyloxynitrogen peracid precursors
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
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
US20080113036A1 (en) * 2004-09-08 2008-05-15 Clariant Produkte (Deutschland) Gmbh Bleach Activator Mixtures
US7504372B2 (en) 2004-09-08 2009-03-17 Clariant Produkte (Deutschland) Gmbh Mixtures of bleaching agents
US7541324B2 (en) 2004-09-08 2009-06-02 Clariant Produkte (Deutschland) Gmbh Bleach activator mixtures

Also Published As

Publication number Publication date Type
GB907357A (en) 1962-10-03 application
CA800223A (en) 1968-12-03 grant
NL97449C (en) grant
DE1149349B (en) 1963-05-30 application
CA678942A (en) 1964-01-28 grant
NL239952A (en) application
BE591624A (en) grant
FI42698B (en) 1970-06-30 application
DE1162967B (en) application
NL252798A (en) application
GB907356A (en) 1962-10-03 application
NL130608C (en) grant
GB907358A (en) 1962-10-03 application

Similar Documents

Publication Publication Date Title
US3532634A (en) Bleaching compositions and methods
US3539518A (en) Low foam surfactants
US5360568A (en) Imine quaternary salts as bleach catalysts
US3962149A (en) Non-phosphate spray dried detergents containing dicarboxylic acid salts
US5114611A (en) Bleach activation
US4013575A (en) Dry cleaning with peracids
US5952282A (en) Sulfonylimine derivatives as bleach catalysts
US4077768A (en) Inhibiting dye transfer in washing or bleaching
US3272750A (en) Process and composition containing an oxygen releasing compound and an organic carbonate
US5093022A (en) Bleaching composition
US4391725A (en) Controlled release laundry bleach product
US2267205A (en) Detergent
US3982892A (en) Activated peroxy bleach composition
US4441881A (en) Detergent compositions containing ethoxylated fatty alcohols with narrow ethylene oxide distributions
US4194987A (en) Peroxygen bleaching and compositions therefor
US4772412A (en) Non-aqueous liquid detergent composition comprising perborate anhydrous
US3075921A (en) Substituted peroxybenzoic acid bleaching agents
US3177148A (en) Bleaching processes and compositions
US3661789A (en) Stabilized oxygen bleach-activator system
US3951879A (en) Detergent that reduces electrostatic cling of synthetic fabrics
US4025444A (en) Fabric softening agents
US3130165A (en) Inorganic peroxy-compounds containing organic activators
US4340382A (en) Method for treating and processing textile materials
US3341459A (en) Detergent compositions
US6007583A (en) Use of aminonitrile N-oxides as bleach activators