Bleaching composition

The present invention relates to a bleaching composition which is suitable for safely bleaching, both colored cloths and figured cloths.
In domestic and industrial bleaching processes, an oxidation reaction is utilized in general and, in most cases, chlorine bleaching agents are used. Although chlorine bleaching agents are useful, the fibers and fabrics for which those chlorine bleaching agents can safely be used are limited. Further, they cannot be used for bleaching colored cloths and figured cloths because of a fear of causing decolorization and color change. Development of bleaching agents usable for all fibers and fabrics and capable of bleaching colored and figured cloths has been demanded and oxygen-containing bleaching agents have been widely suggested recently. The oxygen-containing bleaching agents are put on the market either as a bleaching composition comprising only the oxygen-containing bleaching agent or as a bleaching detergent composition comprising a mixture of the oxygen-containing bleaching agent and detergent component which has both deterging and bleaching effects.
As compared with chlorine bleaching agents, the oxygen-containing bleaching agents are used at a higher temperature, since the latter bleaching agents have an inferior bleaching effect at a lower temperature. Sodium perborate is most generally used among the oxygen-containing bleaching agents. However, sodium perborate has the following problems:
(a) low water-solubility at a low temperature,
(b) influence on the environment of its decomposition products after it has been used,
(c) resources, and
(d) poor amount of available oxygen per unit weight.
The oxygen bleaching agents include peroxy compounds such as sodium percarbonate, sodium perborate, sodium peroxytripolyphosphate, sodium peroxypyrophosphate, hydrogen peroxide adduct of sodium sulfate/sodium chloride and tetrasodium ethane-1,1,2,2-tetracarboxylate/hydrogen peroxide adduct.
Under the circumstances set forth above, sodium percarbonate and tetrasodium ethane-1,1,2,2-tetracarboxylate/hydrogen peroxide adducts have attracted attention and sodium percarbonate has already been put into practice.
However, it has been found that colored and figured cloths are discolored or faded even if they are treated with an aqueous bleaching composition solution of a low concentration (such as 0.3 wt. %) in the bleaching treatment of colored and figured cloths and fibers with a bleaching composition containing, as a main ingredient, sodium percarbonate or a tetrasodium ethane-1,1,2,2-tetracarboxylate/hydrogen peroxide adduct. In the bleaching treatment carried out for a long period of time, the degree of discoloration or fading is particularly high when an incompletely dissolved bleaching composition in the form of powders or granules is contacted directly with the colored and figured fabrics and fibers.
In the use of oxygen-containing bleaching agents, various ideas have been proposed for stabilizing peroxides in an aqueous bleaching agent solution, preventing reduction in the activity of a fluorescent brightening agent and preventing embrittlement of the fabrics and fibers. The developments comprise, for example, addition of a chelating agent (British Pat. No. 1,060,849) and addition of a magnesium salt (U.S. Pat. No. 2,160,391). Although those techniques were developed for the oxygen-containing bleaching agents to be applied to the prevention of colored and figured fabrics from discoloration or fading, the intended effects could not be obtained at all or only insufficient effects were obtained.
For preventing this phenomenon, there have been also proposed processes wherein alanine, lysine, adenine, acetylaminoacetic acid, phenylalanine, arginine, tyrosine, aminobutyric acid, glyoxaloxime, salicylaldoxime, .alpha.-nitroso-.beta.-naphthol, 8-hydroxyquinoline, cupferron and anthranilic acid are used. However, the effects of those processes are not excellent. The effects are unsatisfactory when the colored and figured cloths are domestically bleached with them repeatedly.
Although it is convenient to incorporate those additives in the bleaching composition in view of the ease of use, their incorporation causes the defects that the composition is colored or emits an offensive smell and the composition becomes useless due to its poor resistance to deterioration with lapse of time. Thus, development of novel techniques has been demanded.
After intensive investigations on the prevention of discoloration and fading of colored and figured fabrics due to sodium percarbonate and tetrasodium ethane-1,1,2,2-tetracarboxylate/hydrogen peroxide adduct, the inventors have found the facts described below. The present invention has been attained on the basis of these findings.
The discoloration and fading of colored and figured fabrics are remarkable when an incompletely dissolved bleaching agent is contacted directly with the fabrics. Dyestuffs used for the colored and figured fabrics, thus discolored or faded, were analyzed and it was found that they contain transition metal elements, particularly copper. Copper is used for a dye matrix for imparting a clear color tone to a reactive dyestuff of a high fastness to wetting. Further, in case a metal-containing or non-metal direct cotton dyestuff, applied according to dip dyeing process, is used, the fabrics are generally treated with a non-metal or metal-containing fixing agent or with a metal salt for improving the fastness thereof to wetting or light. As the metal, copper is used mainly.
It is considered that the metals contained in the thus dyed colored and figured fabrics react catalytically with hydrogen peroxide in the bleaching treatment liquid to form active reactants from hydrogen peroxide, thereby causing discoloration and fading of the colored and figured fabrics.
It has been found that, surprisingly, the discoloration and fading of colored and figured fabrics and fibers caused in the bleaching with sodium percarbonate or tetrasodium ethane-1,1,2,2-tetracarboxylate/hydrogen peroxide adduct can be prevented by incorporating therein a compound of following formula (I) or (II): ##STR1## wherein X and Y each represent hydrogen atom or an alkyl group of 1-5 carbon atoms, R.sup.1 represents an alkyl group of 1-5 carbon atoms, an acyl group of 1-5 carbon atoms or a phosphonoalkylene group of 1-5 carbon atoms, R.sup.2 represents a carboxyalkylene group of 1-5 carbon atoms in which the carboxylic acid residue or phosphonic acid residue may be its alkali metal salt, alkaline earth metal salt, ammonium salt or alkylolamine salt having an alkyl group of 2-3 carbon atoms.
As representative compounds of formulae (I) and (II), there may be mentioned, for example, methyliminodiacetic acid, phosphonomethyliminodiacetic acid, phosphonoethyliminodiacetic acid, acetamidonitrilodiacetic acid, carboxyethyliminobis(methylenephosphonic acid) and carboxymethyliminobis(methylenephosphonic acid) as well as alkali metal salts and alkaline earth metal salts of them and mono-, di- and trialkylolamine salts (the alkyl group having 2 or 3 carbon atoms) of them. The most preferred compounds of formulae (I) and (II) are those wherein X and Y represent hydrogen atoms.
With any of compounds of said formulae (I) and (II), the object of the present invention can be attained satisfactorily. By incorporating those compounds either alone or in the form of a mixture in sodium percarbonate and/or tetrasodium ethane-1,1,2,2-tetracarboxylate/hydrogen peroxide adduct and then mixing the resulting mixture with substances to be contained in a usual bleaching composition and bleaching detergent composition, the bleaching composition of the present invention, which is capable of bleaching the colored and figured fabrics and fibers safely without causing discoloration or fading, can be obtained.
The present inventors have furthermore found that a compound of the following formula (III) is also effective in the bleaching composition according to the invention. ##STR2## wherein R represents HOCH.sub.2 CH.sub.2 -- or ##STR3## and M.sub.1, M.sub.2 and M.sub.3 represent an alkali metal or an alkaline earth metal separately or together.
Compounds of formulae (I), (II) and (III) have specific actions.
Compounds of general formula (I), (II) and (III) in the present invention are those having a so-called complex compound-forming capacity. However, it is apparent that such an action is not due to only the complex compound-forming capacity of them in view of the fact that said action is not obtained from other known complex compound-forming compounds such as sodium tripolyphosphate, ethylenediamine tetraacetic acid and diethylenetriamine pentaacetate.
Sodium percarbonate and tetrasodium ethane-1,1,2,2-tetracarboxylate/hydrogen peroxide adduct used as peroxides in the present invention may be used either alone or in the form of a mixture of them. They are incorporated in the bleaching composition in an amount of 40-99.9% by weight (hereinafter referred to as %), preferably 70-95%, particularly 75-90%.
Compound of above general formula (I), (II) or (III) is incorporated in the bleaching composition in an amount of 0.1-20%, preferably 1-10%, particularly 2-6%.
The bleaching composition of the present invention may contain known components which are usually incorporated in bleaching compositions and bleaching detergent compositions, in addition to said sodium percarbonate and/or tetrasodium ethane-1,1,2,2-tetracarboxylate/hydrogen peroxide adduct and compound of above formula (I), (II) or (III). More particularly, the composition may contain a builder such as an inorganic builder, for example, a sulfate, carbonate, bicarbonate, silicate, phosphate, polyphosphate or aluminosilicate or an organic builder, for example, a citrate or ethylenediamine tetraacetate; a known stabilizer for the peroxide or hydrogen peroxide adduct such as magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride or magnesium oxide; a known activator for the peroxide or hydrogen peroxide adduct such as an N-acyl compound, organic acid anhydride or an ester. The bleaching composition may contain further an agent for preventing re-contamination such as carboxymethyl cellulose, polyvinylpyrrolidone or polyethyleneglycol, a surfactant, an enzyme, a fluorescent brightening agent, a dyestuff, a pigment, a perfume, etc.
Thus, by using the bleaching composition of the present invention, colored and figured fabrics can be bleached safely without causing discoloration or fading.
The bleaching composition of the present invention may be used solely or in combination with a known detergent composition.

The following examples illustrate the present invention concretely. The examples do not limit the invention.
EXAMPLE 1
Discoloration-and-fading Test
(i) Preparation of Colored Cloths
Cotton broadcloth #60 was dyed with Color Index Direct Blue 248 under dip dyeing conditions as shown below to obtain a colored cloth for the test for discoloration and fading:
a. Dyeing conditions:
Bath ratio: 1:20
Dye concentration: 4.0% (based on weight of fibers)
Temperature: 90.degree. C.
Time: 45 minutes
30% (based on weight of fibers) of anhydrous Glauber's salt and 1% of sodium carbonate (based on weight of fibers) were added.
After washing with water, the cloth was further dehydrated and subjected to fixing treatment.
b. Fixing treatment conditions:
Treating agent: San Fix 555 C (a product of Sanyo Kasei Co.)
Bath ratio: 1:20
Temperature: 60.degree. C.
Time: 20 minutes
Concentration: 3 g/liter
After washing with water, the cloth was dehydrated and dried to obtain sample cloth for the test for discoloration and fading.
(ii) Discoloration-and-fading Test
Bleaching Conditions
50 Milliliters of city water heated to 50.degree. C. were placed in a laboratory dish (diameter: 12 cm), in which was then immersed a colored cloth (9.times.9 cm) for the discoloration-and-fading test. 10 Grams of a bleaching composition to be tested for discoloration and fading action were sprinkled over the cloth. Directly after the immersion for 30 minutes, the cloth was washed with water and dried. The degree of discoloration or fading was judged with the naked eye.
The results of discoloration-and-fading tests of the following bleaching compositions containing peroxides or hydrogen peroxide adducts, as bleaching agent, are shown in Table 1. It is understood that remarkable discoloration and fading actions are observed in sodium percarbonate and tetrasodium ethane-1,1,2,2-tetracarboxylate/hydrogen peroxide adduct.
Bleaching Composition
Peroxide or hydrogen peroxide adduct: 80 wt. %
Glauber's salt: 15
Magnesium silicate: 5
TABLE 1______________________________________ Degrees of discolorationBleaching agent and fading______________________________________Sodium percarbonate Discoloration and fading were remarkable and the treating liquid was colored remarkably after the treatment.Sodium perborate Discoloration or fading was not recognized and the treat- ing liquid was not colored.Sodium pyrophosphate/ Discoloration or fading washydrogen peroxide adduct not recognized and the treat- ing liquid was not colored.Glauber's salt-sodium Discoloration or fading waschloride/hydrogen not recognized and the treat-peroxide adduct ing liquid was not colored.Tetrasodium ethane-1,1,2,2- Discoloration and fading weretetracarboxylate/hydrogen remarkable and the treatingperoxide adduct liquid was colored remarkably after the treatment.______________________________________
EXAMPLE 2
The effects of compounds of the above general formulae (I) and (II) (agents for preventing discoloration or fading of the present invention) and complex compound-forming substances of preventing discoloration and fading caused by sodium percarbonate and tetrasodium ethane-1,1,2,2-tetracarboxylate/hydrogen peroxide adduct were examined in the same manner as in Example 1 and the results were compared with each other. The bleaching compositions were as shown below.
______________________________________Bleaching composition A:Sodium percarbonate 85 wt. %Sodium carbonate 4Compound of formula (I) or (II) or 0 or 10complex compound-forming substanceMagnesium silicate 1Glauber's salt ad 100Bleaching composition B:Tetrasodium ethane-1,1,2,2-tetracarboxylate/hydrogen 70 wt. %peroxide adductCompound of formula (I) or (II) or 0 or 10complex compound-forming substanceGlauber's salt ad 100______________________________________
The results of bleaching compositions A and B are shown in Tables 2 and 3, respectively. It is apparent from those tables that the compositions of the present invention have remarkable effects of preventing discoloration and fading.
TABLE 2______________________________________Compound of formula (I)or (II) or complex Degree of dis-compound-forming coloration orsubstance fading______________________________________Present Sodium methyliminodiacetate Discoloration orinvention fading was not recognized and the treating liquid was not colored Phosphonomethyliminodi- Discoloration or acetic acid fading was not recognized and the treating liquid was not colored Phosphonoethyliminodi- Discoloration or acetic acid fading was not recognized and the treating liquid was not colored Acetamidonitrilodiacetic Discoloration or acid fading was not recognized and the treating liquid was not colored Carboxymethliminobis Discoloration or (methylenephosphonic acid) fading was not triethanolamine salt recognized and the treating liquid was not colored Sodium salt of carboxy- Discoloration or methyliminobis(methylene- fading was not phosphonic acid) recognized and the treating liquid was not coloredCom- (None) Discoloration andparative fading were remark-examples able and the treat- ing liquid was colored remarkably. Sodium hexametaphosphate Discoloration and fading were remark- able and the treat- ing liquid was colored remarkably. Sodium pyrophosphate Discoloration and fading were remark- able and the treat- ing liquid was colored remarkably. Sodium tripolyphosphate Discoloration and fading were remark- able and the treat- ing liquid was colored remarkably. Ethylenediamine Discoloration and tetraacetic acid fading were remark- able and the treat- ing liquid was colored remarkably. Diethylenetriamine Discoloration and pentaacetic acid fading were remark- able and the treat- ing liquid was colored remarkably.______________________________________
TABLE 3______________________________________Compound of formula (I)or (II) or complex Degree of dis-compound-forming coloration orsubstance fading______________________________________Present Phosphonoethyliminodiacetic Discoloration orinvention acid fading was not recognized and the treating liquid was not colored. Acetamidonitrilodiacetic Discoloration or acid fading was not recognized and the treating liquid was not colored. Sodium carboxymethyl- Discoloration or iminobis(methylenephosphonic fading was not acid) recognized and the treating liquid was not colored. Sodium carboxyethyliminobis Discoloration or (methylenephosphonic acid) fading was not recognized and the treating liquid was not colored.Compara- (None) Discoloration andtive fading were remark-examples able and the treat- ing liquid was colored remarkably Sodium pyrophosphate Discoloration and fading were remark- able and the treat- ing liquid was colored remarkably Diethylenetriamine Discoloration and pentaacetic acid fading were remark- able and the treat- ing liquid was colored remarkably______________________________________
EXAMPLE 3
For determining the amounts of compounds of formulae (I) and (II) used as agent for preventing discoloration or fading according to the present invention, the degrees of discoloration and fading caused by the following bleaching composition were measured in the same manner as in Example 1. The results are shown in Table 4.
Bleaching Composition
Sodium percarbonate: 70 wt. %
Compound of formula (I) or (II): 0-20
Glauber's salt: balance
TABLE 4______________________________________Compound of formula (I) Degree of discolorationor (II) Amount or fading______________________________________Sodium 0 Discoloration and fadingmethyliminodiacetate were remarkable. 0.05 Slight discoloration and fading were recognized. 0.1 Discoloration or fading was not recognized. 1 Discoloration or fading was not recognized. 5 Discoloration or fading was not recognized. 10 Discoloration or fading was not recognized. 20 Discoloration or fading was not recognized.Sodium acetamidonitrilo- 0 Discoloration and fadingdiacetate were remarkable 0.05 Slight discoloration and fading were recognized. 0.1 Discoloration or fading was not recognized. 1 Discoloration or fading was not recognized. 5 Discoloration or fading was not recognized. 10 Discoloration or fading was not recognized. 20 Discoloration or fading was not recognized.______________________________________
EXAMPLE 4
Color Change and Fading Tests
(I) Preparation of Colored Cloth
A cotton knit cloth was dyed with Color Index Direct Blue 248 under the following dip dyeing conditions to obtain a dyed cloth sample for color change and fading tests.
a. Dyeing Conditions
Bath ratio: 1:20
Dye concentration: 4.0% (based on weight of the cloth)
Temperature: 90.degree. C.
Time: 45 Minutes
30% (Based on weight of cloth) of anhydrous Glauber's salt and 1% (based on weight of cloth) of sodium carbonate were added thereto.
After washing with water followed by dehydration, the product was subjected to fixing treatment.
b. Fixing Treatment Conditions
Treating agent: Sanfix 555C (a product of Sanyo Kasei Co.)
Bath ratio: 1:20
Temperature: 60.degree. C.
Time: 20 Minutes
Concentration: 3 g/liter
The treated cloth was washed with water, dehydrated and dried.
After ironing the cloth, a dyed cloth sample for color change and fading tests was obtained.
(II) Color Change and Fading Tests
Bleaching Conditions
One gram of a bleaching composition containing sodium percarbonate was dissolved in 200 ml of city water warmed to 40.degree. C. One piece of said dyed cloth (9.times.9 cm) prepared as above was immersed in that solution for 30 minutes.
After the immersion, the cloth was washed with water and dried. This procedure was repeated five times. Color change and fading of the treated cloth and coloring of the treating solution were examined with the naked eye.
With a bleaching composition comprising the following components, color change and fading test was effected under the above described bleaching conditions. The results are shown in Table 5.
Sodium percarbonate 2Na.sub.2 CO.sub.3.3H.sub.2 O.sub.2 : 80 wt. %
Compound of general formula (III) or another compound: 10 wt. %
Sodium tripolyphosphate: 10 wt. %
TABLE 5______________________________________Compound of general formula Degree of color(III) or another compound change or fading______________________________________Present Sodium hydroxyethylimino- No color changeinvention diacetate or fading was caused and the treating solution was not colored. Sodium hydroxyethylethylene- No color change diamine triacetate or fading was caused and the treating solution was not colored.Compara- None* Color change andtive fading were remark-examples able. Coloring of the treating solution was remarkable. Sodium tripolyphosphate Color change and fading were remark- able. Coloring of the treating solution was remarkable. Sodium ethylenediamine- Color change and tetraacetate fading were remark- able. Coloring of the treating solution was remarkable. Sodium diethylenetriamine- Color change and pentaacetate fading were remark- able. Coloring of the treating solution was remarkable.______________________________________ *In this case, 0.9 g of the composition was used in the test.
EXAMPLE 5
The effects of various salts of compounds of general formula (III) of preventing color change and fading were examined. The bleaching composition was as follows:
Bleaching composition
Sodium percarbonate: 85 wt. %
Sodium pyrophosphate: 5 wt. %
Compound of general formula (III): 10 wt. %
The results are shown in Table 6.
TABLE 6______________________________________ Degree of colorComound of general change orformula (III) fading______________________________________Present Calcium hydroxyethyliminodi- No color changeinvention acetate or fading was caused and the treating solution was not colored. Magnesium hydroxyethylimino- No color change diacetate or fading was caused and the treating solution was not colored. Barium hydroxyethylethylene- No color change diaminetriacetate or fading was caused and the treating solution was not colored. Magnesium hydroxyethylethy- No color change lenediamine triacetate or fading was caused and the treating solution was not colored. Lithium hydroxyethylimino- No color change diacetate or fading was caused and the treating solution was not colored. Barium hydroxyethylaminodi- No color change acetate or fading was caused and the treating solution was not colored. Lithium hydroxyethylethy- No color change lenediaminetriacetate or fading was caused and the treating solution was not colored.______________________________________
EXAMPLE 6
For determining the necessary amount of the compound of general formula (III) used as an agent for preventing color change or fading according to the present invention, the effects of the following bleaching compositions for preventing color change or fading were examined:
Bleaching Composition
Sodium percarbonate: 80 wt. %
Synthetic Zeolite A-4 (a product of Tekko-sha): 10 wt. %
Compound of general formula (III): 1-10 wt. %
Glauber's salt: ad 100
The results are shown in Table 7.
TABLE 7______________________________________Compound of general Amount Degree of colorformula (III) (%) change and fading______________________________________Present Lithium hydroxyethyl- 10 No color changeinven- imiodiacetate or fading wastion caused and the treating solution was not colored. Lithium hydroxyethyl- 6 No color change iminodiacetate or fading was caused and the treating solution was not colored. Lithium hydroxyethyl- 2 No color change iminodiacetate or fading was caused and the treating solution was not colored. Lithium hydroxyethyl- 1 Slight color iminodiacetate change and fading were recognized. Magnesium hydroxyethyl- 10 No color change ethylenediamine or fading was triacetate caused and the treating solution was not colored. Magnesium hydroxyethyl- 6 No color change ethylenediamine or fading was triacetate caused and the treating solution was not colored. Magnesium hydroxyethyl- 6 No color change ethylenediamine or fading was triacetate caused and the treating solution was not colored. Magnesium hydroxethyl- 2 No color change ethylenediamine or fading was triacetate caused and the treating solution was not colored. Magnesium hydroxyethyl- 1 Slight color change and fading were recognized. Magnesium hydroxyethyl- 10 No color change iminodiacetate or fading was caused and the treating solution was not colored. Magnesium hydroxyethyl- 6 No color change iminodiacetate or fading was caused and the treating solution was not colored. Magnesium hydroxyethyl- 2 No color change iminodiacetate or fading was caused and the treating solution was not colored. Magnesium hydroxyethyl- 1 Slight color iminodiacetate change and fading were recognized.______________________________________
EXAMPLE 7
The following bleaching compositions containing the agents for preventing color change or fading were stored at 50.degree. C. for 20 days.
The results are shown in Table 8.
Bleaching Composition
Sodium percarbonate: 80 wt. %
Sodium carbonate: 10 wt. %
Compound of general formula (III) or another compound: 10 wt. %
TABLE 8______________________________________Compound of general formula Appearance and(III) or another compound smell of the powder______________________________________Present Lithium hydroxyethylimino- No coloring orinvention diacetate offensive smell Magnesium hydroxyethylimino- No coloring or diacetate offensive smell Magnesium hydroxyethyl- No coloring or ethylenediamine offensive smell triacetateCompara- Sodium salicylaldoxime Coloring wastive remarkable andexamples offensive smell was emitted. Sodium 8 hydroxyquinoline Coloring was remarkable and offensive smell was emitted.______________________________________

Number	Date	Country	Kind
53-31922	Mar 1978	JPX
53-159624	Dec 1978	JPX

Number	Name	Date
3737385	Wardehausen	Jun 1973
3982892	Gray	Sep 1976
4008167	Wakagawa et al.	Feb 1977
4131562	Lutz et al.	Dec 1978

Bleaching composition

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