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GB2030609A - Bleaching composition - Google Patents

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GB2030609A
GB2030609A GB7835812A GB7835812A GB2030609A GB 2030609 A GB2030609 A GB 2030609A GB 7835812 A GB7835812 A GB 7835812A GB 7835812 A GB7835812 A GB 7835812A GB 2030609 A GB2030609 A GB 2030609A
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water
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Kao Corp
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Kao Soap Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR 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

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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

A bleaching composition comprises (a) a peroxide capable of releasing oxygen in an aqueous solution, (b) a compound having the formula (I): <IMAGE> wherein R1 is hydrogen or alkyl having 1 to 3 carbon atoms, <IMAGE> is a radical of a 5-member or 6- member heterocyclic ring which may be fused to another ring, R2 is hydrogen, alkyl having 1 to 10 carbon atoms, phenyl, pyridyl or pyrrolidonyl, which alkyl, phenyl, pyridyl or pyrrolidonyl may have a substituent thereon, R3 is hydrogen, halogen or substituted or unsubstituted alkyl, phenyl, alkoxy, phenoxy, amino, acyloxy, carbamoyl, acyl, R4 is the same as R3, or a monovalent radical -R5Y, or R4 may form together with R3 a benzo group, R5 is alkylene or alkylene or alkylidene having 1 to 6 carbon atoms or phenylene, and Y is a residue formed by removal of R4 from a compound of the above formula, or dimethylglyoxime or salt thereof, and (c) an aminocarboxylic acid having a coordination number of at least 6, or salt thereof.

Description

SPECIFICATION Bleaching composition The present invention relates to an oxygen-type bleaching agent composition. More particularly, the invention relates to a bleaching composition which can bleach, with safety, fibrous articles dyed by or printed with designs containing metal complex dyes or metal complex pigments.
In general, an oxidation reaction is utilized for household and industrial bleaching, and bleaching agents of the chlorine type are commonly used. However, dyed or printed fibrous articles cannot be bleached with safety by bleaching agents of the chlorine type. Accordingly, bleaching agents of the oxygen type, which can safely be used to bleach dyed or printed fibrous articles have recently been developed and used. However, it has been confirmed that the safety of these bleaching agents is insufficient to make them suitable for bleaching dyed or printed fibrous articles which have been treated by a metal salt or metal-containing fixing agent.
There is known a method in which an aminocarboxylic acid such as NTA (nitrilotriacetic acid), EDTA (ethylenediamine-tetraacetic acid) or DTPA (diethylenetriamine-pentaacetic acid) or a water soluble salt thereof, or an inorganic salt such as a condensed phosphoric acid salt, a magnesium salt or a silicic acid salt, is incorporated in an oxygen-type bleaching agent to stabilize the peroxide in the bleaching bath, to prevent reduction of the activity of a fluorescent whitening agent or to prevent brittleness in textile fibers. However, when dyed or printed design fibrous articles colored by a metal containing dye or pigment, or dyed or printed design fibrous articles treated with a metal salt or metal containing fixing agent, are bleached according to this method, there occur various disadvantages.For example, the amount incorporated of such compound should be increased or the hue of the fibrous article will be changed or degraded.
The mechanism of discoloration or color fading in dyed or printed design fibrous articles will now be described. These dyed or printed design fibrous articles are colored by the dip dyeing method or the printing method. For example, when a woven fabric is dyed with a metal-containing or metal-free direct dye, in order to improve the wet fastness or light fastness, the fabric is ordinarily treated with a metalfree or metal-containing fixing agent or a metal salt. When a cotton woven fabric is colored by the printing method, in order to obtain a good wet fastness and a clear hue, a reactive dye containinga metal in the dye molecule is ordinarily used. As such metal, there are used copper, cobalt, chromium, nickel and the like, and copper is used most popularly.The metal in the thus-colored dyed or printed fabric reacts catalytically with hydrogen peroxide in a bleaching bath to generate a hydroxyl radical from the hydrogen peroxide. It is considered that this hydroxyl radical causes discoloration or color fading in the dyed or printed fabric. This discoloration or color fading is especially conspicuous in the case of copper.In view of the foregoing, in order to prevent discoloration or color fading in a dyed or printed fibrous article, it is important to find a chelating agent which can inactivate the metal in the dyed or printed fibrous article, i.e., a chelating agent which can fill the coordination sites of the metal completely, which does not act as a decomposition catalyst for hydrogen peroxide and which has the characteristic prnpertythafthe chelating agentperse and its rnetal chelateare non-oxidative and itis capable of coordination with the metal which has already been chelated with the dye.
We have proposed a method in which discoloration or color fading of dyed or printed fibrous articles is prevented by incorporating a compound having the following formula (I):
wherein R1 is hydrogen or alkyl having 1 to 3 carbon atoms;
is a monovalent radical of a 5- or 6-membered heterocyclic ring which may be fused to another ring; R2 is hydrogen, alkyl having 1 to 10 carbon atoms, phenyl, pyridyl or pyrrolidonyl group, which alkyl, phenyl, pyridyl or pyrrolidonyl group may optionally have a substituent thereon; Rs is hydrogen, halogen, or a member selected from the group consisting of substituted or unsubstituted alkyl, phenyl, alkoxy, phenoxy, amino, acyloxy, carbamoyl and acyl, or R3 may form together with R4 a benzo group;R4 is the same as R3, or a monovalent radical -R5Y; R5 is alkylene or alkylidene having 1 to 6 carbon atoms or phenylene; and Y is a radical obtained by removing R4 from a compound of the above formula (I), or dimethylglyoxime into a bleaching composition comprising an inorganic peroxide as the main ingredient (see Japanese Patent Application No. 105277/76, corresponding to U.S. Serial No. 823 271, the entire contents of which are incorporated herein by reference).
In U.S. Patent No. 4 046 705 there is disclosed a bleaching detergent composition comprising a peroxide capable of releasing oxygen in aqueous solution, a water-soluble synthetic organic surfactant, water-soluble builders and a compound of the formula (I).
U.S. Patent No. 3 951 840 discloses a bleaching composition comprising a peroxide capable of releasing oxygen in aqueous solution and a chelating agent which agent can be dimethylglyoxime.
There also are disclosed polyamino carboxylic acids as chelating agents capable of forming watersoluble metal chelate compounds.
U.S. Patent No. 3 816 324 discloses a composition comprising hydrogen peroxide or compound capable of releasing hydrogen peroxide and an N-acyl azole as an activator therefor.
However, it has been found that the use of the compound of the formula (I), or dimethylglyoxime or salt thereof, for preventing discoloration or color fading during the step of bleaching a dyed or printed fibrous article such as those mentioned above, still involves some problems remaining to be solved.
More specifically, when the formula (I) compound is incorporated in the bleaching agent in a relatively smail amount, such as about 0.1 to about 0.3% by weight, a sufficient effect of preventing discoloratioin or color fading cannot be attained at a relatively high bleaching temperature, such as 500 to 800C. In this case, the formula (I) compound should be incorporated in a considerably large amount, such as 0.5 to 5% by weight. Further, it sometimes happens that the formula (I) compound acts as decomposing catalystfora peroxide in the bleaching solution or that the formula (I) compound is decomposed catalytically by the heavy metal contained in an aqueous solution of the bleaching agent and the added formula (I) compound does not completely exert its intended function.
SUMMARY OF THE INVENTION As a result of our research made with a view to solving these problems, we have found that the foregoing disadvantages can be eliminated by incorporating a specific aminocarboxylic acid or salt thereof into a bleaching agent containing the formula (I) compound. Based on this finding, we have now completed the present invention.
DETAILED DESCRIPTION More specifically, in accordance with the present invention, there is provided a bleaching composition which does not cause discoloration or color fading in dyed or printed fibrous articles, which comprises as critical components (a) a peroxide capable of releasing oxygen in an aqueous solution, (b) a compound having the above formula (I) or dimethylglyoxime or salt thereof, and (c) an aminocarboxylic acid having a coordination number of at least 6 or salt thereof.
As the 5-member or 6-member heterocyclic ring
in the above formula (I), there can be mentioned, for example, heterocyclic rings containing a nitrogen atom in the ring in addition to carbon atoms and heterocyclic rings containing oxygen and nitrogen atoms in the ring in addition to carbon atoms. The 5-member or 6-member heterocyclic ring can be fused to a benzene ring or another heterocyclic ring to give a polycyclic radical.Specific examples of such 5-member and 6-member heterocyclic rings include triazole, benzotriazole, triazine, tetrazole, tetrazine, imidazole, benzimidazole, indazole, imadazoline, indolenine, pyrazole, benzopyrazole, pyrazolone, pyrazine, pyridazine, pyrimidine, 2-pyrazolone, pyrrolidine, quinoline, quinazoline, isoquinoline, carbazole, pyrrole, pyrrolidine, isoxazole, oxazole, furazane, piperazine, oxazine, morpholine, pyridine, piperidine, indole, isoindole, indoline, benzoxazole, pyrrolidone, pyrroline, imidazolidone and indoxazene.
As specific examples of the substituent R2 on the heterocyclic ring in formula (I), there can be mentioned hydrogen; alkyls (C, to C1O) such as methyl, ethyl, isopropyl and nonyl; substituted alkyls (Ca to C10) substituted with hydroxy, chloro, amino, alkoxy (C1-C10), phenoxy, phenyl, hydroxyphenyl or benzoylamino such as hydroxyethyl, chloromethyl, aminomethyl, butyloxyethyl, ethoxyethyl, phenoxymethyl, phenylmethyl, p-hydroxyphenylethyl and benzoylaminomethyl; phenyl; substituted phenyls wherein the substituents are one or two alkyls (C, or C2), chloro, hydroxy, alkoxy (C, to C,O), acyloxy (C, to C4) or amino such as toluyl, monochlorophenyl, hydroxyphenyl, alkoxyphenyl, acyloxyphenyl and aminophenyl; aroyl (C6 to C) such as xylenoyl; pyridyl and pyrrolidone.
As specific examples of the substituent R3 in the formula (I) compound, there can be mentioned hydrogen; alkyls (C, to C22) such as methyl, ethyl, propyi, isopropyl, butyl, hexyl, 2-ethylhexyl, isodecyl, lauryl, palmityi and stearyl groups; substituted alkyls (C, to C22) wherein the substituents are hydroxy, chloro, alkoxy (Cr to C4), phenoxy, amino or phenyl such as hydroxymethyl, ethoxyethyl, chloromethyl, phenoxymethyl, aminoethyl and phenylmethyl; phenyl; substituted phenyls wherein the substituents are one or 2 alkyls (C1 to C2) or alkoxy (Cr to C1O) such as toluyl, alkoxyphenyl; aroyl (C6 to Cs) such as xylenoyl; alkoxy (C1 to C,O) such as methoxy, butoxy, phenylmethoxy and octoxy; phenoxy; halogen such as chlorine and bromine; alkylamino (C1 to C1O) such as ethylamino; aminosulfonamide; alkanoyloxy (C2 to C6) such as acetoxy; aroyloxy (C6 to C8) such a benzoxy; carbamoyl; and alkoxy (Cr to C,O) carbonyl and aryl (Ce to C8) oxycarbonyl such as methoxycarbonyl, octoxycarbonyl and phenoxycarbonyl.
The compounds in which R3 forms together with R4 a benzo group mean compounds of the formula (I) in which the benzene ring is replaced by a naphthalene ring.
All of the compounds represented by the formula (I) can achieve the objects of the present invention sufficiently, but in the present invention, it is preferred to employ compounds in which R2 is hydrogen or methyl, R3 is hydrogen or methyl, R4 is hydrogen or methyl, or R3 and R4 together form a benzo group, and
is a member selected from the group consisting of triazole, benzotriazole, imidazole, benzimidazole, tetrazole, indazole, pyrazole, benzopyrazole, triazine, pyridine, pyridazine, pyrimidine, pyrazine, piperidine and imidazolidone.
As the aminocarboxylic acid having a coordination number of at least 6 or salt thereof that is used in the present invention, there can be mentioned, for example, ethylenediaminetetraacetic acid, triethylenetetra minehexaacetic acid, diethylenetriamine-pentaacetic acid, propylenediamine-tetraacetic acid, diaminopropanol-tetraacetic acid, tra ns- ,2-cyclohexanediamine-tetraacetic acid, g lycoletherdiamine-tetra acetic acid, dia mi nopropane-tetraacetic acid, tetraethylenepentamine- heptaacetic acid and alkali metal salts thereof.
The term peroxide capable of releasing hydrogen peroxide in water means a peroxide or hydrogen peroxide adduct of a water-soluble inorganic or organic salt. More specifically, there can be mentioned peroxides and hydrogen peroxide adducts of alkali metal carbonates, alkali metal borates, alkali metal phosphates, alkali metal sulfates, alkali metal silicates and alkali metal polycarboxylates.Suitable examples include sodium percarbonate 12Na2CO3-3H202), sodium perborate (NaBO3.4H2O2), sodium peroxypyrophosphate (Na4P207.3H2O2), sodium peroxytripolyphosphate, sodium sulfate-sodium chloride-hydrogen peroxide adduct (4Na2SO4. NaCI-2H202), and tetrasodium ethane-1 1,2,2- tetracarboxylate-hydrogen peroxide adduct ([CH(CO2Na)2]2-H202).
In the bleaching composition of the present invention, the peroxide capable of releasing hydrogen peroxide in water is incorporated in an amount of 5 to 99% by weight, preferably 10 to 95% by weight, especially preferably 40 to 95% by weight.
The amount incorporated of the compound of the formula (I) or dimethylglyoxime or salt thereof is from 0.01 to 10% by weight, preferably 0.1 to 5% by weight, especially preferably 0.5 to 3% by weight.
The amount incorporated of the aminocarboxylic acid having a coordination number of at least 6 or salt thereof is from 0.001 to 3% by weight, preferably 0.01 to 1 % by weight, especially preferably 0.05 to 0.5% by weight. When the amount incorporated of the aminocarboxylic acid having a coordination number of at least 6 is too high, discoloration or color fading of a dyed or printed fibrous article is sometimes promoted. Accordingly, the amount of the aminocarboxylic acid or salt should not exceed 3% by weight. When an aminocarboxylic acid having a coordination number of 5 or less is used in combination with a compound of the formula (I) or dimethylglyoxime or its salt, the effect of preventing discoloration or color fading is lost.
The bleaching composition of the present invention may contain known additives customarily added to conventional bleaching compositions, in addition to the above-mentioned critical components.
For example, as builders, there can be used water-soluble inorganic builders such as sulfates, carbonates, bicarbonates, silicates, phosphates and condensed phosphates, and organic builders such as tartrates and citrates. Further, there can be used known stabilizers for peroxides or hydrogen peroxide adducts, such as magnesium compounds, e.g., magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide and magnesium hydroxide, and silicates, e.g., sodium silicate. Moreover, there can be added re-deposition-preventing agents such as carboxymethyl cellulose, polyvinyl pyrrolidone and polyethylene glycol, and peroxide activating agents such as N-acyl compounds, organic acid anhydrides and esters, according to need.Still in addition, various surface active agents, enzymes, fluorescent whitening agents, dyes, pigments and perfumes can be incorporated in the bleaching composition of the present invention.
When the bleaching composition of the present invention is used, it is possible to bleach a dyed or printed fibrous article colored with a metal complex dye or pigment or treated with a metal salt or metal-containing fixing agent. Even if the bleaching treatment is carried out at a high temperature (for example, 500 to 800C.), no discoloration or color fading is caused and the fastness to washing or hot water is not degraded.
The present invention will now be further described in detail by reference to the following illustrative Examples, in which all references to "parts" and "%" are by weight.
EXAMPLE 1 [Preparation of Dyed Cloth] A cotton broadcloth &num;60 was dyed with Color Index Direct Blue 248 (metal complex-free direct dye) according to the dip dyeing method.
Dyeing Conditions: Bath ratio:/120 Dye concentration: 4.0% o.w.f. (based on the fiber weight) Temperature: 900C Time: 45 minutes Anhydrous Glauber salt: 30% o.w.f. (based on the fiber weight) Sodium carbonate: 1% o.w.f. (based on the fiber weight) After water washing and removal of water, the dyed cloth was subjected to the fixing treatment Fixing Treatment Conditions: Treating agent:Sanfix 555C (metal-containing fixing agent manufactured by Sanyo Kasei) Bath ratio: 1/20 Temperature: 600C Time: 20 minutes Concentration: 3 g/l After water washing and removal of water, the cloth was dried to obtain a sample of a dyed cloth In the category of dyed cloths in which discoloration or color fading is caused, the thus-prepared dyed cloth is characterized by the property that the degree of discoloration or color fading is extremely high.
[Bleaching Test] Bleaching Composition: 2Na2CO3 3H202 70 parts Na2CO3 15 parts Compound of formula (I) ordimethylglyoxime or salt thereof (component X) x parts (See Table 1) Aminocarboxylic acid having coordination number of at least 6 (component Y) y parts (See Table 1) Aminocarboxylic acid having coordination number of 5 or less (component Z) parts (See Table 1) Magnesium silicate 1 part Glauber salt balance Total 100 parts Bleaching Conditions: Bath ratio: 1/50 Concentration: 0.5% Temperature: 500C Time: 30 minutes Water used: service water (3 DH) The dyed cloth was treated under the above conditions.
The degree of discoloration or color fading was evaluated by a gray scale for determination of discoloration or color facing according to the method of JIS L-0804 (1974).
5: not changed (not discolored) 3: detectable change (slightly discolored) 1: considerable change (substantially completely discolored) The results obtained are shown in Table 1.
TABLE 1 X, Y, Z or Combination Thereof Coordination Number Degree of Discoloration Comparisons Symbol of Y or Z x y z or Color Fading not added 1 Component X 3-salicyloylamido-1,2,4-triazole A 0.1 0 0 3 - 4 3-salicyloylamido-benzimidazole B 0.1 0 0 3 5-salicyloylamido-1,2,3,5-tetrazole C 0.1 0 0 3 - 4 2-salicyloylamido-1,3-imidazole D 0.1 0 0 3 3-salicyloylamido-1,2-pyrazole E 0.1 0 0 3 - 4 3-salicyloylamido-1,2-benzopyrazole F 0.1 0 0 3 3-(2-hydroxy-3-naphthoenic)-acid-amido- G 0.1 0 0 3 1,2,4-triazole 5-methyl-3-salicyloylamido-1,2,4-triazole H 0.1 0 0 3 - 4 3-(5-methylsalicyloyl)-amido-triazole I 0.1 0 0 3 3-(5-octylsalicyloyl)-amido-triazole J 0.1 0 0 3 5-methyl-3-(2-hydroxy-3-naphthoenic)-acid-amido- K 0.1 0 0 3 1,2,4-triazole N-methyl-3-salicyloylamido-1,2,4-triazole L 0.1 0 0 3 Dimethylglyoxime M 0.1 0 0 3 - 4 Disodium dimethylglyoxime octahydrate N 0.1 0 0 3 TABLE 1 (Continued) X, Y, Z or Combination Thereof Coordination Number Degree of Discoloration Comparisons Symbol of Y or Z x y z or Color Fading Component Y tetrasodium ethylenediamine-tetraacetate a 6 0 1.0 0 1 diethylenetriamine-pentaacetic acid b 8 0 1.0 0 1 glycoletherdiamine-tetraacetic acid c 8 0 1.0 0 1 trans-1,2-cyclohexanediamine-tetraacetic acid d 6 0 1.0 0 1 hydroxyethylethylenediamine-triacetic acid e 6 0 1.0 0 1 ethylenediamine-di-o-hydroxyphenyl-acetic acid f 6 0 1.0 0 1 diaminopropanol-tetraacetic acid g 7 0 1.0 0 1 ethylenediamine-diacetic-dipropionic acid h 6 0 1.0 0 1 diaminopropane-tetraacetic acid i 6 0 1.0 0 1 metaphenylenediamine-tetraacetic acid j 6 0 1.0 0 1 triethylenetetramine-hexaacetic acid k 10 0 1.0 0 1 Component Z trisodium nitrilo-triacetate l 4 0 0 1.0 2 - 3 imino-diacetic acid m 3 0 0 1.0 3 - 2 TABLE 1 (Continued) X, Y, Z or Combination Thereof Coordination Number Degree of Discoloration Comparisons Symbol of Y or Z x y z or Color Fading hydroxyethylimino-diacetic acid n 4 0 0 1.0 2 ethylenediamine-diacetic acid o 4 0 0 1.0 2 dihydroxyethylglycine p 4 0 0 1.0 2 ethylenediamine-dipropionic aicd q 4 0 0 1.0 2 nitrilo-tripropionic acid r 4 0 0 1.0 2 - 3 A + 1 0.1 0 0.5 1 - 2 B + 1 0.1 0 0.5 1 C + 1 0.1 0 0.5 1 D + 1 0.1 0 0.5 1 - 2 E + 1 0.1 0 0.5 1 F + 1 0.1 0 0.5 1 G + 1 0.1 0 0.5 1 M + 1 0.1 0 0.5 1 H + 1 0.1 0 0.5 1 I + 1 0.1 0 0.5 1 TABLE 1 (Continued) X, Y, Z or Combination Thereof Coordination Number Degree of Discoloration Comparisons Symbol of Y or Z x y z or Color Fading J + 1 0.1 0 0.5 1 K + 1 0.1 0 0.5 1 L + 1 0.1 0 0.5 1 N + 1 0.1 0 0.5 1 A + m 0.1 0 0.5 1 A + n 0.1 0 0.5 1 A + o 0.1 0 0.5 1 A + p 0.1 0 0.5 1 A + q 0.1 0 0.5 1 A + r 0.1 0 0.5 1 D + m 0.1 0 0.5 1 D + n 0.1 0 0.5 1 D + o 0.1 0 0.5 1 D + p 0.1 0 0.5 1 D + q 0.1 0 0.5 1 D + r 0.1 0 0.5 1 TABLE 1 (Continued) X, Y, Z or Combination Thereof Coordination Number Degree of Discoloration Present Invention Symbol of Y or Z x y z or Color Fading A + a 0.1 0.5 0 5 B + a 0.1 0.5 0 5 C + a 0.1 0.5 0 5 D + a 0.1 0.5 0 5 E + a 0.1 0.5 0 5 F + a 0.1 0.5 0 5 G + a 0.1 0.5 0 5 M + a 0.1 0.5 0 5 H + a 0.1 0.5 0 5 I + a 0.1 0.5 0 5 J + a 0.1 0.5 0 5 K + a 0.1 0.5 0 5 L + a 0.1 0.5 0 5 N + a 0.1 0.5 0 5 TABLE 1 (Continued) X, Y, Z or Combination Thereof Coordination Number Degree of Discoloration Present Invention Symbol of Y or Z x y z or Color Fading A + b 0.1 0.5 0 5 A + c 0.1 0.5 0 5 A + d 0.1 0.5 0 5 A + e 0.1 0.5 0 5 A + f 0.1 0.5 0 5 A + g 0.1 0.5 0 5 A + h 0.1 0.5 0 5 A + i 0.1 0.5 0 5 A + j 0.1 0.5 0 5 A + k 0.1 0.5 0 5 D + b 0.1 0.5 0 5 D + c 0.1 0.5 0 5 D + g 0.1 0.5 0 5 D + i 0.1 0.5 0 5 D + k 0.1 0.5 0 5 TABLE 1 (Continued) X, Y, Z or Combination Thereof Coordination Number Degree of Discoloration Present Invention Symbol of Y or Z x y z or Color Fading M + c 0.1 0.5 0 5 M + d 0.1 0.5 0 5 M + e 0.1 0.5 0 5 M + f 0.1 0.5 0 5 M + g 0.1 0.5 0 5 M + h 0.1 0.5 0 5 M + i 0.1 0.5 0 5 M + j 0.1 0.5 0 5 M + k 0.1 0.5 0 5 Comparison A + a 0.1 3.0 0 5 - 4 D + a 0.1 3.0 0 4 - 5 M + a 0.1 3.0 0 5 - 4 A + a 0.1 5.0 0 4 - 5 D + a 0.1 5.0 0 4 M + a 0.1 5.0 0 4 - 5 The structural formulae of compounds A to L used in this Example as the component X a follows: 3-Salicyloylamido-1,2,4-triazole:
3-Salicyloylamido-benzi midazole:
5-Salicyloylamido-1,2,3,4-tetrazole:
2-Salicyloylamido- 1,3-imidazole:
3-Salicyloylamido-1,2-pyrazole:
3-Salicyloylamido-1,2-benzopyrazole:
3-(2-Hydroxy-3-naphthoenic)-acid-amido-1,2,4-triazole:
5-Methyl-3-salicyloylamido-1,2,4-triazole:
3-(5-Methylsalicyloyl)-amido-triazole:
3-(5-Octylsalicyloyl)-amido-triazole:
5-Methyl-3-(2-hydroxy-3-naphthoenic)-acid-amido-1,2,4-triazole:
N-Methyl-3-salicyloylamido- 1 2,4-triazole::
EXAMPLE 2 A dyed cloth was treated under the same bleaching conditions as described in Example 1 except that the bleaching composition set forth below was used instead of the bleaching composition of Example 1. The results obtained are shown in Table 1.
Bleaching Composition: Hydrogen peroxide-releasing compound 80 parts (See Table 2) Compound of formula (1) or dimethylglyoxime or its salt (component X) x parts (see Table 2) Amino-carboxylic acid having coordination number of at least 6 (component Y) y parts (see Table 2) Magnesium silicate 1 part Na2CO3 10 parts Glauber salt balance (to 100 parts) As will be apparent from the results, by the composition of the present invention, discoloration or color fading of dyed cloths can be sufficiently prevented.
TABLE 2 Hydrogen Peroxide-Releasing Combination of Degree of Discoloration Compound X and Y x y or Color Fading A + a 0.1 0.5 5 A + b 0.1 0.5 5 A + c 0.1 0.5 5 4Na2SO4#NaCl#2H2O2 D + a 0.1 0.5 5 M + a 0.1 0.5 5 M + b 0.1 0.5 5 A + a 0.1 0.5 5 A + b 0.1 0.5 5 A + c 0.1 0.5 5 [CH(CO2Na)2]2#H2O2 C + a 0.1 0.5 5 M + a 0.1 0.5 5 M + b 0.1 0.5 5 A + a 0.1 0.5 5 A + b 0.1 0.5 5 A + c 0.1 0.5 5 NaBO3#4H2O2 G + a 0.1 0.5 5 M + a 0.1 0.5 5 M + b 0.1 0.5 5 4NaSO4#NaCl#2H2O2 no 0 0 1 [CH(CO2Na)2]2 # H2O2 no 0 0 1 NaBOa#4H2O2 no 0 0 1 EXAMPLE 3 Among the bleaching compositions of the present invention set forth in Example 1, three compositions (A + a), (D + a) and (M + a) were chosen, and ten commercially available dyed or printed fibrous articles, wherein each of these fibrous articles had been dyed with a metal complex dye or metal complex pigment or treated with a metal salt or metal-containing fixing agent, were bleached by using these bleaching compositions under the following bleaching conditions.
Bath ratio: 1/50 Concentration: 0.5% Temperature: 500C Time: 30 minutes Water used: service water As a result, it was found that each of the foregoing compositions did not cause discoloration or color fading in the commercially available dyed or printed fibrous articles.
When these commercially available dyed or printed fibrous articles were similarly bleached by using the comparative composition free of X, Y or Z shown in Example 1, drastic discoloration or color fading was caused in two of these 10 fibrous articles.

Claims (8)

1. A bleaching composition comprising (a) from 5 to 99 percent by weight of inorganic peroxide capable of releasing hydrogen peroxide in aqueous solution, (b) from 0.01 to 10 percent by weight of a compound having the formula (I):
wherein RX is hydrogen or alkyl having one to 3 carbon atoms,
is a 5- or 6-membered heterocyclic radical which may have a fused ring; R2 is hydrogen, alkyl having one to 10 carbon atoms, phenyl, pyridyl or pyrrolidonyl, which may optionally be substituted or unsubstituted; R3 is alkyl, phenyl, alkoxy, phenoxy, amino, acyloxy, carbamoyl or acyl which may be substituted or unsubstituted, hydrogen, or halogen, or R3 may form a benzo group together with R4:R4 is the same as R3 or a monovalent radical having the formula -R6Y wherein R6 is an alkylene or alkylidene group having 1 to 6 carbon atoms or phenylene, andY is a radical formed by removing R4 from a compound of the formula (I), or dimethylglyoxime or a water-soluble salt thereof, and (c) from 0.001 to 3 percent by weight of an aminocarboxylic acid having a coordination number of at least 6, or a watersoluble salt thereof.
2. A bleaching composition according to Claim 1 which comprises from 10 to 95 percent by weight of (a), from 0.1 to 5 percent by weight of (b), and from 0.01 to 1.0 percent by weight of (c).
3. A bleaching composition according to Claim 1 which comprises from 40 to 95 percent by weight of (a), from 0.5 to 3 percent by weight of (b), and from 0.05 to 0.5 percent by weight of (c).
4. A bleaching composition according to any preceding Claim wherein R2 is hydrogen or methyl.
5. A bleaching composition according to any preceding Claim wherein R3 and R4 each is hydrogen or methyl or together they form a benzo group.
6. A bleaching composition according to any preceding Claim wherein
is triazole, benzotriazole, imidazole, benzimidazole, tetrazole, indazole, pyrazole, benzopyrazole, triazine, pyridine, pyridazine, pyrimidine, pyrazine, piperidine or imidazolidone residue.
7. An aqueous bleaching solution consisting essentially of from 0.3 to 1.0 percent by weight of a composition as claimed in any preceding Claim, and water.
8. A bleaching composition according to Claim 6 which said inorganic peroxide is sodium percarbonate, sodium perborate, sodium peroxytripolyphosphate, 4Na2SO4.NaCl.2H2O2 or (CH(COONa)2)2.H2O2.
8. A process of bleaching fabric which comprises immersing the fabric in an aqueous bleaching solution as claimed in Claim 7 for a period of ti me effective to bleach the fabric.
9. A bleaching composition as claimed in Claim 1, consisting essentially of: a. from40 to 95 percent by weight of an inorganic peroxy compound capable of releasing oxygen in aqueous solution; b. from 0.5 to 3.0 percent by weight of a compound or mixture of compounds having the formula
wherein R is hydrogen or alkyl having one to 3 carbon atoms;
is a monovalent radical of a 5 member of 6 member heterocyclic ring containing in the ring only nitrogen and carbon atoms, or nitrogen, oxygen and carbon atoms, or such a heterocyclic ring fused to a benzene ring or another heterocyclic ring to give a polycyclic radical;R2 is hydrogen, unsubstituted alkyl, having one to 10 carbon atoms, alkyl having one to 10 carbon atoms substituted with hydroxy, choro, amino, alkoxy (C1 to C1O). phenoxy, phenyl, hydroxyphenyl or benzoylamino, unsubstituted phenyl, phenyl substituted with one or two alkyls (C1 toy,), chloro, hydroxy, alkoxy (C1 to C10), acyloxy (Ct to C4) or amino, aroyl having 6 to 8 carbon atoms, pyridyl or pyrrolidone;R3 is hydrogen, unsubstituted alkyl having one to 22 carbon atoms, alkyl having one to 22 carbon atoms substituted with hydroxy, chloro, alkoxy (C to C4), phenoxy, phenyl or amino, phenyl, phenyl substituted with one or 2 alkyls having one or 2 carbon atoms or alkoxy (C, to C10), aroyl having 6 to 8 carbon atoms, alkoxy having one to 10 carbon atoms, phenoxy, halogen, alkylamino (C1 to C1O), aminosulfonamido, alkanoyloxy (C2 to C6), aroyloxy (C6 to Ca), carbamoyl, alkoxy (C1 to C ,0) carbonyl and aryl (C6 to C) oxycarbonyl, or R3 and R4 together form a benzo group; and R4 is hydrogen or -R5Y, in which R9 is alkylene having one to 6 carbons, alkylidene having one to 6 carbons or phenylene, and Y is a radical obtained by removing R4 from a compound of said formula, or dimethylglyoxime or water soluble salt thereof, c. from 0.05 to 0.5 percent by weight of an amino-carboxylic having a coordination number of at least 6 or water-soluble salt thereof, and d. the balance is a substance or mixture of substances selected from water-soluble neutral inorganic builder salts, water-soluble alkaline inorganic builder salts and water-soluble organic builders.
10. A bleaching composition according to Claim 9 in which (c) is selected from ethylenediaminetetraacetic acid, triethylenetetramine-h exa acetic acid, diethylenetriamine-pentaacetic acid, propylenediamine-tetraacetic acid, diaminopropanol-tetraacetic acid, trans-1 ,2-cyclohexanediamine- tetraacetic acid, glycoletherdiamine-tetra acetic acid, diaminopropane-tetraacetic acid, tetraethylenepentamine-heptaacetic acid and alkali metal salts thereof.
11. A bleaching composition according to Claim 9 in which said inorganic peroxide is sodium percarbonate, sodium perborate, sodium peroxypyrophosphate, sodium peroxytripolyphosphate, 4Na2SO4-NaCI 2H202 or (CH(C0ONa)2)2.H2O2.
New claims or amendments to claims filed on 21 May 1979.
Superseded claims 1-11.
New or amended claims:
1. A bleaching composition comprising (a) from 5 to 99 percent by weight of inorganic peroxide capable of releasing hydrogen peroxide in aqueous solution, (b) from 0.01 to 10 percent by weight of dimethyglyoxime or a water-soluble salt thereof, and (c) from 0.001 to 3 percent by weight of an aminocarboxylic acid having coordination number of at least 6, or a water-soluble salt thereof.
2. A bleaching composition according to Claim 1 which comprises from 10 to 95 percent by weight of (a), from 0.1 to 5 percent by weight of (b), and from 0.01 to 1.0 percent by weight of (c).
3. A bleaching composition according to Claim 1 which comprises from 40 to 95 percent by weight of (a), from 0.5 to 3 percent by weight of (b), and from 0.05 to 0.5 percent of weight of (c).
4. An aqueous bleaching solution consisting essentially of from 0.3 to 1.0 percent by weight of a composition as claimed in any preceding Claim, and water.
5. A process of bleaching fabric which comprises immersing the fabric in an aqueous bleaching solution as claimed in Claim 4 for a period of time effective to bleach the fabric.
6. A bleaching composition as claimed in Claim 1, consisting essentially of: a. from 40 to 95 percent by weight of an inorganic peroxy compound capable of releasing oxygen in aqueous solution; b. dimethylglyoxime or water-soluble salt thereof, c. From 0.05 to 0.5 percent by weight of an aminocarboxylic having a coordination number of at least 6 or water-soluble salt thereof, and d. the balance is a substance or mixture of substances selected from water-soluble neutral inorganic builder salts, water-soluble alkaline inorganic builder salts and water-soluble organic builders.
7. A bleaching composition according to Claim 6 in which (c) is selected from ethylenediaminetetraacetic acid, triethylenetetramine-hexaacetic acid, diethylenetriamine-pentaacetic acid, propylenediamine-tetraacetic acid, diaminopropa nol-tetraacetic acid, trans-i 2-cyclohexa nediamine- tetraacetic acid, glycoletherdiamine-tetra acetic acid, dia minopropane-tetraacetic acid, tetraethylenepentamine-heptaacetic acid and alkali metal salts thereof.
GB7835812A 1978-09-06 1978-09-06 Bleaching composition Expired GB2030609B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5801138A (en) * 1994-07-01 1998-09-01 Warwick International Group Limited Bleaching compositions
US5914304A (en) * 1994-07-01 1999-06-22 Warwick International Group, Ltd. Bleaching compositions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5801138A (en) * 1994-07-01 1998-09-01 Warwick International Group Limited Bleaching compositions
US5914304A (en) * 1994-07-01 1999-06-22 Warwick International Group, Ltd. Bleaching compositions

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