JPH0352519B2 - - Google Patents

Abstract

Improved fabric washing detergent composition especially but not exclusively designed for washing mixed coloured fabrics comprising from 0.5 to 25 % by weight of a peracid compound selected from the group consisting of organic peracids, peracid salts and peracid precursors which generate peracids by hydrolysis or perhydrolysis, and from 0.002 to 2.5 % by weight of copper, in the absence or substantial absence of a powerful sequestrant which complexes strongly with copper. The composition is effective in minimizing dye transfer but is non-effective or substantially non-effective with respect to direct fabric dye or stain bleaching.

Description

[Detailed description of the invention]

The present invention relates to a detergent composition particularly suitable for washing colored fabrics or mixed colored fabrics having colored and white areas. However, the present composition is by no means limited to the washing of colored fabrics or mixed-colored fabrics as described above, and can of course be used as a detergent for other items. Traditionally, two types of textile laundry compositions have been used, namely: (1) Unbleached colored textile detergent compositions: These compositions can be safely used without adversely affecting textile dyes, but have the effect of effectively suppressing the tendency of dye release found in certain colored textiles. Not yet. The disadvantage therefore arises that the dye of the colored fabric is liberated and enters the washing liquid, and that this dye transfers to and adheres to other fabrics being washed. (2) Colored textile detergent compositions containing bleaching agents, which have the ability to inhibit the transfer of dyes as described above, but may also bleach and lighten the color of textiles. . Therefore, in the past, there was no way to effectively solve the dye transfer problem other than to separate the fabrics to be washed into dark-colored fabrics and light-colored fabrics and wash them separately. At present, as colored clothing and textile materials, especially multicolored ones, are in fashion, the above-mentioned dye transfer problem has become more and more serious. Various proposals have been made to solve this problem, but so far none have achieved sufficient success. For example, British Patent Application (GB-A) No. 1368400
The patent specification discloses a dye transfer inhibitor composition comprising a peroxide such as an organic peracid and a relatively complex aldehyde or ketone compound as a bleach activator. The composition has some drawbacks, namely that it is a relatively expensive organic compound (i.e. a complex aldehyde or ketone compound)
However, the effects are not very good. Other dye transfer inhibitor compositions are also known, EP 0 024 367 discloses compositions of the type in which organic peracids are activated with bromide ions, and EP 0 024 368 discloses compositions of the type in which organic peracids are activated with bromide ions. The document discloses a composition containing an organic peracid precursor and a bromide ion-based activator.
The main disadvantage of these compositions is that the fabric bleaching action is so strong that colored fabrics become lighter in color. European Patent Application No. 0058444 discloses a low dye transfer textile detergent composition for use at relatively low temperatures, which contains as an essential component an organic peracid or an organic peracid precursor. and a water-soluble iodide type salt. This iodide is a catalyst, but this catalyst has some drawbacks.
That is, (1) there is a risk of undesirable coloring due to iodine formation, and (2) there is also a risk of directly bleaching the dye in the fabric. The purpose of the present invention is to wash various fabrics of one or more colors (including the case of washing colored fabrics and white fabrics together).
It is an object of the present invention to provide a novel detergent composition for textiles which can be used in the above-mentioned manner and which does not have the above-mentioned disadvantages. Another object of the present invention is to effectively bleach dyes in solution, i.e. to minimize said dye transfer, but without direct bleaching of dyes in textiles.
Alternatively, it is an object of the present invention to provide a detergent composition having the characteristic that it does not contain any harmful substances. These and other objects are achieved by a detergent characterized in that it contains a peroxidic acid and a catalyst capable of ionizing copper, but does not contain a strong sequestering agent that strongly reacts with copper to form complexes. It has now been discovered that this can be achieved by the use of compositions,
This will become clearer from the description below. As a result of research by the present inventor, the following was discovered. The transition metal ion has a catalytic effect that enhances the action of the oxygen bleach on the dye in the solution. For example, hydrogen peroxide or hydrogen peroxide adducts and inorganic persalt/bleach activator based compositions,
Alternatively, peracids themselves can all be activated with copper ions. Furthermore, bleach compositions containing a copper catalyst and a peroxide acid may be more effective than bleach compositions containing a copper catalyst and a hydrogen peroxide-based compound (e.g., sodium perborate). discovered. Experiments on the catalytic effect of transition metal ions on the bleaching effect of peracetic acid on direct dyes in solution were conducted under the following experimental conditions. Conditions: Peracetic acid (4.6×10 ^-4
mol/) was added and the dye concentration was measured at the wavelength of maximum absorbance. Various transition metal compounds [CuSO ₄ , MnSO ₄ , CoCl ₂ , FeCl ₃ , NiSO ₄ ,
The above experiment was repeated many times using Ti(SO ₄ ) ₂ ]. This experiment was conducted at pH 9 and 40°C. The results of this experiment are shown in Table 1. In addition, in the dye concentration measurement procedure described above, at the beginning of each experiment, λ _nax (490-510 nm) and maximum absorbance (=100% dye) were measured after addition of the transition metal compound but not before addition of bleach. It was measured.

【table】

[Table] Dye bleaching operations catalyzed by transition metals can only be carried out using transition metal ions that can readily undergo one-electron redox reactions that result in the formation of "reactive groups." Recognizing this is very important in the study of bleaching mechanisms. As shown in Table 1, in addition to copper, cobalt is the only transition metal that exhibits sufficient catalytic activity during dye bleaching with peracetic acid; other transition metals include: All are inert, including chromium and zinc. Although the present inventor is not bound by any theory, it is believed that the dye bleaching reaction using an oxidizing bleach can generally proceed through the following two reaction routes. Path A +D→DM ⁿ⁺ Bl→Oxidized dye (+Bl) Path B Here, M represents a metal, D represents a dye, and Bl represents a bleaching agent. *The term "radical" means a radical capable of undergoing a one-electron reaction. This reactive radical reacts with the dye, but the exact nature of this radical is still unknown. The transition metal ion reacts with the peroxide compound according to the reaction formula shown in reaction path B to decompose the latter and generate a certain radical, and
Although it is already known that this radical is highly oxidizing and can oxidize most unsaturated molecules, no transition metal is as effective as copper in preventing dye transfer. discovered. A possible explanation for the above phenomenon is a reaction mechanism in which transition metal ions strongly react with various dyes to form complexes according to the reaction formula described in Reaction Route A. This reaction mechanism is not particularly well known. The reaction of transition metals with bleach along the above reaction path occurs only after the metals have reacted with the dye, and this appears to only really occur in the case of copper. In addition, the complex formation reaction between transition metals and dyes promotes dye bleaching.
It seems more or less certain. This is because the decomposition reaction of bleach in the presence of a metal catalyst can occur in the vicinity of the dye in the dye-metal-bleach agent complex. The fact that copper ions form complexes more readily than other transition metal ions explains why copper is generally the most useful transition metal when bleaching dyes in solution. It is considered one. The cupric ion, which is the smallest divalent transition metal ion and has the highest charge density, most readily forms stable complexes. Complexes of cobalt and chromium with dyes are also very stable, but unlike copper they are kinetically inert and cobalt and chromium are present in the chemical structure of the dye. In order to introduce (), it is necessary to react under extremely harsh reaction conditions. In fact, copper is not the most powerful decomposer of molecules in bleach compounds. Cobalt is much more powerful in this regard, and if cobalt were used, the production of free radicals or free radical-like intermediates from the oxygen bleach would be much greater. Experiments have shown that cobalt is less effective than copper in dye bleaching because the radicals formed when cobalt is used cause "unhelpful bleach decomposition reactions" and
On the other hand, in the case of copper, the radicals occur near the dye molecules, so cobalt is thought to be more effective in dye bleaching than copper. Although manganese is known to be a very useful catalyst in color bleaching, especially with hydrogen peroxide bleaches in the presence of carbonates, it is also used in dyes. It was found that the effect was low for the purpose of suppressing metastasis. Experiments have also shown that under practical working conditions, manganese interferes with the catalytic action of copper, and therefore it is preferable to avoid the presence of manganese when carrying out the process of the invention. In addition, various experiments were conducted to investigate whether strong metal-dye complex forming ability is necessary as one of the essential conditions for copper to exhibit good catalytic activity in dye bleaching in solution. From UV/visible light spectrum experiments, the dye “CI Direct Red”
81" and "CI Acid Orange 7" were confirmed to form a complex with copper. However, "CI Acid Orange 7", which is an azo dye without an ortho-hydroxyl group,
When copper sulfate is added to ``Acid Orange 52'', the UV/visible spectrum changes only slightly, suggesting that the bond between this dye and copper is very weak. It was confirmed that when copper was added to a solution containing sodium (a type of peroxide), the bleaching rate of the dye increased, but this was due to the fact that copper has a strong ability to form complexes with copper. The dye bleaching rate is similar to that for dye bleaching. The complexing sites of bis-ortho-ortho-dihydroxyazo dyes are “blocked” with chromium.
(Chrome is “CI Acid Blue 161”)
Although the addition of copper alone to this dye hardly changes the visible spectrum, adding copper in the presence of a monopersulfate bleach When added, the dye bleaching rate increases considerably. Thus, these experiments have shown that the complexing power of copper to dyes is not a prerequisite for dye bleaching reactions in the presence of copper catalysts. Copper therefore exhibits the above-mentioned catalytic action even when the complexing power of this metal with the dye is weak or absent. However, the strong complexing power of copper towards dyes under washing operating conditions has some implications for the higher catalytic activity of copper, which has been found as a general fact by comparison with other transition metal ions. This is considered to be a major contribution. There is considerable evidence that dye bleaching in the presence of copper catalysts is closely related to the decomposition of bleach in solution. An increase in copper concentration generally results in an increase in dye bleaching rate and bleach degradation rate. It has been found that peroxide decomposition reactions in the presence of transition metal catalysts often include an induction period, which can be shortened by increasing the amount of copper ions present. In many experiments involving dye bleaching in the presence of copper catalysts, it has indeed been observed that the induction period can be shortened by increasing the copper ion concentration. Although the shortening of the induction period in this case is accompanied by an increase in the decomposition rate of the bleach, acceleration of dye bleaching to avoid dye transfer can be achieved by the following operation. (a) increasing the concentration of bleach and copper() ions and further increasing the radical production rate, such as by: (b) increasing the pH of the bleaching solution; and (c) Adding a suitable reducing agent, for example hydrogen peroxide in the form of a solid hydrogen peroxide adduct such as sodium perborate or sodium percarbonate which can generate hydrogen peroxide in solution. In order to investigate the effect of cupric ion concentration on the dye transfer prevention operation, peracid bleaches such as monopersulfate (commercial product "Oxone" (registered trademark)) and diperisophthalic acid (commercial product "Suprox") were used. ® ] and magnesium monoperphthalate in the presence or absence of sodium perborate. The detergent base used in this experiment had the following composition: Ingredient parts by weight Sodium dodecylbenzenesulfonate 16.0 Coconut ethanolamide 3.0 Sodium toluenesulfonate 2.0 Sodium triphosphate 35.0 Alkali silicate anhydride 11.0 Sodium sulfate 10.6 Water 9.1 The results of this experiment are shown in Table 1.

Table 1 shows the results of experiments investigating the effect of pH on dye transfer inhibition operations using monopersulfate bleach systems in the presence of copper catalysts. In addition, the bleaching of the dye "Direct Red 81" with various peroxidic acid agents, namely diperisophthalic acid (2018), monopersulfate (2012), and peracetic acid (2013) in the presence of a copper catalyst, The effect of increasing pH on bleaching rate is shown in the graph of Figure 1. This graph shows PH (horizontal axis) and dye concentration (g/
; vertical axis), and the experimental conditions in this case were as follows. Experiments were carried out at 40° C. using the dye “Direct Red 81” (0.002 g/) and peroxide acid [4.6×10 ⁻⁴ gram atoms (active oxygen)] at a given pH value. The diperisophthalic acid used here was a commercial product (trade name "Suprox"), and the monopersulfate was also a commercial product (trade name "Oxone"). The peracetic acid used was pretreated with catalase to remove H ₂ O ₂ . As is clear from this data, dye bleaching effectiveness generally increases considerably as pH increases.

[Tables] Tables 1 and 2 present experiments on the effect of the addition of perborate (sodium perborate) when carrying out dye bleaching operations with monopersulfate, diperisophthalic acid or magnesium monoperphthalate. Results are shown. It has been found that, in general, the addition of perborate significantly reduces the amount of dye transfer. It has also been found that the optimum molar ratio of peroxyacid to perborate in this case is about 2:1. Using more perborate than the above values reduces its effectiveness and may even have negative effects in some cases. Experiments on dye bleaching in solution and dye transfer in a tergotometer were performed according to the following method. Dye bleaching device in solution This device is equipped with a spectrophotometer (commercial product; model name “Beckman DB”) equipped with a fluid silica cell (1 cm).
spectrophotometer).
A water bath was used to maintain the entire liquid sample at a predetermined temperature, and a PH-stat was used to control the PH. This cell was connected to a solution container using a small-diameter silicone rubber tube, and the liquid was circulated using a fluid pump (commercially available; model name: "Watson Marlow flow inducer"). To prevent the accident of liquid overflowing into the cell chamber, a return liquid pipe was connected between the cell and the solution container. The silicone rubber tube was introduced into the cell chamber through a small hole in the lid of the spectrophotometer. The small amount of light that enters here has no effect on the data in the visible light spectrum. Fluid Cell (Flow Cell) This fluid silica cell had a path length of 1 cm. A glass supply tube was inserted into this stopper, reaching almost to the bottom of the cell. One side of this glass tube was placed outside the beam path.
A short drain tube was attached to the top of the cell to allow liquid to flow from the top of the cell through the pump and back into the solution container. Method A dye solution (undiluted solution) with a concentration of 0.04% w/v was diluted with distilled water to prepare 250 ml of a 0.004% solution. The dilute solution was placed in a 600 ml beaker placed on a water bath preheated to 40° C. and the pH was adjusted. This liquid was then passed through the cell at a rate of 40 ml per minute using a pump. Under these conditions, the liquid flowed within the cell in a good fluid state, and no turbulent flow that would cause foaming occurred. Ray of light passing through the dye (λ _nax )
The transmittance was measured and recorded on a recorder. Furthermore, 250 ml of distilled water containing 1.137×10 ⁴ moles of peroxide acid was heated to 40° C. to adjust the pH. This was added to the dye solution described above, and the change in transmittance (%) was measured and recorded over 1 hour. During this time,
The liquid was constantly stirred and aliquots of the sample liquid were removed at time intervals and titrated with 1/200M sodium thiosulfate. If agents such as electrolytes, surfactants or bleaching aids were to be used, these were added during the preparation of the first dye solution (stock solution). The bleaching rates were compared using the same active oxygen concentration. Calculation of Dye Concentration In order to find the wavelength of maximum absorbance, the dye solution was sequentially irradiated with light from a wavelength of 700 nm to a wavelength of 400 nm. A graph showing the relationship between absorbance (at wavelength λ _nax ) and concentration (%w/v) was then drawn and the slope measured. Measurements were made for various dye solutions and changes in transmittance (%) were recorded. Therefore, the dye concentration at any given time can be calculated using the following formula. Dye concentration (%w/v)=2-log%T/[slope] Here, the "slope" is the slope of the line showing the relationship between absorbance and concentration in the graph. Dye Transfer Experiment...Test Method Dyed Test Fabrics Various fabrics dyed with different types of dyes were used as samples. 17.5 in each wash operation
A square dyed fabric measuring 17.5 cm was used as a sample. Monitoring Dye Transfer Reactions A mercerized and desized white cotton cloth and white bulked nylon 66 were used as test fabrics to examine dye color transfer. Both fabrics were free of fluorescent dyes. Each of these samples was cut into squares measuring 12 x 12 cm and, regardless of the type of dye tested, was placed in a washing tub and washed at the same ratio of liquid to fabric. Washing Conditions A set of test fabrics was washed in a tergotometer. This washing was carried out for 30 minutes at a constant temperature (40°C). The rotation speed of the washing machine was 100 rpm. The concentration of the detergent composition is 0.4% w/v (in hard water at 18°)
The ratio of liquid to cloth was 50:1. Each set of test fabrics was rinsed separately three times with 600 ml of cold water (18° hard water). Washing method: Pour 450ml of 18° hard water into a tergopot and heat to 40°C. The previously weighed ingredients were then added. 1 piece of dyed test fabric,
One piece each of cotton and nylon white test cloths were placed in the pot and washed for 30 minutes. The rotation speed was 100 rpm. After washing, each set of test fabrics was removed from each pot and placed separately in 600 c.c. of cold water (18° hard water). This washing operation was continued, i.e. each set of test fabrics was washed separately with 600 ml of cold water (18° hard water).
Washed 3 times with water in cc. After washing with water, each test fabric was separated, covered with paper towels to remove excess moisture, and dried in a drying oven at 60°C. Measurement of dye absorption amount (transfer amount) The reflectance of the test cloth was measured using a spectrophotometer (commercially available; model name: Beckmann DB GD grating).
spectrophotometer) at the wavelength of maximum absorption of the dye. This spectrophotometer is
Used with a diffuse reflection attachment attached.
When measuring the test cloth, barium sulfate was used for standardization of the apparatus and as a reference sample. As can be seen from the above experimental results, it is preferred that the compositions of the present invention contain at least 0.002% copper by weight, i.e. approximately
It is preferable that the composition contains copper in an amount equivalent to 0.1 ppm or more, and the pH of the composition is
is preferably about 7-11 in 5 g/solution, and the composition preferably comprises a hydrogen peroxide adduct in a molar ratio of the adduct to peroxide acid of about 1:100 to 2:1. It is preferable that the content is 1:25 to 1:1. For practical reasons, the upper limit for copper concentration may be set at about 2.5% by weight (based on the total weight of the composition). Any copper salt can be used as a source of copper in the practice of the present invention, examples of which include copper sulfate, copper carbonate, copper chloride, copper phosphate, and the like. As mentioned above, sequestration of copper by strong sequestering agents should be minimized, which can promote the detergent/copper reaction and the generation of radicals from the bleach. On the other hand, excessive decomposition of the bleaching agent during storage of the powder composition must be avoided. To this end, relatively weak sequestering agents such as salts of ethylenediaminetetraacetic acid (EDTA) may be present in very small amounts in the present invention, generally less than 0.2% by weight, preferably less than about 0.1% by weight. (based on the total amount of the composition). The allowable amount of sequestering agent added will vary depending on the amount of copper added. When applying the present invention to detergent compositions containing common types of phosphate builders, it is generally necessary to incorporate relatively high amounts of copper in the composition. The amount of copper added to such compositions is generally about 0.02% by weight.
It is preferable that it is above. From theoretical considerations, chromophores in contaminants present on textiles generally have quinonoid properties, which behave very differently from dyes in dye bleaching reactions. A variety of dyes such as azo dyes, quinonoid dyes and indigoid dyes can all be bleached in solution by the catalysis of transition metal ions. Dyes can be bleached in solution (by homogeneous reaction), but when bleaching dyes on fabric, the bleach must be transferred from the solution phase onto the fabric, i.e. onto the substrate phase. . According to the present invention, it has surprisingly been found that copper added to the wash liquor does not catalyze the bleaching reaction of dyes or colored stains on textiles. Copper in solution is a transferable bleaching agent (bleach anion ROO ^- and especially non-dissociated ROOH) in the solution.
It appears to have the effect of reducing the direct bleaching of the fabric by reducing the concentration of bleach and thereby reducing the amount of bleach transferred to areas on the fabric where the dye or color is present. It will be done. Although the present specification specifically describes the use of peroxyacids in accordance with the present invention, the present invention may also utilize peroxyacid precursor systems. This peroxide acid precursor system is capable of producing an organic peroxide acid upon hydrolysis in the aqueous phase. Organic peroxide acids that can be used in the present invention are materials well known in the art. It can be aliphatic or aromatic and has the general formula: In the above formula, R is an alkylene group having 1 to 16 carbon atoms or an arylene group having 6 to 8 carbon atoms, and Y is hydrogen, halogen, an alkyl group, an aryl group, or an anionic group in an aqueous solution. represents a group capable of forming, examples of which include:

【formula】

[expression] or

[Formula] In the above formula, M is hydrogen or a water-soluble salt-forming cation. Examples of aliphatic peroxide acids include peracetic acid, monoperazelaic acid, diperazelaic acid, diperadipic acid, diperoxydodecanoic acid, and decylbutane-diperoxoic acid. Examples of aromatic peroxyacids include monoperoxyphthalic acid, perbenzoic acid, m-chloro-perbenzoic acid, diperisophthalic acid, and mixtures thereof. Examples of peroxide salts include magnesium monoperphthalate, potassium monopersulfate, and potassium peroxymonophosphate. Mixtures of peroxyacids, which may be mixtures with or without hydrogen peroxide adducts, can also be used advantageously in practice. A reaction system containing a precursor that can generate peroxide acid in situ will be described. In this case, peroxyacid precursors can also be used which can produce peroxyacids upon hydrolysis. Accordingly, various types of peroxide acid warfare precursors may be used within the compositions of the present invention. Examples of peroxide acid precursors include:
Mention may be made of benzoyl peroxide and diphthaloyl peroxide, both of which can form the following peroxyacids: perbenzoic acid and monoperoxyphthalic acid, respectively. The amount of peroxide-based compounds in the compositions of the invention is generally 0.5-25% by weight, preferably 1-15% by weight. The above amounts of peroxide-based compounds are applicable to organic peroxide acids, peroxide salts and peroxide acid precursors (those capable of producing peroxide acids upon hydrolysis). . In systems containing an organic peroxide acid precursor and a persalt, it may be advantageous to use a stoichiometric ratio of the organic peroxide acid precursor to the persalt. However, the ratio of acid peroxide to organic precursor can be increased, especially if a persalt bleach scavenger such as catalase is present.
Preferred persalts are sodium perborate and sodium percarbonate. Accordingly, the present invention provides 0.5-25% by weight of peroxyacid or peroxyacid precursor as defined above;
Limited only to mixed-color fabrics that contain 0.002% by weight or more of copper cations and are characterized by not containing or substantially not containing strong sequestrants that strongly bind and form complexes with copper. However, the present invention provides a textile detergent composition particularly suitable for laundering such textiles. Preferably, the detergent composition of the invention contains a surfactant. The surfactant may be anionic, nonionic, cationic, semipolar, amphoteric or zwitterionic, or a mixture thereof. Typical surfactant mixtures are anionic/nonionic mixtures and cationic/nonionic mixtures. These surfactants can be used at about 5-50% by weight, preferably about 10-35% by weight (based on the weight of the composition). Typical anionic non-soap type surfactants are:
Alkylbenzenesulfonates having 8-16 carbon atoms in the alkyl group, such as sodium dodecylbenzenesulfonate; aliphatic sulfonates, such as C ₈ -C ₁₈ alkanesulfonates; α-olefin and trioxide diluted with gas. Olefin sulfonates of 10-20 carbon atoms obtained by reaction with sulfur and hydrolysis of the reaction product; alkyl sulfates such as tallow alcohol sulfates; ethoxylated and/or propoxylated fats Alcohol, 8 carbon atoms in the alkyl group
-15 alkylphenols, 1-8 ethylene oxide or propylene oxide groups;
It is a sulfated product of fatty acid amide containing moles. Other anionic surfactants that can be used in the present invention are alkali metal soaps (e.g. _C8 - _C22 fatty acid soaps). Typical nonionic surfactants have 5 carbon atoms
- condensates of alkylphenols having 15 alkyl groups and ethylene oxide, such as nonylphenols and 6-30 units of ethylene oxide;
Condensates of higher fatty alcohols such as C ₁₀ -C ₁₅ alcohols and ethylene oxide [for example, "Tergitol", a commercial product manufactured by Union Carbide;
(registered trademark)]; a condensate of a fatty acid amine and 8-15 units of ethylene oxide; and a condensate of polypropylene glycol and ethylene oxide. Examples of representative cationic surfactants include conventional quaternary ammonium compounds and _C10 - _C25 alkylimidazolinium salts. Preferred quaternary ammonium compounds include ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, dihydrogenated-tallow dimethyl ammonium chloride or -methyl sulfate, dioctadecyl dimethyl ammonium chloride, dicoconut alkyl dimethyl ammonium chloride. Di(C ₁₆ -C ₂₀ alkyl)-di(C ₁ -C ₄ alkyl) ammonium salt. Furthermore, quaternary ammonium compounds having one long chain such as a _C10 - _C22 alkyl group or -alkenyl group are also suitable. Among the C ₁₀ -C ₂₅ alkylimidazolinium salts, 1-methyl-2-tallow-3-
(2-tallowamidoethyl)imidazolinium chloride “Varisoft”
455” and “457” (manufacturer: Ashland)
Chemical), and “Stemoquat M 5040/
H” (Manufacturer: Chemische Werke Rewo)
It is. Details of the surfactants which can be advantageously used in the present invention can be found in the book “Surface Active Agents”, Vol.
, Schwartz, Perry (Interscience Publishers;
1949) and “Surface Active Agents and
Detergents”, Vol., Schwartz, Perry,
It is described in Berch (Interscience Publishers; 1958) and others. Detergent compositions of the present invention generally may also contain one or more detergent builders and alkaline substances. Generally, the detergent builder will be present in a total amount of about 5-70% by weight (based on the weight of the detergent composition).
Many detergent builders are known and those skilled in the formulation of textile detergent compositions will be familiar with these builders. Examples of known detergent builders include sodium triphosphate; sodium orthophosphate; sodium pyrophosphate; sodium trimetaphosphate; sodium carbonate; sodium silicate; _{sodium oxydiacetate} ; ); sodium salts of α-sulfonated long-chain monocarboxylic acids; polycarboxylic acids, i.e., unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, such as maleic acid, acrylic acid, Polycarboxylic acids derived from itaconic acid, methacrylic acid, crotonic acid, aconitic acid and the anhydrides of these acids, as well as polycarboxylic acids derived from the aforementioned acids and anhydrides with small amounts of other monomers (e.g. vinyl chloride, vinyl acetate, methacrylate). Sodium salt of polycarboxylic acid obtained by copolymerization with methyl acid, methyl acrylate, styrene; modified starch such as starch oxidized with sodium hypochlorite etc. The ring of the hydroglucose unit is open and becomes a dicarboxyl unit). Other suitable builders include British Patent No. 1429143;
Examples include insoluble aluminosilicates such as zeolite A described in specifications No. 1470250 and No. 1529454. Furthermore, the detergent composition of the present invention may contain any amount of components that are commonly used in known detergent compositions. Examples of such additional formulation ingredients include foam promoters such as coconut monoethanolamide and palm kernel monoethanolamide; foam control agents; inorganic salts such as sodium sulfate and magnesium sulfate; and redeposition agents such as sodium carboxymethyl cellulose. inhibitors; and minor additional ingredients such as fragrances, colorants, fluorescent additives, corrosion inhibitors and bactericides. The detergent composition of the present invention can be advantageously used for relatively long-term (soaking) washing or relatively short-time washing operations of colored fabrics at temperatures below 60°C, that is, around room temperature. , dye transfer is minimized and there is no risk of direct bleaching (decolorization) of the fabric. The present invention can also be used to incorporate washing and bleaching aids to improve the effectiveness of existing detergent compositions. The composition in this case contains as essential ingredients a dry mixture of 0.5-25 parts by weight of a peracid compound and 0.002-2.5 parts by weight of a copper catalyst (e.g. cupric sulfate or cupric chloride) and optionally and an inert filler such as sodium sulfate. The detergent composition of the present invention is preferably prepared in the form of powder or granules such as flowable powder or aggregates thereof. The composition can be manufactured according to conventional manufacturing techniques commonly used for the manufacture of granular detergent compositions, for example, by dry mixing operations, or by forming a slurry mixture and then spray drying. Alternatively, it can be prepared by spray cooling and then dry addition of unstable components (sensitive components), such as solid organic peroxide compounds, peroxide acid precursors, inorganic peroxyhydrate salts, etc. In addition, these may be used to improve storage stability or to prevent undesired reactions between the bleaching agent and the copper or other ingredients in the composition from occurring excessively during storage of the composition. Any conventional technique such as milling, granulating, pelletizing, or coating any of the ingredients can be used as desired.

[Brief explanation of drawings]

The accompanying drawings are graphs showing the results of the experiments described herein.

Claims (1)

[Scope of Claims] 1. A textile cleaning detergent composition particularly suitable for cleaning mixed colored textiles, comprising a surfactant, a detergent builder, a bleaching agent and a heavy metal compound, comprising: (a) as a bleaching agent: () 0.5; Organic peroxide acid or peroxide salt in an amount of ~25% by weight and ()1:
a hydrogen peroxide adduct in a molar ratio to said peroxide acid or peroxide salt of 100 to 2:1;
and (b) contains a copper compound as a heavy metal compound in an amount of copper ions of 0.002 to 2.5% by weight, and (c) the composition has a solution pH of 7 to 11 (5 g/
) and may be present in an amount of less than 0.2% by weight, being substantially free of strong sequestering agents that strongly complex with copper, other than ethylenediaminetetraacetate, which has Detergent composition for use. 2. The detergent composition according to claim 1, wherein the molar ratio of hydrogen peroxide adduct to organic peroxide acid or peroxide salt is from 1:25 to 1:1. 3 Claim 2 in which the molar ratio is about 1:2
The detergent composition described in Section. 4. A detergent composition according to claim 1, 2 or 3 containing 0.02 to 2.5% by weight of copper ions.