JPH0245600A - Stabilized system of liquid hydrogen peroxide composition - Google Patents

Abstract

PURPOSE: To provide a stabilized composition comprising an aqueous system composed of peroxidiene component and so on, and a stabilizing system composed of chelate agent and so on.

CONSTITUTION: An intented composition comprises (A) an aqueous system composed of (i) peroxidiene component such as hydrogen peroxide or the like, or an organic component composed of non-ionic surface active agent such as polyethoxyl alcohol or the like, (ii) fluorescent bleaching agent, and (iii) aqueous system composed of a dye, and (B) a stabilizing system composed of (i) chelate agent such as amino polyphosphonate or the like, and (ii) free radical scavenging agent of aromatic amine such as substitutional diaryl amine or the like.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fabric bleaching composition for household use, particularly a liquid peracid compound, such as hydrogen peroxide based surfactant, fluorescent whitening agent. BACKGROUND OF THE INVENTION This application is filed in U.S. Patent Application No. 06/745,617 (No.
U.S. Patent No. J21107/144,616 (No. 198, filed on June 17, 1985, currently abandoned)
This is a partial continuation of the original application (filed on January 11, 2008), and is entirely assigned to the applicant, The Clorox Company.

Accordingly, the original application is hereby incorporated by reference, although fully written, to facilitate disclosure of the present invention.

Liquid bleach has long been used in households as an aid in bleaching and cleaning fabrics. Hypochlorite bleach is most widely used for this purpose because it is highly effective and cheap and easy to manufacture.

Other bleach systems have been introduced in recent years in an attempt to extend the usefulness of household bleach. Predominant among these are dry powder or granular compositions, most commonly based on peroxy or perboro compositions. Such materials must be placed in an aqueous solution to release the active bleaching ingredients.

Liquid bleaching compositions containing peroxy compounds are generally less available in the household market than the solid forms mentioned above. Hydrogen peroxide compositions effectively bleach a wide range of textile materials and are less harsh to the touch than hypochlorite bleaches.
Although they do not emit unpleasant gases or odors, hypochlorite bleach has not found much use in the household market.

This lack of use in the household market is due in part to the instability of peroxide solutions. Instability is primarily mediated by metal ion contamination even at very low concentrations. Considerable effort has been expended in researching stabilizers for hydrogen peroxide compositions.

Perhaps one reason why stabilized hydrogen peroxide compositions have not been successful is that other than commercial bleaching compositions, especially if the composition is intended to be used as a pre-spotter. Such "pre-spotter" compositions most advantageously contain surfactants for detergent effect, fabric reflectivity and white color. Contains fluorescent whitening agents (also known as optical brighteners) to enhance the consumer's impression of intensification, and dyes to produce a pleasing color in the bleaching solution.In addition to the bleaching compound itself, these All of the ingredients have been recognized as essential to liquid peroxide bleaching compositions to achieve sufficient acceptability for the household market.

Unfortunately, liquid bleaching compositions based on peroxides are not only degraded by the presence of contaminants such as trace metal cations (0.5 ppm or more), but also contain strong surfactants, fluorescent whitening agents and dyes. Another problem is that it is attacked by peroxide itself, which is a powerful oxidizing agent. Thus, peroxide-based bleaching compositions containing surfactants, fluorescent whitening agents, and dyes degrade very rapidly. When surfactants are oxidized, they lose their cleaning properties. Fluorescent whitening agents lose their effectiveness when oxidized. Dyes also lose their color or change to an undesirable color when oxidized.

SUMMARY OF THE INVENTION The present invention is directed to a method of stabilizing compositions based on liquid hydrogen peroxide, particularly liquid peroxide bleaches that also contain surfactants, fluorescent whiteners and dyes. The present invention is also directed to the composition itself produced by such a method.

Specifically, the present invention relates to bleaches stabilized by the addition of metal chelating agents as well as free radical scavengers to liquid hydrogen peroxide bleaching compositions (including the additional components described above).

The presence of both a chelating agent and a free radical scavenging agent is necessary to achieve the desired stability.

The metal chelating agent or sequestering agent may be selected from known metal chelating agents. A suitable group of such chelating agents is mentioned in the original application, for example Fe4
Aminopolyphosphonates are known to sequester metal ions such as Cu40 and Cu44.

The free radical scavenging agent may be selected from organic antioxidants, particularly substituted mono- and di-hydroxybenzenes and their congeners, also as described in the original application cited above.

Combined fluorescent whitening agents (also known as optical brighteners)
The stabilization of hydrogen peroxide compositions containing surfactant and dye components relies on the presence of both metal chelating agents and free radical scavenging agents. In order to effectively prevent the deterioration of various components and maintain the desired strength over a long period of time, the stabilizer needs to be present in a very small amount, for example, about 10% of the weight of the liquid composition. It is.

As used herein, "stabilization" refers to the retention of the physical and chemical properties of the components of the bleaching composition at or slightly below their initial levels over an extended period of time; This means that the rate of deterioration is significantly reduced compared to unstabilized formulations. Thus, in the presence of the stabilizer, the peroxide component retains most of its initial oxidation ability, the surfactant component retains most of its detergency, and the fluorescent whitening agent is improved to the fabric. It retains most of its ability to give a beautiful appearance, and the dye component is completely prevented from oxidizing.

The above original application discloses that a peroxide oxidizing agent, a surfactant,
A liquid peroxide bleach containing a fluorescent whitening agent and a dye with small amounts of a metal chelating agent (or sequestering agent) such as an aminopolyphosphonate and a scavenging agent such as substituted hydroxybenzene. Disclosed are methods for stabilizing components in compositions.

In accordance with the present invention, an effective stabilizing system for liquid peroxide bleaching compositions comprises a metal chelating agent (or sequestering agent) such as an aminopolyphosphonate and an aromatic amine free radical scavenging agent. It was discovered that it can also contain

It is therefore an object of the present invention to incorporate into a liquid peroxide bleaching composition a stabilizing system consisting of a stabilizing effective amount of a chelating agent (or sequestering agent) and an aromatic amine free radical scavenging agent. An object of the present invention is to provide a stabilizing system and method for liquid peroxide bleaching compositions.

A related object of the present invention is to provide a peroxide-containing composition containing degradable organic components comprising a stabilizing effective amount of a chelating agent (or sequestering agent) and an aromatic amine free radical scavenging agent. The object of the present invention is to provide a stabilizing system and method for peroxide-containing compositions by incorporating a stabilizing system.

The aromatic amine free radical scavenging agent preferably has (1) a hydrogen attached to the nitrogen in the amine substituent that is susceptible to attack by free radicals, and (2)
) is selected as having an aromatic ring attached to the same nitrogen to stabilize the radical formed on the nitrogen by the removal of a proton. Examples of reactions between aromatic amine free radical scavenging agents and free radicals, such as in peroxide-containing compositions (or bleaches), are detailed below.

According to the two features mentioned above, the aromatic amine free radical scavenging agent more preferably has at least 1. primary or secondary aromatic amines so that one hydrogen atom is obtained. Commercially available amine antioxidants are generally tertiary arylamines (discussed in more detail below).

Aromatic amine free radical scavenging agents contemplated by the present invention may also be fused ring amines of the type as detailed below.

The one or more hydrogens on one or more aromatic rings of the aromatic amine free radical scavenging agent are functional groups, preferably to enhance the antioxidant power of the aromatic amine free radical scavenging agent. The substitution may also be by other alkyl groups having one or more carbon atoms, so as to realize additional benefits as detailed below. It can be done.

Similar substitution of Il'F, suitably with an alkyl group, can also be carried out on one of the two hydrogens attached to the nitrogen in the amine substituent of the primary aromatic amine. In this case, the alkyl group could replace the hydrogen atom in two different primary aromatic amine free radical scavenging agents as described below.

Other objects and advantages of the invention will be apparent from the following description and claims.

Liquid household bleaching compositions based on hydrogen peroxide can be stabilized by the addition of small amounts of a two-component system, namely a metal chelating agent (or sequestering agent) and a free radical scavenging agent. be done.

The liquid bleaching composition comprises a hydrogen peroxide bleaching component, at least one surfactant, a fluorescent whitening agent, a dye, optionally a fragrance, and a final solution pH in the range of 1 to 8, more preferably about 1 to 8. 6, most preferably by adding an appropriate amount of acid or base to maintain the ratio between about 2 and 4.

A small amount of stabilizer and, of course, water are added to complete the bleaching composition.6 The peroxide component may be significantly diluted. In one preferred embodiment, hydrogen peroxide is present at about 3.5% (by weight). Surfactants are present at a level of approximately 3-4% (heavy Jt)6
The whitening agent is present at a level of about 0.15-0.6% (by weight). The dye comprises about 0,0002 to 0,0002 to 0,000% (
weight), a small amount of aromatic oil, e.g. about o, oos to 0
．． 1% (heavy!#,) may also be present. The stabilizer is about 0.05-0.2% (by weight) for chelating agents and about 0.005-0.05% (by weight) for free radical scavenging agents.
% (weight) is sufficient.

Sufficient pl+ regulator is added to maintain the ρ11 of the product between about 1 and 6, preferably between about 2 and 4. Water, which usually makes up the remaining percentage of the solution, should be deionized to reduce metal ion contamination to as low a level as possible. However, metal ion contamination is 2 to 1. Even if levels of Oppm or higher are reached, the stabilizers of the present invention are still effective.

As will be seen later, stabilizers appear to have a synergistic effect on the stability of bleaching compositions. Both the chelating agents of the present invention and the aromatic ttA'7mine free radicals should be present to fully stabilize the composition.

The reason for the stabilizing effect is not completely understood.

However, without being specifically bound, it is theorized that hydrogen peroxide and organic compounds such as non-ionic surfactants such as ethoxylated alcohols, and fluorescent whitening agents such as stilbenes, distyrylbiphenyl, etc. In the presence of peroxide, a reaction occurs between the peroxide and/or its decomposition products to generate free radicals.

- Once free radicals are generated, they further react with organic components and continually degrade the composition.

More specifically, free radical reactions in aqueous solutions.

For example, it can be initiated by a peroxide which serves to scavenge a hydrogen ion from one of the ethylene groups present in the nonionic surfactant molecule. Such a reaction would be as follows.

(Free Radical Formation) Alternatively, hydrogen peroxide itself can generate free radicals by homolysis of either O11 bonds or 0-0 bonds. That is, 110: O) I −−−−−−−−−−>
'II + @0011 or 110: 0
In any case, there are many reaction mechanisms by which free radicals can be generated in peroxide-organic compositions. According to the few mechanisms that are understood, the presence of heavy metal cations also appears to promote the generation of free radicals. Such free radicals appear to be particularly reactive towards compounds with military double bonds, such as dyes and brighteners.

In the stabilizing system of the present invention, the chelating agent appears to serve to sequester heavy metal cations, especially polyvalent metal ions such as copper and iron, which are always present in small amounts in minerals in water. The ability of heavy gold gt cations to catalyze peroxide homolysis is thus hindered. Similarly, the ability of single heavy metal cations to mediate free radical generation is eliminated or significantly reduced.

Free radical scavengers appear to work by binding to free radicals that are initially formed in solution. In this way, the ability of free radicals to degrade organic components is eliminated, and the explosive reactions of self-propagating free radicals are stopped. Such a reaction mechanism halts or greatly reduces the destruction of desirable surfactants, optical whiteners, dyes, and fragrance ingredients.

The above description has been made as a possible explanation for the extraordinary stability afforded to peroxide bleaching compositions, and the present invention is not intended to be bound by such explanations. Other possible reactions may contribute to improved stability.

The individual functions of the chelating agents and free radical scavengers also cannot explain why such surprisingly improved stability is achieved by the present invention. When a two-component stabilizing system is used in a liquid peroxide bleaching composition, the degradation of the organic components therein is dramatically reduced, and the stabilizing capabilities of the chelating agent and free radical scavenger are considered individually. It far exceeds. It is therefore believed that the combination of a chelating agent and a free radical scavenger has a synergistic effect in improving the stability of liquid peroxide compositions containing organic components.

Regarding the stabilized peroxide compositions of the present invention, the peroxide source is present as the primary active ingredient and functions as a bleaching agent. The peroxide is usually present as hydrogen peroxide and is about 0.05-50% (by weight), more preferably about 0.1
~35%, most preferably about 0.5-15% (by weight) of 1
exists in Hydrogen peroxide is a commercial raw material available from many sources. To make bleaching compositions, peroxide is usually purchased as a concentrated aqueous solution (eg, 70%) and diluted with deionized water to the desired strength. FMC Corporation of Philadelphia, Pennsylvania is one source of hydrogen peroxide.

A surfactant is desirable for use in the bleaching composition, as it not only provides traditional stain removal action, but also helps emulsify the free radical scavenger into the aqueous bleaching composition in the formulations of the present invention. It also works to help. As will be seen later, free radical scavenger components are rather hydrophobic. Surfactants therefore assist in incorporating free radical scavengers into the bleaching composition.

As will also be seen below, the surfactant component provides a thickening effect. This is particularly the case when used at high concentrations, such as greater than about 5% (by weight).

The most preferred surfactants are nonionic. Suitable nonionic systems include polyethoxylated alcohols, ethoxylated alkylphenols, polyoxyethylene- or polyoxypropylene-block copolymers, anhydrosorbitol esters, alkoxylated anhydrosorbitol esters, and the like. Other suitable surfactants are listed in Kirk-Osmer 12 Encyclopedia of Chemical Technology, 3rd Edition, Volume 22, 360-377.
Page (1983). Such nonionic surfactants are available from a variety of commercial sources. One source of poly-1-oxylated alcohols is Shell Chemical Company of Hyuston, Texas;
There is one known under the trademark "Neodol".

One suitable surfactant is ethoxylated alcohol “N”
eodol 25-7", this alcohol has 12 to 15 carbon atoms with seven ethoxys attached to it. Anhydrosorbit esters (including sorbitan esters) are available from Atlas Chemical Industries under the trademarks "Tween" and " Available at ``Ar1acel''.

The surfactant may be present in the composition at about 3-4% (by Jt), but this is not critical. Concentrations of surfactants both lower and higher within the above ranges are acceptable. The preferred range of surfactant is 0-50%.

More preferably 0 to 20%, most preferably 0 to 10% (by weight). At high concentration levels, surfactants exert a beneficial thickening effect on liquid compositions as described above.

Such thickening helps disperse particulate ingredients such as dyes and whitening agents. Also as mentioned above, surfactants help emulsify liquid compositions, and also act as free radical scavengers and neutralizers (as they tend to be poorly soluble in water). . Mixtures of several surfactants are also suitable.

Fluorescent whitening agents (also known as optical brighteners or FIiA) are also included in the bleaching composition. Such whitening agents are also commercially available products. These products are fluorescent materials, often substituted stilbenes and biphenyls, that fluoresce by absorbing ultraviolet wavelengths of light and emitting visible light in the Bruch wavelength range. The whitening agent is deposited or adhered to the fabric during laundering to provide the desired whiteness.The whitening agent is present in the compounded acid in an amount of from several hundredths to about 5% (by weight), more preferably from about 0 to 1%, most preferably Preferably about 0 to 0
It suffices if it exists on the order of 6%. One source of such whitening agents is Tinop, a trademark of Chill Geigy Corporation of Greensboro, North Carolina.
Other useful whitening agents are U.S. Pat.
il).

A variety of different whitening agents may be incorporated into the composition.

Such selection is dictated by the fact that some whitening agents are compatible with cellulosic fibers such as cotton, while other whitening agents are compatible with synthetic fibers such as nylon.

Since the bleaching compositions of the present invention are made for all types of fabrics, natural and synthetic, it is advantageous to include both types of whitening agents.

One stilbene-based product “Tinopal”
R[3S" has an affinity for synthetic fibers. The distylbiphenyl product "Tinopal CBS-X" has an affinity for cellulose fibers.

Small amounts of dyes are also included in suitable bleaching compositions.

Although dyes constitute a very small percentage of the composition (perhaps < 0.0005% by weight, they play an important role in the consumer acceptance of the product. Such dyes account for approximately 0 to 1%, more preferably is preferably present in the range O-0.1%, most preferably in the range of about O-0.001% (by weight). Dyes such as anthraquinones are particularly suitable. Such anthraquinone dyes are A suitable dye available from Charlotte's Sandra Company is their "Nylosan ZAL"; other dyes of desirable color and bleach fastness may also be used.

Inorganic pigments can also be used. Suitable pigments are substantially or fully complexed metal cations, such as copper phthalocyanine.

Fragrances can also be included in the bleaching composition if desired.

Any aromatic oil may be used, usually in small amounts, such as 0.01%, as long as it is stable with the other ingredients.

A preferred range is about 0 to 5% (by weight). A more preferred range is about O to 1%, most preferably about O to 0.1%.

In addition to the above ingredients, a P11 modifier is added to the composition to adjust the final P1+ to a range of 1-8, more preferably about 1-6, most preferably about 2-4. When acidic pH is desired,
Phosphoric acid and sulfuric acid are suitable for this purpose.

Other inorganic acids such as nitric acid can also be used, as can water-soluble organic acids such as acetic acid, citric acid, etc., and hydrochloric acid.

On the other hand, if it is necessary or desirable to increase the ρl of the 5 composition, an iai amount of base may be used.

As mentioned above, stabilizing systems are critical to bleaching compositions. Both a quenching agent and a free radical scavenger must be present. Tests have shown that neither substance alone is as effective as when present in combination. It is only when both substances are present that there is a clear synergistic effect in stabilizing the bleaching composition and long-term stability is achieved.

As the chelating agent, a number of known chelating agents can be selected.

Care must be taken that the one chosen is effective in chelating heavy metal FK cations such as Cu44 and Fe++4. The chelating agent should also be resistant to hydrolysis and not easily oxidized by hydrogen peroxide. Preferably the chelating agent should have an acid dissociation constant, or pKa, of about 1-9, which is a low pKa.
It shows that it can dissociate at H level and bind to metal cations.

In this regard, aminopolyphosphonates have been found to be most useful in the bleaching compositions of the present invention.

Aminopolyphosphonates are commercially available compounds, such as those sold under the trademark "Deq uest" by Monsando Company (St. Louis, Missouri). These compounds have the following structures.

(II□O, PC11□) -N-CIl□-CIlt
-N-((1:II□PO, I+2)zCIl□PO,
I+.

11□0. PCI+2-N-Cl1. PO3I+□
and ()1□03PCI+□), -N-(CI□), -N
-(CIl□)t -N (CIl, PO, 11□)
2Cl1tPO,I+.

Such "Dequest" compounds are highly effective as chelating agents for bleaching compositions. Other related chelating agents may also be utilized, such as birophosphate.

The selected chelating agent should be present in the composition in an amount sufficient to bind the heavy metal rfC cations present in the aqueous solution. 1/10 or 2% is sufficient. The chelating agent is about 0.02-5%, more preferably about 0.04-0.
．． 3%, most preferably in the range of about 0.06-0.12% (by weight).

The second most important stabilizer is the aromatic amine free radical scavenger mentioned above. As mentioned above, aromatic amine free radical scavengers have two distinguishing features. Initially, at least one hydrogen atom is attached to the nitrogen of the amine substituent of the aromatic amine, making it susceptible to free radical attack. On the 21st Pi,
An aromatic ring is attached to the same nitrogen and stabilizes the radical formed on the nitrogen due to the removal of a proton as a result of free radical attack. As contemplated by the present invention,
An example of a reaction sequence between an aromatic amine and a free radical is shown below: Subject to the requirement that the nitrogen of the amine substituent of the aromatic amine must have at least one hydrogen atom attached, the aromatic amine is preferably a primary or secondary amine.

A number of commercially available substituted arylamines are shown in Table 1.

One or more hydrogens on the aromatic ring(s) of the aromatic amine free radical scavenging agent may contain a functional group, preferably itself, to enhance the antioxidant power in the aromatic amine. It may be substituted with a hydroxyl group that acts as an antioxidant. Substitutions may also include other alkyl groups or aryl rings containing one or more carbon atoms. For example, a number of substituted diarylamines are included in Table 1.

It may also be possible to replace the hydrogen atom on the nitrogen of the amine substituent of the primary aromatic amine by an alkyl group (in order to retain at least one hydrogen atom on the nitrogen according to the requirements mentioned above); Substitution by groups can also occur on hydrogen atoms on two different primary arylamines. This results in a product with the following structure: Table! The ring may also consist of an electrofused ring structure, resulting in a product such as naphthylamine. Other fused ring aromatic amines according to the invention include, for example, anthracene and phenanthrene.

In accordance with the above discussion, a number of commercially available aromatic amine antioxidants are listed in Table I.

dust rechemi table ■-continued It is 1 to 0.02% (weight).

As a general example, a typical stabilized bleaching formulation is shown below.

C2I+, 0- 5antoflex AN Monsando free radical scavenging agents generally must be resistant to oxidation by peroxides, such as hydrogen peroxide, and therefore should not be subject to excessively strong reductions that would react with the peroxide itself. It must not be a drug.

In general, all of the products summarized below and mentioned in Table 1 meet the above requirements.

Only a small amount of free radical scavenger is required in a bleaching composition.6 Generally, a few hundredths of a percent will provide an effective free radical scavenger.

A preferred range is about 0.005-0.1%, more preferably about 0.007-0.04, most preferably about 0.0 Fluorescent Colorant - Distyrylbiphenyl 0.1-0.7 −
Stilbene 0. O1~0.3 Blue dye - Anthroquinone 0.0002~
0.001 fragrance
0.01~0.05]! t0□
3-7 aminopolyphosphonate・
Chelating Agent 0.06-0.25 Free Radical Scavenger 0.005-0.02 Phosphoric Acid Sufficient amount to adjust the pl+ to 2.3 H,0- ion The remainder Stable as prepared and tested in accordance with the present invention A number of more specific examples of bleaching agents having the formulation immediately following are formulation A), and the respective stabilizing systems are shown in Table II.

15 Glue Mechanism 1 Completed 11□0□ Brightener 1 dye 2 Surfactant 3 fragrance Free radical scavenger 4 Chelating agent 5 ρ11 regulator (II, PO,) water 0.0005 3.5005 O5O1 O,12 rest weight% Note 1 Fluorescent whitening agent, distyrylbiphenyl compound.

For example, Tinopal CBX, Chill Geigy Anthraquinone Dye, Acid Blue 25, Sandra Company Neodol 25-7, C12-1i'llt-like ethoxylated alcohol, less than 7 moles of polyethylene oxide per mole of alcohol.See table below ■Dequest 2010 Dequest 20i0 Dequest 2010 Dequest 2060 Dequest 2060 Dequest 2060 Dequest 2041 Dequest 2041 Dequest 2 041 0.12 0.12 0.12 Naphthylamine 6 Anox N5M 5antoflex ^V Naphthylamine Anox N5M 5antoflex Naphthylamine Anox N5M 5antoflex All Naphthylamine 0, OI Footnotes to Table ■ ' Dequest 2010 (60% activity) is obtained from Monsando Company and has the following structure.

” Dequest 2060 (Active 50 Phantom is obtained from Monsando Company and has the following structure.

” Dequest 2041 (90% active) is obtained from Monsando Company and is of primary structure.

6゜5antoflex Avg 0.01 Available from Stoli Shemish Alikylated diphenylamine with the following structure: ■ '5antoflex AW (100% active) Available from Monsando Company. Dihydroquinoline of the following structure: 6 Naphthylamine available from Aldrich Chemical Company and stabilizing chelating agent and free radical scavenger added in each of Examples 1-16. To confirm the effect, the sample was first exposed to available oxygen (by iodine titration) and dye (undiluted).
and brightener (dilution level: brightener 3!l1 per 1000 resistant water)
1) was measured per amount. The amounts of dye and brightener were measured in absorption units on a Betstaman spectrometer set at wavelengths of 598 nm and 344 nm, respectively.

Each sample was then inoculated with 6 ppm of heavy metal ions (3 ppm Fe(III) and 3 ppm Cu(■)) and stored at 100° C. for 3 hours. The available oxygen for hydrogen peroxide and absorption values for dyes and brighteners were read again. (Note=100
(3 hours of storage at ℃ corresponds to long-term storage of about 5 months at room temperature) The observed data was collected and shown in Table ■.

Table ■ JfL Hada "Shobeige Saiton Handi 1 Ei Kabuto 11792010080560.1710004430
021792016160900.172000.43
70.1233172801568091016800
04410.122751808013280730.
1990004660061760012000680
．． 210004660071792017280960
172000.4750.3116581736016
960980.1660.169604680.444
95917360172801000.207000.
4730.34473to1744017440100
0,170.1951150,4830.454941
117120168009802160.155720
．． 4610.3828312]7360 16960
98 0.208 0 0 0.465 0.3
6 771317600 17120 97 0.18
1 0.167 92 0.48 0.436 911
417440 16480 94 0.209 0
0 0.483 0.296 611517280
15680 91 0.207 0 0 0.4
83 0.133 281617600 16720
95 0.183 0 0 0.491 0.3
97 813FVAI=first reading of brightener;
The above results in the FWAp final reading table ■ demonstrate that a surprising and dramatically improved stability is synergistically obtained when using the free radical scavenger and metal chelator stabilizing system of the present invention. ing.

Example 1 used no chelating agent or free radical scavenger and had no stabilizing effect on the dye or brightener.

Examples 2 to 4 contain only metal chelating agents, but have no stabilizing effect on dyes.

Shows minimal or no effect on brighteners.

Examples 5-7 contain only aromatic amine free radical scavengers and have no stabilizing effect on the dye and only minimal or no effect on the brightener.

In contrast, Examples 8-10 contain both a metal chelator and an aromatic free radical scavenger and show dramatic improvements in stability. Depending on the case, examples (9, 12,
14-16), lack a stabilizing effect on the dye, but overall show increased stability over Examples 1.2-4 and 5-7.

Therefore, these data demonstrate that free radical scavengers and metal chelators work synergistically to stabilize dyes and brighteners in extremely harsh environments of high temperatures (water boiling point) and high concentrations of heavy metals. has been done.

Other aromatic amines (other than those used in Examples 5-16)
can also be used in accordance with the present invention to achieve similar synergistic effects. For example, aromatic amines of all types specified in Table I and summarized elsewhere.

Additionally, other formulations than Formulation A above may be used. Bleach stabilized according to the invention (tested as above) includes, without limitation, the following formulation (Formulation B:
and C).

Condition I L Good - W Hydrogen peroxide whitening agent (distyrylbiphenyl) Acid blue dye surfactant (Dyriton X-100) Chelating agent (
Aminopolyphosphonate) p++ regulator (sulfuric acid) Free radical scavenger water 4.0 0.3 0.001 4.0 0.18 0.035 0, Ol Residual hydrogen peroxide whitening agent (Phorwite CNA) Acid blue dye interface Activator (Neodol 25-9) Chelating agent (amino polyphosphonate) ρ1 (Modifier (sulfuric acid) Free radical scavenger Water 3.0 0.3 o, ooi 3.0 0.2 0.035 0.01 Residual notes : Phorwite CNA is characterized as follows: 4.4'-bis(4-phenyl-2)1-1.2.3-
Thorazol-2-yl)-2,2' stilbenedisulfonic acid is used to stabilize liquid peroxide compositions, particularly liquid bleaching compositions containing hydrogen peroxide. A variety of aromatic free radical scavenging agents have been disclosed for inclusion in stabilizing systems containing chelating agents (or sequestering agents). It will be apparent to those skilled in the art that various modifications may be made to the invention in addition to those specifically listed, and the scope of the invention is therefore defined only by the claims.

Claims (1)

[Claims] 1. An aqueous system containing a peroxydiene component, an organic component selected from nonionic surfactants, a fluorescent whitening agent, a dye, and a mixture thereof, and a chelating agent and an aromatic amine free radical scavenging agent. and a stabilizing system comprising a stabilizing effective amount. 2. The composition according to claim 1, wherein the peroxydiene component is hydrogen peroxide. 3. The composition according to claim 2, further comprising a fragrance. 4. The composition of claim 1, wherein the nonionic surfactant is selected from the group consisting essentially of polyethoxylated alcohols, ethoxylated alkylphenols, polyoxypropylene or polyoxyethylene block copolymers, and mixtures thereof. . 5. The composition according to claim 1, wherein the chelating agent is capable of forming a chelate compound with a polyvalent heavy metal cation. 6. The composition according to claim 5, wherein the chelating agent is an aminopolyphosphonate. 7. The composition of claim 1, wherein the aromatic amine free radical scavenging agent has at least one hydrogen remaining on the nitrogen. 8. The composition according to claim 7, wherein the aromatic ring is attached to nitrogen. 9. The composition according to claim 1, wherein the aromatic amine is a primary or secondary aromatic amine. 10, one or more hydrogens on the aromatic ring are functional groups,
The composition according to claim 9, which is substituted with an alkyl group or other aryl group. 11. The composition according to claim 10, wherein the substituted functional group is a hydroxyl group. 12. Claim 1, wherein the aromatic amine is a secondary aromatic amine.
The composition described in . 13. 1 on the nitrogen where the aromatic amine is substituted by an alkyl group or a functional group containing one or more carbon atoms
2. The composition of claim 1 comprising a primary aromatic amine having 5 hydrogens. 14. Claim 1, wherein the aromatic amine consists of a fused polyaromatic ring.
The composition described in . 15. The composition of claim 1, wherein the aromatic amine is selected from the group consisting of substituted diarylamines, p-phenylenediamines, substituted dihydroquinolines, and -naphthylamines. 16. A method for stabilizing an aqueous bleaching formulation comprising hydrogen peroxide and at least one organic component selected from the group consisting of a surfactant, a fluorescent whitening agent, and a dye, the formulation comprising a chelating agent. and an aromatic amine free radical scavenging agent in a stabilizing effective amount. 17. The method of claim 16, wherein the chelating agent is selected to form a chelate with a polyvalent heavy metal cation. 18. Claim 16, wherein the aromatic amine free radical scavenging agent leaves at least one hydrogen on the nitrogen.
The method described in. 19. The method according to claim 18, wherein the aromatic ring is attached to the nitrogen. 20, one or more hydrogens on the aromatic ring are functional groups,
19. The method according to claim 18, wherein the method is substituted with an alkyl group or other aryl group. 21. The method according to claim 18, wherein the aromatic amine is a primary or secondary aromatic amine. 22. Claim 1, wherein the aromatic amine consists of a fused polyaromatic ring.
8. The method described in 8. 23. The method of claim 18, wherein the aromatic amine is selected from the group consisting of substituted diarylamines, p-phenylenediamines, substituted dihydroquinolines, and -naphthylamines. 24. A method of stabilizing a peroxide-based oxidizing liquid composition, the method comprising admixing thereto a stabilizing effective amount of a chelating agent and an aromatic amine free radical scavenging agent. 25. Claim 24, wherein the aromatic amine free radical scavenging agent leaves at least one hydrogen on the nitrogen.
The method described in. 26. The method of claim 25, wherein the aromatic ring is attached to the nitrogen. 27. An improved stabilization system for liquid compositions containing easily decomposed organic components and containing peroxides, the improved stabilization system comprising a stabilizing effective amount of a chelating agent and an aromatic amine free radical scavenging agent. Chemical system. 28. Claim 27, wherein the aromatic amine free radical scavenging agent leaves at least one hydrogen on the nitrogen.
Improved stabilization system described in. 29. The improved stabilizing system of claim 28, wherein the aromatic ring is attached to the nitrogen. 30. The improved stabilizing system of claim 29, wherein the aromatic amine is a primary or secondary aromatic amine. 31. Claim 2, wherein the aromatic amine consists of a fused polyaromatic ring.
9. The improved stabilization system described in 9. 32. The improved stabilizing system of claim 29, wherein the aromatic amine is selected from the group consisting of substituted diarylamines, p-phenylenediamines, substituted dihydroquinolines, and -naphthylamines.