JP2559062B2 - Aqueous alkali metal chlorite composition containing colorant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to alkali metal chlorites such as sodium chlorite, NaClO ₂ , and alkali metal carbonates that are incompatible with the above chlorites in an aqueous medium but within the composition, It relates to an aqueous alkaline cleaning composition comprising a stabilizing colorant which is compatible when mixed with a stabilizing amount of a stabilizer selected from the group consisting of alkali metal borates and mixtures thereof.

BACKGROUND OF THE INVENTION Aqueous alkali metal halite compositions are well known for textile industry applications, and halites, especially sodium chlorite, are a source of strong bleaching agents, chlorine dioxide gas. A pH of about 9.0 or less is a H ⁺ ion concentration sufficient to start the conversion of chlorite ions into chlorine dioxide, especially at high temperatures.
As the concentration of dioxide ions in the aqueous solution increases, the aqueous alkali metal halite composition becomes more acidic and the conversion rate increases.

Sodium chlorite is used in the paper manufacturing industry to prevent mold and mucus growth in paper mill "white" water. This is disclosed in US Pat. No. 3,046,185 to Buonanno.

The Applicant has revealed that an alkali metal chlorite solution, in particular a sodium chlorite solution, is suitable for use in cleaning homes and housekeepers, such as cleaning tiles, pottery surfaces and drains. .

Coloring agents are preferred for this composition, especially for household compositions. The colorant provides the user with a pleasing color and the composition is well visible when applied to the surface to be cleaned. In some cases the colorant is an indicator that the product composition has been washed away.

However, many colorants, including those used in household cleaners, are not stable in the alkali metal chlorite compositions referred to herein. Instability of the colorant becomes apparent due to chlorine dioxide gas generation within the composition, colorant loss of the colorant, and lowering of the composition pH. Alkali metal chlorite loss occurs simultaneously with the generation of chlorine dioxide. Furthermore, the chlorine dioxide odor is unpleasant and can be detected by the composition user even in the presence of trace concentrations.

It has been invented that many colorant additions that are unstable in aqueous alkali metal chlorite compositions can be accomplished by successfully stabilizing the system with alkali metal carbonates, borates and mixtures thereof.

It is therefore an object of the present invention to provide a detergent composition comprising an aqueous alkali metal chlorite solution containing a colorant retaining color value.

Further, the main object of the present invention is to provide a composition in which the contained colorant does not react with sodium chlorite to release a trace amount of chlorine dioxide gas at the composition pH.

These objects and advantages of the present invention will be easily understood by reading the following detailed description of the present invention.

SUMMARY OF THE INVENTION The aqueous alkaline composition of the present invention comprises an alkali metal chlorite, such as sodium chlorite, NaClO ₂ , a stabilizing colorant that is chemically incompatible with chlorite, usually in aqueous media. , And an effective amount of a stabilizer that stabilizes the composition as well as the colorant substantially as evidenced by the absence of chlorine dioxide in the composition. Stabilizers are selected from the group consisting of alkali metal, preferably sodium and potassium carbonates, borates and mixtures thereof.

Surfactants may optionally be included in the composition to provide its cleanliness and enhance its cleansing effect.

Generally, the alkali metal chlorite is about 5% by weight of the composition or less, with sodium chlorite being preferred. The colorant is selected from the group consisting of dyes, lakes and pigments, and dyes are preferred because of its high water solubility, and the amount of colorant is generally about 0.01 to about 3% by weight of the composition.
(Based on active colorant), preferably about 0.1 to about 2%.

The stabilizer comprises an effective amount which prevents reaction of the colorant with the chlorite ion formed by the dissociation of the alkali metal chlorite in the aqueous medium. The amount of stabilizer is preferably 0.5 to about 3% by weight of the composition.

Many other labile colorants can be stabilized by the practice of this invention. However, it has been discovered that better stability of some colorants can be obtained if the colorant is first neutralized with a base to remove reactive sites or acidic contaminants from the colorant.

The stable compositions of the present invention are alkaline and generally have a pH
Stability increases with increase. The best stable pH of the composition is about 9 and above, with about 9.0 to 10.5 being preferred.

Furthermore, it is known that the stability is further increased when the composition comprises an anionic surfactant. Conversely, the presence of a nonionic surfactant reduces stability, but the stability of a nonionic surfactant-containing composition that includes an effective amount of a stabilizer component in the colorant does not include a stabilizer. I know that it is better than a dog.

Preferred colorants are Color Index Dyes No. 42,090 and No. 52,035.

Detailed Description of the Preferred Embodiments It has been found that the compositions generally obtained in the aqueous detergent composition production test with sodium chlorite and a colorant contain an unsuitable amount of chlorine dioxide gas. This chlorine dioxide gas is unacceptable due to its unpleasant odor. Furthermore, the dye in the composition was consumed and disappeared.

Chlorine dioxide formation was surprising in compositions that were generally said to be incapable of producing chlorine dioxide at pH 9 and above of compositions containing sodium chlorite and a colorant, typically a dye. This chlorine dioxide evolution also occurred during the study when the colorant was neutralized with a base.

It is believed that the interaction of the colorant with sodium chlorite is not the usual acid-base neutralization reaction as is the case with so-called hydrochloric acid and sodium hydroxide. Rather, it is believed that the chromophore position of the colorant molecule is responsible for the conversion of chlorite ion, ClO ₂ ⁻ to chlorine dioxide and H ⁺ ion, and then for the further conversion of chlorite ion to chlorine dioxide. The pH of the system decreased in the rabbit as the concentration of chlorine dioxide increased, and the system pH reached 7.
It fell below 0. The chlorine dioxide formation rate accelerated as the system pH decreased toward the acid region.

Attempts have been made to use many substances to prevent chlorine dioxide formation in the sodium chlorite-colorant system. Although it is known that alkali metal carbonates and borates and their mixtures greatly improve the composition stability,
_{^{O 3 -, CH 2 COO -}} , PO 3 = salt been made unsuitable. It is surprising to consider their use as buffers at pH 8-10. pH
The NH ₄ OH and NaCl mixture in the composition with 13 was also unsuitable.

Accordingly, the composition of the present invention is selected from the group consisting of up to 5% by weight of alkali metal chlorite, dyes, lakes and pigments and is usually chemically incompatible with the above chlorite in an aqueous alkaline medium. 0.01 to 3% by weight, based on the activity of the stabilizing colorant, and a stabilizer selected from the group consisting of alkali metal carbonates, alkali metal borates and mixtures thereof, wherein chlorine dioxide is substantially present in the composition. Aqueous alkaline cleaning compositions containing a composition stabilizing effective amount as evidenced by its absence.

According to the practice of the present invention, an incompatible colorant-containing sodium chlorite composition which does not produce a trace amount or more of chlorine dioxide within 1 month, preferably within 3 months, and most preferably within 6 months after production is provided. Can be manufactured. The trace level means the level of chlorine dioxide that can be detected by an ordinary analytical method and / or an olfactry sensory test, and is usually about 10 ppm or less, preferably about 5 ppm or less in the above composition.

Sodium chlorite is about 0.5 to about 5 by weight of the composition.
%, Preferably about 1 to about 3%. Generally, about 5% or more of chlorite produces a composition whose ionic strength is too high to be sufficiently stabilized, although higher sub-dilutions can be achieved by the correct choice of dye, stabilizer and optionally anionic surfactant. Sodium chlorate concentration may be suitable.

There are many types of incompatible colorants. Therefore, as for dyes, Acid Blue 185 (Cibacrolin Blue 8G) and Color Index Dye No.22,610 (Direct Blue
6), 42,090 (Hidacid Azure Blue), 52035 (Hidacid
Aque Blue) and 74,180 (Direct Blue 86) have been used to obtain stable compositions according to the present invention. These dyes include phthalocyanine, diazo, thiazine and triarylmethane dyes. Here, regarding the colorants not particularly touched, the stabilizing potentials can be easily confirmed by ordinary experiments as described in detail in Examples below.

Generally the composition pH is about 9 and above, preferably about
A value of 9.0 to about 10.5 is preferred. In the composition having this pH value, the dyes are stable, and the composition is stable and does not release chlorine dioxide.

In the present invention, in order for the composition to be initially stable and for stability to be maintained for an appropriate period of time, it is advisable to first mix the composition liquid containing the chlorite and the stabilizer and then mix the dye component.

The composition of the present invention may also contain a surfactant for improving the cleaning power and enhancing the cleaning effect. It has been discovered that many common anionic activators are stable in the compositions of this invention and that the compositions remain stable when the above effective amount of stabilizer is added to stabilize the colorant. Generally, anionic surfactants are water-soluble alkyls whose alkyl has from about 8 to about 22 carbons and which have a sulphate or sulphonate substituent which is neutralized with a base to give an alkali metal, such as sodium or potassium or ammonium anion. Alternatively, it is an alkylaryl compound. Such compounds are, for example, (1) straight or branched chain alkyl and alkylaryl sulphates and sulphonates having 10 to 18 carbons in the alkyl group, such as sodium lauryl sulphate and sodium dodecylbenzene sulphonate; Alpha-olefin aryl sulfonates having about 10 to 18 carbons, such as a mixture of long-chain sulfonates produced by sulfonation of C _14-16 alpha-olefins, mainly from sodium alkene sulfonate and sodium hydroxyalkane sulfonate. C _14-16 sodium olefin sulfonate; (3) Sulfated and sulfonated monoglycerides produced from coconut oil fatty acids;
(4) Ethoxylated sulfuric acid esters of 1-10 moles of ethylene oxide, for example sulfuric acid esters of polyoxyethylene (7 moles EO) sodium lauryl ether sulphate and 10 moles of ethylene oxide and ethoxylations having 8 to 12 carbons in the alkyl. Alkyl phenols such as polyoxyethylene (4 mol EO) nonyl phenyl ether ammonium sulfate; (5) base neutralized esters of fatty acids and isethionic acid such as sodium lauroyl isethionate; (6) fatty acid amides of methyl tauride; For example sodium methyl cocoyl taurate phosphate;
(7) Beta-acetoxy- or beta-acetamide-alkane sulfonates in which the alkane has 8 to 22 carbon atoms; and (8) acyl sarcosinate having 8 to 18 carbon atoms in the acyl moiety, such as sodium lauroyl sarcosinate. .

Preferred Anionix are alkyl and alkylaryl sulphates and alpha-olefin aryl sulphonates.

Anionic surfactant is 0 to about 20% by weight of the composition,
It may preferably be included in an amount of about 0.5 to about 10%, most preferably about 2 to about 8%.

Anionic surfactants have a composition stabilizing effect, and compositions containing chlorite, a colorant, and a stabilizer produce chlorine dioxide with and without anionic surfactant. Was found to be small. It is believed that this stabilization is due to the micellar interaction between the colorant and the surfactant anion.

It has been found that anionic overfluorinated hydrocarbon surfactants have the same stability-enhancing benefits as anionic surfactants in the compositions of the present invention, but at increasingly lower concentrations. A suitable anionic fluorosurfactant is EI du P
Zonyl series manufactured by ont de Nemours, especially Zonyl FS
Flourad series manufactured by A, FSJ and RP and 3M, especially F
Lourad 120 and 128. Further general description of fluorosurfactants is given in US Pat. No. 4,511,489 to Requejo et al., Which is incorporated herein by reference.

The perfluorinated hydrocarbon surfactant is present in the composition of the present invention in an amount up to about 1% by weight, preferably from about 0.005 to about 0.1%.
Included in the amount of. Mixtures of anionic surfactants and anionic superfluorinated hydrocarbon surfactants may also be included in the compositions of this invention.

Nonionic surfactants may also be included in the compositions of the present invention. The addition of stabilizers has the benefit of stabilizing this nonionic surfactant-containing solution. Such a composition contains a nonionic surfactant and a colorant, but exhibits very good stability as compared with a composition containing no stabilizer, but the stability of the composition of the present invention is Generally, it decreases due to the inclusion of agents. For this reason, nonionic surfactants may be included in amounts of up to about 3%, preferably up to 1% by weight of the composition, but should not be added. It is therefore possible to add auxiliaries which are able to solubilize small amounts of nonionic surfactants. The stability of compositions containing both anionic and nonionic surfactants is proportional to each concentration in the composition.

Cationic surfactants can also be added to the composition, but should not be mixed with compositions containing it, as they are incompatible with anionic surfactants. Similarly, a quaternary surfactant can be added. Cationic and quaternary surfactants are generally good in low concentrations to obtain special activity. For example, these surfactants are known fungicides.

Other adjuncts may optionally be added to the compositions of the present invention.
For example, fragrances, chelating agents, sequestrants, builders and the like may be included. Considering that there are substituents that are reactive with chlorite ion, it is necessary to carefully consider the fragrance when using it.

 The invention will be illustrated by the following examples.

General Principles In the examples, a composition sample was considered stable if it did not produce chlorine dioxide gas within one month of manufacture and had a dye half-life of about 2 weeks or more.

In some cases, chlorine dioxide gas can be easily detected by its special odor. If this perceptual test does not show the presence of ClO _2, then the following analytical methods: (1) spectrophotometry of the sample, ClO ₂ has a unique 356 mm peak absorbance among the oxychloro species; (2) in the presence of potassium iodide. Titration of an alkaline sample with sodium thiosulfate; and (3) expelling ClO ₂ gas from the sample with an inert gas and passing it through a potassium iodide solution.

The dye concentration of the sample that does not generate ClO ₂ gas can be measured by spectrophotometry of the absorbance peak peculiar to the dye.

Unless otherwise specified, the concentrations of samples are shown on the basis of active ingredients.

Example 1. Compositions AD were prepared and analyzed as described above. It was placed in a 180 ° F oven for about 1.5 hours to accelerate the test.

Compositions A and B without sodium borate produced ClO ₂ gas. Compositions C and D showed no ClO ₂ gas production detected.

Example 2. Compositions E-H were made and analyzed as described above and stored at room temperature. Compositions E and F produced ClO ₂ gas within 5 days.
Compositions G and H showed no ClO ₂ gas or pH drop after one month.

Example 3. (1) The dye concentration was reported as it was from the manufacturer, and the activity is shown in the table below.

The dyes contained in composition H-N 'are as follows: The stability test results at room temperature are as follows.

Example 4. Dye common name color index No. test No. activity,% Acid Blue No. 1 42045 1 100 Acid Blue No. 7 42080 2 100 Acid Blue No. 9 42090 3 67 Base Blue No. 1 4 100 These The dye was added in the composition reported below.

No ClO ₂ gas was produced in any composition from P1 to P4. Dye Base Blue No.1 in Composition P4
However, I was sorry.

Example 5. Composition P'-R was prepared: Composition P'was evolved ClO ₂ , but compositions Q and R were not evolved.

Example 6. None of the compositions S1 to S10 generated ClO ₂ gas.

Example 7. ClO ₂ gas was not generated.

Example 8. ClO ₂ gas was generated in the compositions HH, OO, and PP,
It did not occur in II-NN. Chlorite 1.6% and fragrance 0.1
% Stability requires a sodium borate concentration above about 0.05%.

Example 9. Compositions QQ and SS evolved ClO ₂ gas but not RR.

The above detailed description is not meant to limit the scope of the invention. All concentrations are on the basis of active ingredient.

Claims (27)

(57) [Claims] 1. An alkali metal chlorite of not more than 5% by weight, 0.01 to 3% by weight of a coloring agent which is usually chemically incompatible with the above chlorite in an aqueous medium, and an alkali metal carbonate.
A stabilizer selected from the group consisting of alkali metal borates and mixtures thereof, characterized in that it contains a composition stabilizing effective amount as evidenced by the substantial absence of chlorine dioxide in the composition. Aqueous alkaline cleaning composition. 2. The composition of claim 1 wherein the composition has a pH of 9 or greater. 3. The composition according to claim 1, wherein the colorant is a dye. 4. A composition according to claim 3, wherein the composition has a pH of 9 to 10.5. 5. A composition according to claim 4, wherein the dye is selected from the group consisting of phterocyanine, diazo, thiazine and triarylmethane dyes. 6. A composition according to claim 4, wherein the dye is a triarylmethane dye. 7. The dyes are acid blue dye 185 and color index dyes Nos. 22,610, 42,090, 52,035 and 74,
A composition according to claim 4 selected from the group consisting of 180. 8. The dye is a color index dye No. 42,090.
The composition according to claim 4, which is 9. The dye is a color index dye No. 52,035.
The composition according to claim 4, which is 10. The composition according to claim 1, wherein the chlorite is sodium chlorite. 11. The composition according to claim 5, wherein the chlorite is sodium chlorite. 12. The composition according to claim 7, wherein the chlorite is sodium chlorite. 13. Sodium chlorite 0.5 to 5% by weight,
0.01 to 3% by weight of a stabilizing dye, which is usually chemically incompatible with the above-mentioned sodium chlorite in an aqueous composition, and an alkali metal carbonate, an alkali metal borate and mixtures thereof. Aqueous alkaline cleaning compositions containing a stable stabilizer in a composition stabilizing effective amount as evidenced by the absence of chlorine dioxide in the composition and a dye half-life of at least about 2 weeks. Composition. 14. A composition having a pH of 9.0 to 10.5 and dyes of Acid Blue Dye 185 and Color Index Dye No.
14. The composition of claim 13 selected from the group consisting of 22,610, 42,090, 52,035, and 74,180. 15. The dye is a color index dye No. 42,09.
15. The composition of claim 14, which is 0. 16. The dye is a color index dye No. 52,03.
15. The composition of claim 14, which is 5. 17. The composition according to claim 14, further comprising 0.1 to 20% by weight of an anionic surfactant. 18. The composition of claim 14 further comprising about 0.005 to about 1% by weight anionic fluorosurfactant. 19. Sodium chlorite 0.5 to 5% by weight,
Acid blue dye 185 and color index dye No.
Stabilizing dyes selected from the group consisting of 22,610, 42,090, 52,035, and 74,180 and usually chemically incompatible with sodium chlorite in aqueous compositions having a pH of 9.0 to 10.5.
0.01 to 3% by weight, 0.15 to 3% by weight of a stabilizer selected from the group consisting of alkali metal carbonates, alkali metal borates and mixtures thereof, this amount being substantially free of chlorine dioxide in the composition. And an anionic surfactant which is a composition stabilizing effective amount as evidenced by a dye half-life of at least about 2 weeks, and which may be included in the composition in an amount up to 20% by weight. An aqueous alkaline cleaning composition, characterized in that it contains a surfactant selected from the group consisting of anionic fluorosurfactants, which may be included in an amount of up to% by weight. 20. The dye is a color index dye No. 42,09
20. The composition of claim 19, which is 0. 21. The dye is a color index dye No. 52,03
20. The composition of claim 19, which is 5. 22. The composition according to claim 19, which comprises sodium chlorite in an amount of 1 to 3% by weight. 23. The composition according to claim 22, wherein the dye is contained in an amount of 0.1 to 2% by weight. 24. The composition according to claim 23, which comprises 1 to 10% by weight of an anionic surfactant. 25. The composition of claim 24, which comprises 0.01 to 0.1% by weight fluorosurfactant. 26. The dye is a color index dye No. 42,09
25. The composition of claim 24, which is 0. 27. The dye is a color index dye No. 52,03
25. The composition of claim 24 which is 5.