JPH0742480B2 - Method and composition for producing a stabilized active halogen composition - Google Patents

Description

BACKGROUND OF THE INVENTION A common ingredient in detergent compositions in general is a bleaching compound that produces active halogen ions, such as Cl ⁺ or Br ⁺ , in water. Some sources of active halogen commonly used in detergent compositions include sodium hypochlorite, calcium hypochlorite, lithium hypochlorite, trisodium chlorinated phosphate, and organic compositions such as 1 , 3-Dichloro-5,5
-Dimethylhydantoin, chlorobromohydantoin,
Examples include trichloro-isocyanuric acid, dihaloisocyanuric acid and salts thereof, and others known in the art.

In addition to active halogen or bleaching ingredients, detergent compositions are generally alkaline, and one or more additional detergent ingredients such as alkaline agents, caustic builders, compounds that sequester and suspend hard water ions, such as inorganic phosphate. Either or both of a salt or an organic polymer polyelectrolyte, and a defoaming agent are included.

Incorporation of a source of active halogen ions into a highly alkaline system, with or without antifoam, generally results in degradation or loss of available halogen. Degradation of effective halogen is temperature-dependent, and occurs as follows, for example.

2NaOCl → 2NaCl + O ₂ This change not only gradually makes the compound progressively less effective in bleaching, but can also potentially cause product swelling. As oxygen gas evolves by decomposition, it diffuses through the system and is released into the atmosphere.

It is known that N-sodium-N-chloro-p-toluenesulfonamide (hereinafter referred to as chloramine-T) is storage stable when used as an effective chlorine source for bleaching and disinfection. However, the bleaching capacity of this compound is somewhat limited. Because its chlorine becomes available by hydrolysis of chloramine-T, and chloramine-T has a very low dissociation constant of only 4.9 × 10 ^-8 . In the detergent industry, chloramine-T is considered a source of active halogen. However, due to the low dissociation constant of chloramine-T, it is not a highly efficient source of chlorine. Practically chloramine-T shows little bleaching action.

Hypochlorite is known to be unstable in the presence of free water. Hunt et al U.S. Pat. No. 3,0
No. 54,753 discloses the incorporation of certain aromatic sulfonamides in powder detergents containing dry organic hypozinc salts to stabilize their hypochlorite. Hunt et al. More specifically discloses dry-drying a detergent component with hypochlorite and an aromatic sulfonamide. However, it has been found that dry blending of sulfonamide with a detergent containing dry hypochlorite does not provide any stabilization.

Therefore, there is a need for better storage stability of solid or slurry detergents containing efficient sources of active halogen. For use in machine washers, there is a need for a balanced formulation in which the halogen source is in a relatively readily available form. The composition should have a shelf life of several months, even at the high temperatures encountered in summer warehouses.

SUMMARY OF THE INVENTION In the present invention, an active and effective halogen source is that which is mixed with a (anhydrous) detergent builder that is sufficiently hydratable in the presence of free water, such as anhydrous inorganic phosphate or silicate. Is stabilized by reacting with active water and converting the mixture into a solid form. Stability is preferably further improved by adding one or more organic water-soluble sulfonamides to the halogen source in the presence of free water, preferably before incorporating the detergent builder. The sulfonamide improves the stability of the detergent and allows the detergent to be prepared as a stable slurry or solid. Furthermore, sulfonamides improve the stability of detergents at elevated temperatures.

The active halogens in these solid or slurry detergents are storage stable and are particularly suitable for use in high performance applications such as automatic product washer. The detergents are easily dissolved and / or dispensed by the automatic washer.

These and other features of the present invention will be fully understood in light of the following detailed description and drawings.

DETAILED DESCRIPTION Active halogen-generating compounds that can be stabilized according to the present invention are hypochlorite-generating or hypobromite-generating compounds suitable for use in detergent compositions. is there. These detergent compositions are water soluble and upon dissolution in water have active halogen ions (ie, Cl
⁺ Or Br ⁺ ) must be generated. Examples of compounds that generate some specific active halogens include chlorinated isocyanuric acid and its salts, such as trichlorocyanuric acid, dichlorocyanuric acid, sodium dichloroisocyanurate and potassium dichloroisocyanurate. Other suitable halogen sources are hydantoins, such as 1,3-dichloro-5,5-dimethylhydantoin, N-monochloro-C, C-dimethylhydantoin, methylene-bis (N-chloro-C, C-dimethyl). Hydantoin), 1,3-dichloro-5-methyl-5
-Isobutylhydantoin, 1,3-dichloro-5-methyl-5-ethylhydantoin, 1,3-dichloro-5-methyl-5-N-amylhydantoin, chlorobromohydantoin and the like. Other useful hypochlorite-releasing agents are water-soluble inorganic salts such as lithium hypochlorite, calcium hypochlorite, sodium hypochlorite and chlorinated trisodium phosphate.

The halogen source must also be an effective halogen source. An effective halogen source is one that provides an effective or efficient bleaching action when used. Chloramine-T and dichloramine-T do not provide any substantial bleaching action, so they are not effective halogen sources. Therefore, the term effective halogen source will not specifically include chloramine-T and dichloramine-T.

The water solubility of the active active halogen is prepared to have the desired level of active halogen, for example 0.5-2% active halogen. This aqueous solution is stabilized by adding sufficient hydratable (anhydrous or partially hydrated) detergent builder to form a solid detergent. Wettable detergent builders are known and generally include all detergent builders that react with water to form the hydrated form of the detergent builders. Examples of particularly suitable wettable detergent builders include inorganic anhydrous phosphates, anhydrous carbonates, caustic soda, anhydrous silicates, anhydrous sulfates, and anhydrous borates. More specifically,
Anhydrous trisodium phosphate, trisodium phosphate monohydrate, sodium tripolyphosphate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, anhydrous sodium carbonate and its partially hydrated form, borax, trisodium phosphate hemihydrate , Trisodium phosphate hexahydrate, trisodium phosphate octahydrate, anhydrous disodium phosphate and all its partially hydrated structures (ie dihydrate, heptahydrate, octahydrate) , Anhydrous tripotassium phosphate, tripotassium phosphate trihydrate, tripotassium phosphate heptahydrate, potassium tripolyphosphate and the like.

Stabilization is achieved by simply mixing the aqueous solution containing the active and effective halogen with the wettable detergent builder. Water is chemically removed by hydration of the detergent ingredients.
The hydration reaction is exothermic. Cooling (ie 38 ° C
Is desirable, but not required. The hydratable builder, when reacted with water, forms a solid detergent with active chlorine evenly dispersed in the detergent. The amount of hydratable builder must be sufficient to bind substantially all of the free water (ie, form a solid). This amount will of course vary depending on the particular hydratable ingredient added.

In order to obtain the best stability at relatively high temperatures, such as those encountered under storage conditions, and especially when kept at temperatures above about 52 ° C for a considerable time, the sulfonamide should be incorporated It is desirable to put in. Sulfonamides suitable for use in the present invention include aliphatic and aromatic sulfonamides. In particular, suitable sulfonamides include substituted and unsubstituted alkyl sulfonamides, substituted and unsubstituted aryl sulfonamides and substituted and unsubstituted alkaryl sulfonamides. Preferred sulfonamides include phenol sulfonamides and halogenated phenol sulfonamides. p-Toluenesulfonamide and N-sodium-N-chloro-p-toluenesulfonamide (chloramine-T) are particularly suitable for use in the present invention.

For use in the present invention, the sulfonamide must contain a sulfonamide group or radical having the formula:

Where x and y represent a member selected from the group consisting essentially of hydrogen, alkali or alkaline earth metal ions, halogens, C ₁ -C ₁₅ and alkyl groups, and in the above formula x or y At least one must be hydrogen or a metal ion. When x or y is hydrogen or a metal ion, it is the reactive site of the sulfonamide. Chloramine-T has a sulfonamide group of the formula:

Therefore, chloramine-T has only one reactive site on its sulfonamide. Di-chloramine-T has a sulfonamide group of the formula:

Therefore, di-chloramine-T is not suitable for use in the present invention because it has no reactive site on its sulfonamide group.

When a sulfonamide is included, the active halogen source and an aqueous solution of the sulfonamide are first compounded at a temperature in the range of room temperature (usually about 17 ° C) to about 87 ° C. If dry sulfonamide is added to the dry detergent, ie no free water is present, no stabilization is obtained. The stabilization reaction between sulfonamide and active halogen is 1: 1
That is, 1 mol of active available halogen ion is stabilized by each reactive sulfonamide moiety. Therefore, 2 moles of active available halogen are 1 mole of p
-Stabilized with toluene sulfonamide. Only 1 mol of active available halogen is stabilized by the addition of 1 mol of chloramine-T.

This solution is then stabilized by adding anhydrous detergent builder as disclosed above. When the sulfonamide is used in a detergent, the amount of hydratable builder may be limited so that a slurry is made rather than a solid. Due to the sulfonamide, the active halogen is effectively stabilized even in slurry form. As used in the present invention, a slurry is an aqueous suspension of solid particles of detergent builder.

Other suitable detergent ingredients can also be included in the detergents of the present invention. For example, alkaline builders, sequestering agents, polymers and fillers.

The detergent compositions of the present invention include known organic and inorganic builder salts such as tetrasodium and tetrapotassium pyrophosphate, pentasodium and pentapotassium tripolyphosphate, sodium or potassium carbonate, sodium or potassium silicate, hydrated or non-aqueous. It can include Japanese borax, sodium or potassium sesquicarbonate, and zeolites.

The present invention may also include surfactants including nonionic, anionic and zwitterionic surfactants.

The detergent compositions of the present invention may further include fillers such as alkali metal sulfates, hydrochlorides, carbonates, sesquicarbonates, and other inert ingredients known in the art.

The composition of the present invention preferably has a composition in the range below. That is, 1) 0.5 to 7% of at least one sulfonamide, 2) 0.4 to 2.5% of a compound containing hypochlorite or other active halogen, 3) 25 to 65% of water, and 4) 5. -40% anhydrous phosphate, 5) 0-25% anhydrous silicate, 6) 0-10% polyelectrolyte, 7) 0-35% sodium carbonate, 8) 0-5% desorption Foam, 9) 0-5% surfactant.

The present invention may be more fully understood by reference to the following examples.

Example 1 A detergent was formulated to have the following ingredients.

This detergent was formulated by first mixing sulfonamide, NaOCl and water to form an aqueous solution. The other remaining ingredients were then added with mixing. As a result, a solid detergent was formed. This is an example of the present invention using p-toluenesulfonamide as the sulfonamide. The detergent was tested for stability and bleaching efficiency. The results are shown in FIGS. 1 and 2.

Example 2 A detergent was formulated to have the following ingredients.

This detergent was first prepared with sulfonamide (chloramine-T), Na
It was formulated by mixing OCl and water to make an aqueous solution. The other remaining ingredients were then mixed into the aqueous solution.
This mixture solidified to form a solid detergent. The stability of this detergent is shown in FIG.

Example 3 A detergent was formulated from the following ingredients.

The NaOCl and water were mixed and then the remaining ingredients were mixed into the aqueous solution. This mixture solidified to form a solid detergent. This is an example of an embodiment of the invention where no sulfonamide is included. The composition was tested for stability at 52 ° C and 27 ° C. The results are also shown in FIGS. 1 and 3.

Example 4 A detergent was formulated from the following ingredients.

This detergent was formulated by mixing chloramine-T and water. No effective chlorine source was added. When the remaining ingredients were mixed into this aqueous solution, the mixture solidified.
This example is provided to show the stability and bleaching efficiency of chloramine-T. The results are shown in FIGS. 1 and 2.

Example 5 A detergent was prepared from the following ingredients.

This detergent was formulated by mixing chloramine-T and water to form an aqueous solution. The remaining ingredients were then added to the solution to make a mixture which solidified to form a solid detergent. The stability of this detergent is shown in FIG. This example demonstrates the stability of a 3.1% chloramine-T detergent and is presented only for comparison with Example 7 which contains approximately the same amount of chloramine-T.

Example 6 A detergent was formulated with the following ingredients.

This detergent was formulated by mixing water, NaOCl and sulfonamide to make an aqueous solution. The remaining ingredients were then mixed into the solution and the mixture solidified to form a solid detergent. This detergent has a relatively low ratio of sulfonamide to active available chlorine. The stability of this detergent is shown in FIG. This example illustrates the effect of the sulfonamide to chlorine ratio on overall detergent stability.

Example 7 A detergent was formulated from the following ingredients.

This detergent was formulated by mixing water and NaOCl to form an aqueous solution. All remaining ingredients except chloramine-T were mixed into this aqueous solution. The mixture solidified to form a solid mass. The solid mass was scraped into flakes and then mixed dry with chloramine-T. This example partially follows the teaching of US Pat. No. 3,054,753. First
As can be seen, this example demonstrates that the addition of chloramine-T in the dry state does not improve the stability of chlorine.

Figures 1 and 2 show the data obtained by testing these various detergents for stability and bleaching efficiency. FIG. 1 shows the amount of chlorine present over time. Available chlorine was measured by titration. The data depicted in Figure 1 demonstrate that Examples 1 and 2, which are practices of the preferred embodiment of the present invention, exhibit excellent stability at elevated temperatures. Example 3 illustrates a less preferred embodiment of the present invention in which an aqueous solution of chlorine source is mixed with a hydratable detergent ingredient and a builder to form a self-solidifying mass. Although this method provides considerable stability at moderate temperatures (see Figure 3), its stability is extremely temperature dependent. At the high temperatures tested, 52 ° C, the stability is significantly reduced.

The most stable detergent was made according to Example 4, where the only chlorine source was chloramine-T.
This detergent has a high level of titratable chlorine. But,
As shown by the results depicted in Figure 2, the chlorine source is present by titration but is not an effective chlorine source.

Example 6 is provided to illustrate the stoichiometric relationship of sulfonamides to the active chlorine source. The molar ratio of sulfonamide to active chlorine should preferably be at least 0.5 when the sulfonamide has two reaction sites and 1 when the sulfonamide has only one reaction site. In Example 6, the sulfonamide was p-toluenesulfonamide having two reactive sites. According to the invention, the molar ratio should have been 0.5. In Example 6, the molar ratio was 0.33. A decrease in stability was shown in comparison with Examples 1 and 2.
Examples 5 and 7 are used to compare the invention with the prior art. Example 7 demonstrates that chloramine-T does not improve the stability of the chlorine source when added to dry detergents. In Example 7, the detergent is chloramine-T.
Was formed into a solid without blending. The solid was then flaked and mixed with Chloramine-T as a dry blend. The titratable amount of chlorine is considerable. But,
Compared to Example 5, the titratable chlorine obtained was from chloramine-T and the sodium hypochlorite was not stabilized. Example 5 is, of course, a detergent formulated in the same manner as Example 4, except that only 3.0% of chloramine-T is used, which is the amount of chloramine-T used in the formulation of Example 7. Is almost the same as.
Therefore, when mixing Chloramine-T with a dry detergent,
Almost no stabilization is observed at all.

The data shown in FIG. 2 was obtained as follows. That is, a piece of white cloth of polyester / cotton 50/50 composition is totally dipped for 3 minutes in a solution of 4 containing 24 g of soluble tea. The cloth was rinsed in deionized water and then dried with a heat gun. The same operation was repeated at 20 hour intervals to make a double contaminated cloth. (Artificially contaminated fabric was chosen as the substrate to contrast with contaminated porcelain because of the reliability and reproducibility of the test method. This method demonstrates the differences between individual chlorine sources. The fabric was then cut into 2 inch by 2 inch squares.

The detergents prepared in Examples 1, 3 and 4 were tested as shown in FIG. In test 1, these detergents were used to prepare 0.3% standard stock solutions with 8 grains of hard water.
Heat to 60 ° F. The tea-dyed cloth is then added to the solution 1
Soak for a minute, remove, rinse with 8 grains of water, and let dry. A control test was also conducted at 160 ° F with only 8 grains of tap water. In test 2, the same procedure was repeated with an exposure time of 2 minutes.

The samples were compared using a photoelectric reflectometer by the zero compression method and using magnesium carbonate as an absolute reflectance of 97%. Using this Suppressed 0 method, a clean white polyester / cotton cloth can be collected on a galvanometer 10
Place it on 0 and the soiled cloth on 0. The dried, treated sample was then measured for reflectance. Next, the obtained reading is the following formula Was used to measure the absolute reflectance R _x . During the above formula
Re is the reflectance of the white cloth, Rd is the reflectance of the contaminated cloth, and
G _x is the galvanometer reading. The results are shown graphically in FIG.

There is essentially no difference in reflectance between tap water and the product containing chloramine-T (Example 4). Therefore, no effective bleaching is seen. However, a mixture of sulfonamide and hypochlorite is a product containing only sodium hypochlorite.
It produces reflection values of more than 85%. Accordingly, the present invention provides a product having a bleaching capacity almost comparable to a product formulation containing all its chlorine as sodium hypochlorite and having excellent stability. The obvious difference between these two mixtures is that in the above-mentioned invention in comparison with the reactive but less stable compounds containing all available chlorine in the inorganic hypochlorite. It is stable and effective in stable chlorine.

Example 8 To evaluate the stabilizing effect of a solid detergent (as in Example 3) made without the addition of sulfonamide, a comparative detergent solution was made from the following ingredients.

Water 19.9 Trisodium phosphate 8.84 Potassium hydroxide (46%) 15.00 Sodium polyacrylate 0.2 Soda ash 35.06 NaOCl (13.5%) 10.00 Sodium tripolyphosphate 11.00 100.00 This formed a suspension. This suspension was compared to a solid detergent composition made according to Example 3 without the addition of sulfonamide. The result of the comparison is shown in FIG. This comparison clearly shows that the solidification of the hypochlorite solution by the addition of the hydratable detergent component has the effect of stabilizing its chlorine content when stored at low temperatures.

Other examples illustrate other aspects of the invention.

Example 9 A detergent in slurry form was prepared from the following ingredients.

Water 40.5 Sodium hypochlorite (13.5% solution) 10.3 p-Toluenesulfonamide 1.7 Sodium silicate (anhydrous) 17.7 Sodium hydroxide 13.0 Sodium carbonate (anhydrous) 4.0 Sodium tripolyphosphate (anhydrous) 12.0 Sodium polyacrylate 0.8 100.0 This The detergent was formulated by mixing water, NaOCl and p-toluenesulfonamide. This formed an aqueous solution. Add the remaining ingredients listed above to this solution,
A viscous, fluid slurry was made. This slurry showed excellent chlorine stability.

Example 10 A slurry detergent was formulated from the following ingredients.

Water 44.25 Sodium hypochlorite (13.0% solution) 5.2 Chloramine-T 2.75 Sodium silicate (anhydrous) 17.7 Sodium hydroxide 13.0 Sodium carbonate (anhydrous) 4.0 Sodium tripolyphosphate (anhydrous) 12.0 Sodium polyacrylate 0.8 This detergent is water , NaOCl and chloramine-T were blended. It formed an aqueous solution. The remaining ingredients listed above were added to this solution to make a viscous, fluid slurry. This slurry showed excellent chlorine stability.

Example 11 A solid detergent was formulated from the following ingredients.

Water 35.4 Trisodium phosphate (anhydrous) 6.0 Sodium hydroxide 18.0 Sodium polyacrylate 1.0 Chloramine-T 3.0 Sodium hypochlorite (13.5% solution) 6.6 Sodium carbonate (anhydrous) 18.0 Sodium tripolyphosphate (anhydrous) 12.0 This detergent is Prepared by mixing water, chloramine-T and NaOCl to form an aqueous solution. The remaining ingredients were mixed into this solution. The solution solidified to form a solid detergent. The solid detergent showed excellent chlorine stability.

Example 12 Water 24.32 Trisodium phosphate (anhydrous) 4.00 Sodium hydroxide 9.68 Sodium tripolyphosphate 11.00 Sodium carbonate (anhydrous) 21.00 Sodium metasilicate (anhydrous) 11.00 Sodium polyacrylate 1.00 Sodium hypochlorite (13.5% solution) 18.00 This detergent was formulated by mixing water and NaOCl to make an aqueous solution. The remaining ingredients were mixed into the solution. The solution coagulated to form a solid detergent, which showed excellent stability at moderate temperatures despite the absence of sulfonamide.

Example 13 Water 29.1 Trisodium phosphate (anhydrous) 8.84 Sodium tripolyphosphate (anhydrous) 11.00 Sodium carbonate (anhydrous) 25.06 Sodium metasilicate (anhydrous) 15.00 Sodium polyacrylate 1.00 Sodium hypochlorite (13.5% solution) 10.00 The detergent was formulated by mixing water and NaOCl to make an aqueous solution. The remaining ingredients were mixed into the solution. The solution solidified to form a solid detergent, which showed excellent chlorine stability.

These examples demonstrate that the present invention provides stable and effective halogen containing detergents. Further, these examples demonstrate that the prior art fails to solve the chlorine stability problem.

[Brief description of drawings]

FIG. 1 is a graph comparing the time stability of various chlorine-containing detergents at 52 ° C (125 ° F). FIG. 2 is a graph comparing the relative bleaching efficiencies of various chlorine containing detergents. FIG. 3 is a graph comparing the time stability of solid and slurry detergents.

Claims (9)

[Claims] 1. One or more sulfonamides selected from the group consisting of free water, water-soluble alkyl sulfonamides and water-soluble aryl sulfonamides, and water-soluble hypochlorites, halogenated hydantoins, halogenated phosphors. An effective amount of the active effective halogen source selected from the group consisting of phthalates, chlorinated isocyanuric acids and salts thereof to form a solution of sulfonamide and a halogen source, the solution being effective to form a solid detergent. Of at least one hydratable detergent builder of claim 1, wherein said sulfonamide is defined by the formula: Wherein x and y are selected from the group consisting of hydrogen, halogens, alkyl groups and alkali or alkaline earth metal ions, and at least x or y is hydrogen or a metal ion, stabilized And method for producing an active halogen composition. 2. The method according to claim 1, wherein an aqueous solution of an active and effective halogen source is prepared, the aqueous solution is mixed with the sulfonamide, and the hydratable detergent builder is added to the solution. 3. The method according to claim 2, wherein the effective halogen source is a chlorine source. 4. The process according to claim 1, wherein the sulfonamide is selected from the group consisting of p-toluenesulfonamide and N-sodium-N-chloro-p-toluenesulfonamide. 5. A sulfonamide selected from the group consisting of water-soluble alkyl sulfonamides, water-soluble aryl sulfonamides and water-soluble alkyl aryl sulfonamides,
Water-soluble hypochlorites, halogenated hydantoins,
An active halogen source selected from the group consisting of halogenated phosphates, chlorinated isocyanuric acids and salts thereof,
And free water to form a solution of the sulfonamide and the active halogen source, and further by adding at least an effective amount of at least one wettable detergent builder to form a solid, wherein The sulfonamide comprises a sulfonamide group defined by the formula: Where x and y are selected from the group consisting of hydrogen, alkyl groups, halogens and alkali or alkaline earth metals, and x and y are hydrogen or metal ions, a stabilized activity. Halogen composition. 6. A composition according to claim 5 wherein the sulfonamide is selected from the group consisting of p-toluenesulfonamide and N-sodium-N-chloro-p-toluenesulfonamide. 7. A molar ratio of sulfonamide to halogen source is at least about 0.5 when both x and y are hydrogen or an alkali or alkaline earth metal ion, and only x is hydrogen or The composition of claim 5 which is at least about 1 when it is a metal ion. 8. A sulfonamide selected from the group consisting of about 0.5-7% p-toluenesulfonamide and N-sodium-N-chloro-p-toluenesulfonamide, 0.
4-2.5% hypochlorite, 25-65% water, 5-40% anhydrous phosphate, 0-25% anhydrous silicate, 0-10% polyelectrolyte, 0-35 % Sodium carbonate, and 0-5%
A composition according to claim 7 which comprises the defoamer of 9. The composition of claim 8 further comprising up to 40% metal hydroxide.