CA1231612A - Stabilized active halogen-containing detergent compositions and methods - Google Patents
Stabilized active halogen-containing detergent compositions and methodsInfo
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- CA1231612A CA1231612A CA000474405A CA474405A CA1231612A CA 1231612 A CA1231612 A CA 1231612A CA 000474405 A CA000474405 A CA 000474405A CA 474405 A CA474405 A CA 474405A CA 1231612 A CA1231612 A CA 1231612A
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- sulfonamide
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3951—Bleaching agents combined with specific additives
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
STABILIZED ACTIVE HALOGEN-CONTAINING
DETERGENT COMPOSITIONS AND METHODS
Abstract of the Disclosure A detergent composition containing a stabilized active halogen source is disclosed. An active halogen source, such as a hypochlorite, in aqueous solution, is stabilized by combining it with known anhydrous or partially anhydrous builders, as well as fillers, defoamers, polyelectrolytes, and hydroxides to form a solid detergent composition.
Preferably, the aqueous solution of the active halogen source is first combined with at least one sulfonamide. It is found that inclusion of the sulfonamide further improves stability, particularly at higher temperatures and permits the active halogen source to be stabilized as a slurry. The destaining activity of the halogen remains effective even after a prolonged storage period.
DETERGENT COMPOSITIONS AND METHODS
Abstract of the Disclosure A detergent composition containing a stabilized active halogen source is disclosed. An active halogen source, such as a hypochlorite, in aqueous solution, is stabilized by combining it with known anhydrous or partially anhydrous builders, as well as fillers, defoamers, polyelectrolytes, and hydroxides to form a solid detergent composition.
Preferably, the aqueous solution of the active halogen source is first combined with at least one sulfonamide. It is found that inclusion of the sulfonamide further improves stability, particularly at higher temperatures and permits the active halogen source to be stabilized as a slurry. The destaining activity of the halogen remains effective even after a prolonged storage period.
Description
Stabilized ACTIVE HALOGEN-CONTAINING DETERGENT
COMPOSITIONS AND METHODS
Background of the Invention A common component of detergent compositions is a bleaching compound which yields active halogen ions e.g., Of or By , in water. Some of the active halogen sources commonly used in detergent compost-lions are sodium hypochlorite, calcium hypochlorite, lithium hypochlorite, chlorinated trisodium phosphate, and organic compositions such as 1,3-dichloro-5,5-dimethyhydantoin, chlorobromohydantoin, trichloro-isocyanuric acid, and dihaloisocyanuric acids and their salts others are known in the art.
In addition to the active halogen or bleach-in component, detergent compositions are generally alkaline and include one or more additional detergent components, such as alkaline agents, caustic alkaline builders, compounds for sequestering and suspending hard water ions either as inorganic phosphates or polyorganic polyelectrolytes, or both, and defamers, as well as others.
''4 ye I
Incorporation of a source of active halogen ion into a highly alkaline system with or without a defamer generally causes a degradation or loss of the available halogen. Degradation of available halogen is temperature-dependent and tends to occur, for example, as Nikolai Nikolai + 2 This change not only gradually renders the 1 compound increasingly ineffective with respect to ; bleaching, but also could potentially cause product expansion. As the oxygen gas is generated by the decomposition, it will diffuse through the system to release into the atmosphere.
The use of N-sodium-N-chloro-para Tulane sulfonamide, i.e., referred to hereinafter as Chloramine-T, as the source of available chlorine for bleaching and sanitizing is known to be shelf stable.
The bleaching ability of this compound, however, is somewhat limited because the chlorine is made avail-able by the hydrolysis of Chloramine-T, which has a very low dissociation constant of only 4.9 x 10 8. In the detergent industry, Chloramine-T is considered a source of active halogen However, due to Sheller-mine-T's low dissociation constant, it is not an efficient source of chlorine. In effect, it provides little bleaching activity.
Hypochlorites are known to be unstable in the presence of free water. Hunt et at US. Patent ~X3~
3,05~,753 discloses that incorporation of certain aromatic sulfonamides in a powder detergent, whisk has a dry organic hypochlorite, stabilizes the hype-chlorite. Hunt et at more specifically discloses the dry blending of the detergent components together with the hypochlorite and aromatic sulfonamide. However, it has been found that the dry blending of a cellophane-aside with a dry hypochlorite containing detergent does not provide any stabilization.
Thus, there exists a need for a more storage stable solid or slurries detergent which includes an efficient source of active halogen. For use in mechanical ware-washing machines, a balanced formula-lion is required where the halogen source is present in a reactive, readily available form. The compost-lion should have a shelf life of several months, even at the high temperatures encountered in a warehouse in summer.
Summary of the Invention In the present invention, an active and efficient halogen source is stabilized by mixing it in the presence of free water, with sufficient hydra table (an hydrous) detergent builders such as an hydrous inorganic phosphates or silicates, to react with the active water and to convert the mixture to a solid form. Stability is preferably further improved by adding one or more organic water-soluble sulfonamides to the halogen source and in the presence of free ~23~
water, prior to incorporating the detergent builders.
The sulfonamide improves the stability of the deter-gent and permits the detergent to be formulated as a stable slurry or solid. Further, the sulfonamide improves the stability of the detergent at higher temperatures.
The active halogen in these solid or slur-fled detergents is storage stable and is particularly suitable for use in high performance applications such ; as automatic ware-washing machines. The detergents are easily dissolved and/or dispensed by an automatic washing machine.
These and other features of the present invention will be appreciated in light of the follow-; 15 in detailed description and drawings, in which:
Brief Description of the Drawings Fig. 1 is a graph comparing the time stabilities of various chlorine-containing detergents at 52~C (125F);
Fig 2 is a graph comparing the relative bleaching efficiency of various chlorine-containing compositions; and Fig. 3 is a graph comparing the time stabilities of a solid and a slurries detergent.
25 Detailed Description The active halogen generating compounds which can be stabilized by the present invention are hypochlorite-generating compounds or hypobromite-generating compounds suitable for use in detergent compositions. These compositions must be water-soluble and generate an active halogen ion (i.e., Of or By ) upon dissolution in water. Examples of some specific active halogen generating compounds include chlorinated isocyanuric acids and their salts such as trichlorocyanuric acid, dichlorocyanuric acid, sodium dichloroisocyanurate and potassium dichloroisocya-curate. Additional suitable halogen sources are the hydantoins such as 1,3-dichloro5,5-dimethylhydantoin, N-monochloro-C,C-dimethylhydantoin, ethylene-bis(N-chloro-C,C-dimethylhydantoin), 1,3-dichloro-5-methyl-5-isobutylhydantoin, 1,3-dichloro-5-methyl-5-ethylhydantoin, 1,3-dichloro-5-methyl-5-N-amyl-hydantoin, sheller broom hydantoin, and the like Other useful hypochlorite liberating agents are water-soluble inorganic salts such as lithium hype-chlorite, calcium hypochlorite, sodium hypochlorite and chlorinated trisodium phosphate.
The halogen source must also be an efficient halogen source. An efficient halogen source is one which provides effective or efficient bleaching activity in use. Chloramine-T and di-chloramine T are not efficient halogen sources because they do not provide any substantial bleaching activity. Accord-tingly, hereinafter the term efficient halogen source specifically excludes chloramine-T and di-chloramine-T.
I
An aqueous solution of active efficient halogen is prepared with a desired level ox available halogen, or example, 0.5-2% available halogen, This aqueous solution is stabilized by adding sufficient hydra table (an hydrous or partially hydrated) detergent builders to form a solid detergent. Hydra table detergent builders are well known and generally include any detergent builder which reacts with water to form a hydrated form of the detergent builder.-; Particularly suitable hydra table detergent builders include inorganic an hydrous phosphates, an hydrous carbonates, caustic soda, an hydrous silicates, ashy-dross sulfates, and an hydrous borate. More specific gaily, these include trisodium phosphate an hydrous, trisodium phosphate MindWrite, sodium Tripoli-phosphate, twitter sodium pyrophosphate, twitter potassium pyrophosphate, sodium carbonate an hydrous and partial-lye hydrated forms, borax, trisodium phosphate whom-drape, trisodium phosphate hexahydrate, trisodium phosphate octahydrate, disodium phosphate an hydrous and all partially hydrated structures, i.e., Dow-drape, heptahydrate, octahydrate, tripotassium pros-photo an hydrous, tripotassium phosphate trihydrate, tripotassium phosphate heptahydrate, and potassium tripolyphosphate.
Stabilization is achieved simply by mixing the hydra table detergent builders with the aqueous active efficient halogen-containing solution. Water I
is chemically removed by hydration of the detergent components. The hydration reaction is exothermic.
Cooling is preferred (i.e., to 38C), but is not essential. The hydra table builders, upon reacting with the water, form a solid detergent in which the active chlorine is uniformly dispersed throughout the detergent. The amount of hydra table builders should be sufficient to bind substantially all of the free water (i.e., form a solid). This amount will, of ; course, vary depending on the particular hydra table components added.
To achieve the best stability at higher temperatures, such as those encountered under storage conditions, and more specifically, at temperatures exceeding about 52C for a substantial period, it is preferred to incorporate a sulfonamide in the compost-lion. Suitable sulfonamides for use in the present invention include alkyd and aromatic water soluble sulfonamides. More particularly, the suitable sulfa-nomads include substituted and unsubstituted alkylsulfonamides, substituted and unsubstituted aureole sulfonamides and substituted and unsubstituted alkaryl sulfonamides. Preferred sulfonamides include phenol sulfonamide and halogenated phenol sulfonamide.
Tulane sulfonamide and N-sodium-N-chloro-p-toluene sulfonamide (Chloramine-T) are particularly suited for use in the present invention.
~3~6,12 For use in the present invention, the sulfonamide must includes a sulfonamide group or radical having the following formula:
If /x S - N
wherein x and y represent a member selected from the group consisting essentially of hydrogen, an alkali or alkaline earth metal ion, halogen, Cluck and alkyd radical and wherein at least one of x or y must be hydrogen or a metal ion. When x or y is hydrogen or a metal ion, it is a reactive site on the sulfonamide.
Chloramine-T has a sulfonamide group having the following formula:
No S No If \ Of Accordingly, chloramine-T has only one reactive site on the sulfonamide. Di-chloramine-T has a sulfonamide group having the following formula:
I
g o Of S - N
If \ Of O
Accordingly, di-chloramine-T has no reactive sites on the sulfonamide group and is unsuitable for use in the present invention.
If a sulfonamide is to be included, the aqueous solution of active halogen source and cellophane-mode are first combined at temperatures ranging from room temperature (generally about 17C) to about 87C.
If dry sulfonamide were added to a dry detergent, i.e., when no free water is present, no stabilization is provided. The stabilization reaction between the sulfonamide and active halogen is a one to one no-action, i.e., one mole of active efficient halogen ion is stabilized by each reactive sulfonamide site.
Therefore, two moles of active efficient halogen are stabilized by one mole of Tulane sulfonamide. Only one mole of active efficient halogen is stabilized by the addition of one mole of Chloramine-T.
This solution is then stabilized by adding an hydrous detergent builders, as disclosed above.
When a sulfonamide is employed in the detergent, the amount of hydra table builders may be limited so that a slurry is formed as opposed to a solid. With the sulfonamide, the active halogen is effectively stabile iced even in a slurry fox. For use in the present invention, a slurry represents an aqueous suspension of solid particles of detergent builders.
Other suitable detergent components can also be included in the detergent of the present invention, such as alkaline builders, sequestrants, polymers, surfactants and fillers.
The detergent composition of the present invention may contain well known organic or inorganic builder salts, for example, tetrasodium and twitter-potassium pyrophosphate, pentasodium and pent-potassium tripolyphosphate, sodium or potassium carbonate, sodium or potassium silicates, hydrated or an hydrous borax, sodium or potassium sesquicarbonate and zealots.
The present invention may also include surfactants including non-ionic, anionic and twitter-ionic surfactants.
The detergent composition of the present invention can further include fillers such as alkali metal sulfates, chlorides, carbonates, Suzuki-carbonates and other inert ingredients well known to the art.
Preferred approximate ranges of components include:
1) 0.5 Jo 7% at least one sulfonamide, ~q~3~
COMPOSITIONS AND METHODS
Background of the Invention A common component of detergent compositions is a bleaching compound which yields active halogen ions e.g., Of or By , in water. Some of the active halogen sources commonly used in detergent compost-lions are sodium hypochlorite, calcium hypochlorite, lithium hypochlorite, chlorinated trisodium phosphate, and organic compositions such as 1,3-dichloro-5,5-dimethyhydantoin, chlorobromohydantoin, trichloro-isocyanuric acid, and dihaloisocyanuric acids and their salts others are known in the art.
In addition to the active halogen or bleach-in component, detergent compositions are generally alkaline and include one or more additional detergent components, such as alkaline agents, caustic alkaline builders, compounds for sequestering and suspending hard water ions either as inorganic phosphates or polyorganic polyelectrolytes, or both, and defamers, as well as others.
''4 ye I
Incorporation of a source of active halogen ion into a highly alkaline system with or without a defamer generally causes a degradation or loss of the available halogen. Degradation of available halogen is temperature-dependent and tends to occur, for example, as Nikolai Nikolai + 2 This change not only gradually renders the 1 compound increasingly ineffective with respect to ; bleaching, but also could potentially cause product expansion. As the oxygen gas is generated by the decomposition, it will diffuse through the system to release into the atmosphere.
The use of N-sodium-N-chloro-para Tulane sulfonamide, i.e., referred to hereinafter as Chloramine-T, as the source of available chlorine for bleaching and sanitizing is known to be shelf stable.
The bleaching ability of this compound, however, is somewhat limited because the chlorine is made avail-able by the hydrolysis of Chloramine-T, which has a very low dissociation constant of only 4.9 x 10 8. In the detergent industry, Chloramine-T is considered a source of active halogen However, due to Sheller-mine-T's low dissociation constant, it is not an efficient source of chlorine. In effect, it provides little bleaching activity.
Hypochlorites are known to be unstable in the presence of free water. Hunt et at US. Patent ~X3~
3,05~,753 discloses that incorporation of certain aromatic sulfonamides in a powder detergent, whisk has a dry organic hypochlorite, stabilizes the hype-chlorite. Hunt et at more specifically discloses the dry blending of the detergent components together with the hypochlorite and aromatic sulfonamide. However, it has been found that the dry blending of a cellophane-aside with a dry hypochlorite containing detergent does not provide any stabilization.
Thus, there exists a need for a more storage stable solid or slurries detergent which includes an efficient source of active halogen. For use in mechanical ware-washing machines, a balanced formula-lion is required where the halogen source is present in a reactive, readily available form. The compost-lion should have a shelf life of several months, even at the high temperatures encountered in a warehouse in summer.
Summary of the Invention In the present invention, an active and efficient halogen source is stabilized by mixing it in the presence of free water, with sufficient hydra table (an hydrous) detergent builders such as an hydrous inorganic phosphates or silicates, to react with the active water and to convert the mixture to a solid form. Stability is preferably further improved by adding one or more organic water-soluble sulfonamides to the halogen source and in the presence of free ~23~
water, prior to incorporating the detergent builders.
The sulfonamide improves the stability of the deter-gent and permits the detergent to be formulated as a stable slurry or solid. Further, the sulfonamide improves the stability of the detergent at higher temperatures.
The active halogen in these solid or slur-fled detergents is storage stable and is particularly suitable for use in high performance applications such ; as automatic ware-washing machines. The detergents are easily dissolved and/or dispensed by an automatic washing machine.
These and other features of the present invention will be appreciated in light of the follow-; 15 in detailed description and drawings, in which:
Brief Description of the Drawings Fig. 1 is a graph comparing the time stabilities of various chlorine-containing detergents at 52~C (125F);
Fig 2 is a graph comparing the relative bleaching efficiency of various chlorine-containing compositions; and Fig. 3 is a graph comparing the time stabilities of a solid and a slurries detergent.
25 Detailed Description The active halogen generating compounds which can be stabilized by the present invention are hypochlorite-generating compounds or hypobromite-generating compounds suitable for use in detergent compositions. These compositions must be water-soluble and generate an active halogen ion (i.e., Of or By ) upon dissolution in water. Examples of some specific active halogen generating compounds include chlorinated isocyanuric acids and their salts such as trichlorocyanuric acid, dichlorocyanuric acid, sodium dichloroisocyanurate and potassium dichloroisocya-curate. Additional suitable halogen sources are the hydantoins such as 1,3-dichloro5,5-dimethylhydantoin, N-monochloro-C,C-dimethylhydantoin, ethylene-bis(N-chloro-C,C-dimethylhydantoin), 1,3-dichloro-5-methyl-5-isobutylhydantoin, 1,3-dichloro-5-methyl-5-ethylhydantoin, 1,3-dichloro-5-methyl-5-N-amyl-hydantoin, sheller broom hydantoin, and the like Other useful hypochlorite liberating agents are water-soluble inorganic salts such as lithium hype-chlorite, calcium hypochlorite, sodium hypochlorite and chlorinated trisodium phosphate.
The halogen source must also be an efficient halogen source. An efficient halogen source is one which provides effective or efficient bleaching activity in use. Chloramine-T and di-chloramine T are not efficient halogen sources because they do not provide any substantial bleaching activity. Accord-tingly, hereinafter the term efficient halogen source specifically excludes chloramine-T and di-chloramine-T.
I
An aqueous solution of active efficient halogen is prepared with a desired level ox available halogen, or example, 0.5-2% available halogen, This aqueous solution is stabilized by adding sufficient hydra table (an hydrous or partially hydrated) detergent builders to form a solid detergent. Hydra table detergent builders are well known and generally include any detergent builder which reacts with water to form a hydrated form of the detergent builder.-; Particularly suitable hydra table detergent builders include inorganic an hydrous phosphates, an hydrous carbonates, caustic soda, an hydrous silicates, ashy-dross sulfates, and an hydrous borate. More specific gaily, these include trisodium phosphate an hydrous, trisodium phosphate MindWrite, sodium Tripoli-phosphate, twitter sodium pyrophosphate, twitter potassium pyrophosphate, sodium carbonate an hydrous and partial-lye hydrated forms, borax, trisodium phosphate whom-drape, trisodium phosphate hexahydrate, trisodium phosphate octahydrate, disodium phosphate an hydrous and all partially hydrated structures, i.e., Dow-drape, heptahydrate, octahydrate, tripotassium pros-photo an hydrous, tripotassium phosphate trihydrate, tripotassium phosphate heptahydrate, and potassium tripolyphosphate.
Stabilization is achieved simply by mixing the hydra table detergent builders with the aqueous active efficient halogen-containing solution. Water I
is chemically removed by hydration of the detergent components. The hydration reaction is exothermic.
Cooling is preferred (i.e., to 38C), but is not essential. The hydra table builders, upon reacting with the water, form a solid detergent in which the active chlorine is uniformly dispersed throughout the detergent. The amount of hydra table builders should be sufficient to bind substantially all of the free water (i.e., form a solid). This amount will, of ; course, vary depending on the particular hydra table components added.
To achieve the best stability at higher temperatures, such as those encountered under storage conditions, and more specifically, at temperatures exceeding about 52C for a substantial period, it is preferred to incorporate a sulfonamide in the compost-lion. Suitable sulfonamides for use in the present invention include alkyd and aromatic water soluble sulfonamides. More particularly, the suitable sulfa-nomads include substituted and unsubstituted alkylsulfonamides, substituted and unsubstituted aureole sulfonamides and substituted and unsubstituted alkaryl sulfonamides. Preferred sulfonamides include phenol sulfonamide and halogenated phenol sulfonamide.
Tulane sulfonamide and N-sodium-N-chloro-p-toluene sulfonamide (Chloramine-T) are particularly suited for use in the present invention.
~3~6,12 For use in the present invention, the sulfonamide must includes a sulfonamide group or radical having the following formula:
If /x S - N
wherein x and y represent a member selected from the group consisting essentially of hydrogen, an alkali or alkaline earth metal ion, halogen, Cluck and alkyd radical and wherein at least one of x or y must be hydrogen or a metal ion. When x or y is hydrogen or a metal ion, it is a reactive site on the sulfonamide.
Chloramine-T has a sulfonamide group having the following formula:
No S No If \ Of Accordingly, chloramine-T has only one reactive site on the sulfonamide. Di-chloramine-T has a sulfonamide group having the following formula:
I
g o Of S - N
If \ Of O
Accordingly, di-chloramine-T has no reactive sites on the sulfonamide group and is unsuitable for use in the present invention.
If a sulfonamide is to be included, the aqueous solution of active halogen source and cellophane-mode are first combined at temperatures ranging from room temperature (generally about 17C) to about 87C.
If dry sulfonamide were added to a dry detergent, i.e., when no free water is present, no stabilization is provided. The stabilization reaction between the sulfonamide and active halogen is a one to one no-action, i.e., one mole of active efficient halogen ion is stabilized by each reactive sulfonamide site.
Therefore, two moles of active efficient halogen are stabilized by one mole of Tulane sulfonamide. Only one mole of active efficient halogen is stabilized by the addition of one mole of Chloramine-T.
This solution is then stabilized by adding an hydrous detergent builders, as disclosed above.
When a sulfonamide is employed in the detergent, the amount of hydra table builders may be limited so that a slurry is formed as opposed to a solid. With the sulfonamide, the active halogen is effectively stabile iced even in a slurry fox. For use in the present invention, a slurry represents an aqueous suspension of solid particles of detergent builders.
Other suitable detergent components can also be included in the detergent of the present invention, such as alkaline builders, sequestrants, polymers, surfactants and fillers.
The detergent composition of the present invention may contain well known organic or inorganic builder salts, for example, tetrasodium and twitter-potassium pyrophosphate, pentasodium and pent-potassium tripolyphosphate, sodium or potassium carbonate, sodium or potassium silicates, hydrated or an hydrous borax, sodium or potassium sesquicarbonate and zealots.
The present invention may also include surfactants including non-ionic, anionic and twitter-ionic surfactants.
The detergent composition of the present invention can further include fillers such as alkali metal sulfates, chlorides, carbonates, Suzuki-carbonates and other inert ingredients well known to the art.
Preferred approximate ranges of components include:
1) 0.5 Jo 7% at least one sulfonamide, ~q~3~
2) 0.4 to 2.5% hypochlorite or other active halogen-containing compound,
3) 25 to 65% water,
4) 5 to 40~ an hydrous phosphate, I 0 to 25~ an hydrous silicate, 6) 0 to 10% polyelectrolyte, I 0 to 35~ sodium carbonate, and 8) 0 to 5% defamer, 9) 0 to 5% surfactant.
10 ; The present invention can be further apple-elated by reference to the following examples.
Example 1 A detergent was formulated having the following components:
Water 33.4%
Nikolai 11.8% (13.5% solution) Tulane sulfonamide 1.9%
Trisodium phosphate 8.84%
(an hydrous) Sodium tripolyphosphate 11.0%
(an hydrous) Soda ash 21.06%
Sodium metasilicate 11.0%
(an hydrous) Sodium polyacrylate 1.0~ (20~ solution) 100.00 The detergent was formulated by mixing the sulfonamide, Nikolai and water to form an aqueous Lo solution. The remaining components were then added with mixing. A solid detergent was formed. This is a working example of the present invention using p-Tulane sulfonamide as the sulfonamide. This was tested for stability and bleaching efficiency. The results are shown in Figs. 1 and 2.
Example 2 A detergent was formulated having the following components:
10 ; Water 37.3~
Nikolai 6.6% (13.5% solution) Chloramine-T 3,0%
No Tripoli phosphate 8.84%
(an hydrous) Try sodium phosphate 11.0%
(an hydrous) Soda ash 21.06%
No Polyacrylate 1.2% (20% solution) Sodium Metasilicate 11.0%
(an hydrous) 100.00 The detergent was formulated by mixing the sulfonamide (Chloramine-T) Nikolai and water to form an aqueous solution. The remaining components were then mixed into the aqueous solution. This mixture set to form a solid detergent. The stability of this deter-gent is shown in Fly. 1.
glue Example 3 A detergent was formulated from the follow-in components:
Water 34.7%
Try sodium polyphosphate 8.84 (an hydrous) Sodium tripolyphosphate 11.0%
(an hydrous) Nikolai 12.4% (13.5% solution) 10 `; Soda ash 21.06 Sodium metasilicate 11.0%
Polyacrylate 1.0% (20% solution) 100 . 00 The Nikolai and water were combined and the remaining components were then mixed into this aqueous solution. This mixture set forming a solid detergent.
This is a working example of the embodiment of the present invention wherein the sulfonamide is not included. This composition was tested for stability at 52C and at 27C and the results are again shown in Figs. 1 and 3.
Example 4 A detergent composition was formulated from the following components:
Water 41.0%
Try sodium polyphosphate 8.84 (an hydrous) Sodium tripolyphosphate 11.0%
.
-14~
Soda ash 21.06%
Sodium metasilicate 11.0%
(an hydrous) No Polyacrylate 1.0% (20% solution) Chloramine-T 6.1%
100.00 The detergent was formulated by combining the chloramine-T and water. No efficient chlorine source was added. The remaining components were mixed ; into this aqueous solution and the mixture set. This example is presented to show the stability and bleach-in efficiency of chloramine-T. The results are shown in Figs. 1 and 2.
Example 5 A detergent was formulated with the follow-in detergent components:
Water 44.0~
Try sodium polyphosphate 8.84%
(an hydrous) Sodium tripolyphosphate 11.0%
(an hydrous) Soda ash 21.06%
Sodium metasilicate 11.0%
an hydrous Polyacrylate 1.0% (20% solution) Chloramine-T 3.1%
100.00 ~Z3~
The detergent was formulated by combining the chloramine-T and water to form an aqueous soul-lion, The remaining components were then added to this solution to form a mixture which set and formed a solid detergent. The stability of this detergent is shown in Fig. 1. This example demonstrates the stability of a 3.1~ Chloramine-T detergent and is shown only for comparison with Example 7 which also includes approximately the same amount of Sheller-.
mine-T.
Example 6 A detergent was formulated with the follow-in components:
Water 34.1%
Meekly 11.8% (13.5% solution) Try sodium polyphosphate 8.84%
(an hydrous) Sodium tripolyphosphate 11.0%
(an hydrous) Soda ash 21.06%
Tulane sulfonamide 1.2~
Sodium metasilicate 11.0%
(an hydrous) - Polyacrylate 1.0% ~20% solution) 100.00 The detergent was formed by combining the water Nikolai and sulfonamide to form an aqueous soul-lion. The remaining components were then mixed into I
this solution to form a mixture which set to form a solid detergent. This detergent has a lower ratio of sulfonamide to active efficient chlorine. The stabile fly of this detergent is shown in Fig. 1. This example demonstrates the effect of the sulfonamide to chlorine ratio on the overall stability of the deter-gent.
Example 7 A detergent was formulated from the follow-in components:
Water 37.5%
Nikolai 6.53% (13.5% solution) Try sodium polyphosphate 8.84%
(an hydrous) Sodium tripolyphosphate 11.0%
(an hydrous) Soda ash 21.06%
Sodium metasilicate 11.0%
tundras) 20 Polyacrylate 1.0% (20% solution) Chloramine-T 3.07 100.00 The detergent was formed by combining the water and Nikolai to form an aqueous solution. All of the remaining components except the Chloramine-T were mixed into this aqueous solution. The mixture set forming a solid mass. The solid mass was flaked and mixed in a dry state with chloramine-l. This example ~23~Z
follows in part the teaching of US. Patent No.
sly. As seen in Fig. 1, this example demon striates that adding Chloramine-T in a dry state does not improve the stability of the chlorine.
Figs. 1 and 2 show data obtained testing various of these detergents with respect to stability and bleaching efficiency. Fig. 1 shows the amount of chlorine present versus time. The available chlorine was measured by titration. The data depicted in Fig.
10 `; 1 demonstrates that Examples 1 and 2, which are a practice of the preferred embodiment of the present invention, exhibit superior stability at elevated temperatures. Example 3 is a demonstration of a less preferred embodiment of the present invention wherein an aqueous solution of a chlorine source is combined with hydra table detergent components and builders to form a self-solidifying mass. Although this method provides substantial stability at moderate tempera-lures (see Fig. 3), the stability is extremely tempt erasure dependent. At elevated temperatures, such as those tested, i.e., 52C, stability is substantially reduced.
The most stable detergent was that made according to Example 4 wherein the only chlorine source was chloramine-T. This detergent has high levels of titratable chlorine. However, as will be shown with the results depicted in Fig. 2, the I
chlorine source, although identifiable by titration, is not an efficient chlorine source.
Example 6 is presented to demonstrate the stoichiometric relationship of sulfonamide to active chlorine source. The molar ratio of sulfonamide to active chlorine source should preferably be at least 0.5 if the sulfonamide has two reactive sites and 1 if the sulfonamide has only one reactive site. In Example 6, the sulfonamide was paratoluene sulfonamide 10 ` having two reactive sites. According to the present invention, the molar ratio should have been 0.5. In Example 6, the molar ratio was 0.33. reduction in stability was demonstrated compared to Examples 1 and 2. Examples 5 and 7 are used to compare the present invention to the prior art. Example 7 demonstrates that chloramine-T, when added to a dry detergent, does not improve the stability of the chlorine source. In Example 7, the detergent was formulated without Chloramine-T to form a solid. The solid was then flaked and combined with chloramine-T as a dry mix-lure. There is a substantial amount of titratable chlorine. However, a comparison with Example 5 demonstrates that the available titratable chlorine is from the chloramine-T and the sodium hypochlorite has not been stabilized. Example 5, of course, is a deterrent formulated in the same manner as Example 4 with the exception that the chloramine-T was only 3.0%
which is approximately the same amount of chloramine-T
I
used in the formulation of Example 7. accordingly, when mixing the chloramine T with a dry detergent, little, if any, stabilization is observed.
The data shown in Fig. 2 was obtained as follows: A white cloth, composition 50/50 polyester cotton, was totally immersed in a four liter solution containing 24 grams of soluble tea for three minutes.
The cloth was rinsed in de-ionized water and dried with a heat gun. The same procedure was repeated with 20 hours elapsed between the repetition to create a double stained cloth. (The artificially stained cloth was chosen as the substrate as opposed to stained ceramic because of the reliability and reproduce-ability of the test method. This method allowed for better distinction between the individual chlorine sources.) The cloths were then cut into two by two inch squares.
As shown in Fig. 2, the detergents prepared in Examples 1, 3 and 4 were tested. In test 1, these detergents were used to prepare 0~3~ stock solutions with 8 grains hard water and heated to 160F. The tea-stained cloths were then added to the solution for one minute, removed, rinsed with 8 grain water, and air dried. A blank was also run which was tap water only 8 grain at 160F. In test 2, this same procedure was followed again with an exposure time of two minutes.
~23~ Eye I
The samples were compared using a photo-voltaic reflectometer using the suppressed O method and magnesium carbonate as 97~ of absolute reflect lance. Using this suppressed O method, the unstained white polyester/cotton cloth was set at 100 on the galvanometers and the stained cloth was set at 0. The dried, treated samples were then measured for reflect lance. Thy reading obtained was then used to deter-mine absolute reflectance Rx with the equation Rx = rod + go (roared) where Rye is reflectance of white cloth, Rod is reflectance of stained cloth, and Go is galvanometers reading. The results are graph icily displayed in Fig. 2.
There is essentially no difference in reflectance between tap water and the product contain-in chloramine-T (Example 4). Therefore, no efficient bleaching is apparent. However, the sample with the blended sulfonamide and hypochlorite produces a reflective value which is in excess of 85% of the product containing all sodium hypochlorite. Thus, this invention provides a product with bleaching ability nearly equivalent to a product formulation having all its chlorine as sodium hypochlorite and with superior stability. The apparent distinction between these two mixes is the stabilized yet reactive available chlorine in the aforementioned invention compared with the reactive yet less stable compound ~2;~6~-~
containing all the available chlorine in an inorganic hypochlorite.
Example 8 To evaluate the stabilization effect of forming a solid detergent formed without the addition of a sulfonamide (as in Example 3), a comparative detergent solution was formed from the following components:
H20 19.9 10 ; Trisodium phosphate 8.84 Potassium Hydroxide (46%) 15.00 Sodium polyacrylate 0.2 Soda Ash 35.06 Nikolai%) 10.00 Sodium Tripolyphosphate 11.00 100 . 00 This formed a liquid suspension. The suspension was compared to the detergent composition formed according to Example 3 which was a solid formed without any sulfonamide. The results of the compare iron are shown in Fig. 3. This comparison clearly indicates that the solidification of the hypochlorite solution by the addition of hydra table detergent components acts to stabilize the chlorine content when stored at lower temperatures.
The remaining examples demonstrate alternate embodiments of the present invention.
~3~G~
Example 9 A slurries detergent was formulated from the following components:
Water 40.5 Sodium Hypochlorite (13.5 Solution) 10.3 Tulane Sulfonamide 1.7 Sodium Silicate (anhydrous)17.7 Sodium Hydroxide 13.0 Sodium Carbonate (an hydrous) 4.0 Sodium Tripolyphosphate (an hydrous) 12.0 ' Sodium Polyacrylate I
100 . O
The detergent was formulated by combining the water, Nikolai and Tulane sulfonamide. This formed an aqueous solution. The remaining components listed above were added to this solution to form a viscous plowable slurry. The slurry exhibited excel-lent chlorine stability.
Example 10 A slurries detergent was formulated from the following components:
Water 44.55 Sodium Hypochlorite (13.0 Sown) 5.2 Chloramine-T 2.75 Sodium Silicate (an hydrous) 17.7 Sodium Hydroxide 13.0 Sodium Carbonate (an hydrous) 4.0 Sodium Tripolyphosphate (an hydrous) 12.0 -23~ 2 Sodium Polyacrylate 0.8 The detergent was formulated by combining the water, Nikolai and chloramine-T. This formed an aqueous solution. The remaining components listed above were added to this solution to form a viscous plowable slurry. The slurry exhibited excellent chlorine stability.
Example 11 A solid detergent was formed from the following components:
Water 35.~
Trisodium Phosphate (an hydrous) 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 (an hydrous) 12.0 The detergent was formulated by combining the water chloramine-T and Nikolai to form an aqueous solution. The remaining components were mixed into the solution. The solution set to form a solid detergent which exhibited excellent chlorine stabile fly.
Example 12 Water 24.32 Trisodium Phosphate (an hydrous) 4.00 Sodium Hydroxide 9.68 ~23~
Sodium Tripolyphosphate 11.00 Sodium Carbonate (an hydrous) 21.00 Sodium Metasilicate (an hydrous) 11.00 Sodium Polyacrylate 1.00 Sodium Hypochlorite (13.5% Solution) 18.00 The detergent was formulated by combining the water and Nikolai to form an aqueous solution. The remaining components were mixed into the solution.
The solution set to form a solid detergent which ; exhibited excellent stability at moderate temperatures ` even in the absence of a sulfonamide.
Example 13 Water 29.1 Trisodium Phosphate (an hydrous) 8.84 Sodium Tripo]yphosphate (an hydrous) 11.00 Sodium Carbonate (anhydrous)25.06 Sodium Metasilicate (an hydrous) 15.00 Sodium Polyacrylate 1.00 Sodium Hypochlorite (13.5 solution) 10.00 The detergent was formulated by combining the water and Nikolai to form an aqueous solution. The remaining components were mixed into the solution.
The solution set to form a solid detergent which exhibited excellent chlorine stability.
These examples demonstrate that the present invention provides a stable, efficient halogen-containing detergent. Further, these examples I
demonstrate that the prior art fails to solve the problem of chlorine stability.
Accordingly, in light of the preceding disclosure and advantages of the present invention, we claim:
,.
10 ; The present invention can be further apple-elated by reference to the following examples.
Example 1 A detergent was formulated having the following components:
Water 33.4%
Nikolai 11.8% (13.5% solution) Tulane sulfonamide 1.9%
Trisodium phosphate 8.84%
(an hydrous) Sodium tripolyphosphate 11.0%
(an hydrous) Soda ash 21.06%
Sodium metasilicate 11.0%
(an hydrous) Sodium polyacrylate 1.0~ (20~ solution) 100.00 The detergent was formulated by mixing the sulfonamide, Nikolai and water to form an aqueous Lo solution. The remaining components were then added with mixing. A solid detergent was formed. This is a working example of the present invention using p-Tulane sulfonamide as the sulfonamide. This was tested for stability and bleaching efficiency. The results are shown in Figs. 1 and 2.
Example 2 A detergent was formulated having the following components:
10 ; Water 37.3~
Nikolai 6.6% (13.5% solution) Chloramine-T 3,0%
No Tripoli phosphate 8.84%
(an hydrous) Try sodium phosphate 11.0%
(an hydrous) Soda ash 21.06%
No Polyacrylate 1.2% (20% solution) Sodium Metasilicate 11.0%
(an hydrous) 100.00 The detergent was formulated by mixing the sulfonamide (Chloramine-T) Nikolai and water to form an aqueous solution. The remaining components were then mixed into the aqueous solution. This mixture set to form a solid detergent. The stability of this deter-gent is shown in Fly. 1.
glue Example 3 A detergent was formulated from the follow-in components:
Water 34.7%
Try sodium polyphosphate 8.84 (an hydrous) Sodium tripolyphosphate 11.0%
(an hydrous) Nikolai 12.4% (13.5% solution) 10 `; Soda ash 21.06 Sodium metasilicate 11.0%
Polyacrylate 1.0% (20% solution) 100 . 00 The Nikolai and water were combined and the remaining components were then mixed into this aqueous solution. This mixture set forming a solid detergent.
This is a working example of the embodiment of the present invention wherein the sulfonamide is not included. This composition was tested for stability at 52C and at 27C and the results are again shown in Figs. 1 and 3.
Example 4 A detergent composition was formulated from the following components:
Water 41.0%
Try sodium polyphosphate 8.84 (an hydrous) Sodium tripolyphosphate 11.0%
.
-14~
Soda ash 21.06%
Sodium metasilicate 11.0%
(an hydrous) No Polyacrylate 1.0% (20% solution) Chloramine-T 6.1%
100.00 The detergent was formulated by combining the chloramine-T and water. No efficient chlorine source was added. The remaining components were mixed ; into this aqueous solution and the mixture set. This example is presented to show the stability and bleach-in efficiency of chloramine-T. The results are shown in Figs. 1 and 2.
Example 5 A detergent was formulated with the follow-in detergent components:
Water 44.0~
Try sodium polyphosphate 8.84%
(an hydrous) Sodium tripolyphosphate 11.0%
(an hydrous) Soda ash 21.06%
Sodium metasilicate 11.0%
an hydrous Polyacrylate 1.0% (20% solution) Chloramine-T 3.1%
100.00 ~Z3~
The detergent was formulated by combining the chloramine-T and water to form an aqueous soul-lion, The remaining components were then added to this solution to form a mixture which set and formed a solid detergent. The stability of this detergent is shown in Fig. 1. This example demonstrates the stability of a 3.1~ Chloramine-T detergent and is shown only for comparison with Example 7 which also includes approximately the same amount of Sheller-.
mine-T.
Example 6 A detergent was formulated with the follow-in components:
Water 34.1%
Meekly 11.8% (13.5% solution) Try sodium polyphosphate 8.84%
(an hydrous) Sodium tripolyphosphate 11.0%
(an hydrous) Soda ash 21.06%
Tulane sulfonamide 1.2~
Sodium metasilicate 11.0%
(an hydrous) - Polyacrylate 1.0% ~20% solution) 100.00 The detergent was formed by combining the water Nikolai and sulfonamide to form an aqueous soul-lion. The remaining components were then mixed into I
this solution to form a mixture which set to form a solid detergent. This detergent has a lower ratio of sulfonamide to active efficient chlorine. The stabile fly of this detergent is shown in Fig. 1. This example demonstrates the effect of the sulfonamide to chlorine ratio on the overall stability of the deter-gent.
Example 7 A detergent was formulated from the follow-in components:
Water 37.5%
Nikolai 6.53% (13.5% solution) Try sodium polyphosphate 8.84%
(an hydrous) Sodium tripolyphosphate 11.0%
(an hydrous) Soda ash 21.06%
Sodium metasilicate 11.0%
tundras) 20 Polyacrylate 1.0% (20% solution) Chloramine-T 3.07 100.00 The detergent was formed by combining the water and Nikolai to form an aqueous solution. All of the remaining components except the Chloramine-T were mixed into this aqueous solution. The mixture set forming a solid mass. The solid mass was flaked and mixed in a dry state with chloramine-l. This example ~23~Z
follows in part the teaching of US. Patent No.
sly. As seen in Fig. 1, this example demon striates that adding Chloramine-T in a dry state does not improve the stability of the chlorine.
Figs. 1 and 2 show data obtained testing various of these detergents with respect to stability and bleaching efficiency. Fig. 1 shows the amount of chlorine present versus time. The available chlorine was measured by titration. The data depicted in Fig.
10 `; 1 demonstrates that Examples 1 and 2, which are a practice of the preferred embodiment of the present invention, exhibit superior stability at elevated temperatures. Example 3 is a demonstration of a less preferred embodiment of the present invention wherein an aqueous solution of a chlorine source is combined with hydra table detergent components and builders to form a self-solidifying mass. Although this method provides substantial stability at moderate tempera-lures (see Fig. 3), the stability is extremely tempt erasure dependent. At elevated temperatures, such as those tested, i.e., 52C, stability is substantially reduced.
The most stable detergent was that made according to Example 4 wherein the only chlorine source was chloramine-T. This detergent has high levels of titratable chlorine. However, as will be shown with the results depicted in Fig. 2, the I
chlorine source, although identifiable by titration, is not an efficient chlorine source.
Example 6 is presented to demonstrate the stoichiometric relationship of sulfonamide to active chlorine source. The molar ratio of sulfonamide to active chlorine source should preferably be at least 0.5 if the sulfonamide has two reactive sites and 1 if the sulfonamide has only one reactive site. In Example 6, the sulfonamide was paratoluene sulfonamide 10 ` having two reactive sites. According to the present invention, the molar ratio should have been 0.5. In Example 6, the molar ratio was 0.33. reduction in stability was demonstrated compared to Examples 1 and 2. Examples 5 and 7 are used to compare the present invention to the prior art. Example 7 demonstrates that chloramine-T, when added to a dry detergent, does not improve the stability of the chlorine source. In Example 7, the detergent was formulated without Chloramine-T to form a solid. The solid was then flaked and combined with chloramine-T as a dry mix-lure. There is a substantial amount of titratable chlorine. However, a comparison with Example 5 demonstrates that the available titratable chlorine is from the chloramine-T and the sodium hypochlorite has not been stabilized. Example 5, of course, is a deterrent formulated in the same manner as Example 4 with the exception that the chloramine-T was only 3.0%
which is approximately the same amount of chloramine-T
I
used in the formulation of Example 7. accordingly, when mixing the chloramine T with a dry detergent, little, if any, stabilization is observed.
The data shown in Fig. 2 was obtained as follows: A white cloth, composition 50/50 polyester cotton, was totally immersed in a four liter solution containing 24 grams of soluble tea for three minutes.
The cloth was rinsed in de-ionized water and dried with a heat gun. The same procedure was repeated with 20 hours elapsed between the repetition to create a double stained cloth. (The artificially stained cloth was chosen as the substrate as opposed to stained ceramic because of the reliability and reproduce-ability of the test method. This method allowed for better distinction between the individual chlorine sources.) The cloths were then cut into two by two inch squares.
As shown in Fig. 2, the detergents prepared in Examples 1, 3 and 4 were tested. In test 1, these detergents were used to prepare 0~3~ stock solutions with 8 grains hard water and heated to 160F. The tea-stained cloths were then added to the solution for one minute, removed, rinsed with 8 grain water, and air dried. A blank was also run which was tap water only 8 grain at 160F. In test 2, this same procedure was followed again with an exposure time of two minutes.
~23~ Eye I
The samples were compared using a photo-voltaic reflectometer using the suppressed O method and magnesium carbonate as 97~ of absolute reflect lance. Using this suppressed O method, the unstained white polyester/cotton cloth was set at 100 on the galvanometers and the stained cloth was set at 0. The dried, treated samples were then measured for reflect lance. Thy reading obtained was then used to deter-mine absolute reflectance Rx with the equation Rx = rod + go (roared) where Rye is reflectance of white cloth, Rod is reflectance of stained cloth, and Go is galvanometers reading. The results are graph icily displayed in Fig. 2.
There is essentially no difference in reflectance between tap water and the product contain-in chloramine-T (Example 4). Therefore, no efficient bleaching is apparent. However, the sample with the blended sulfonamide and hypochlorite produces a reflective value which is in excess of 85% of the product containing all sodium hypochlorite. Thus, this invention provides a product with bleaching ability nearly equivalent to a product formulation having all its chlorine as sodium hypochlorite and with superior stability. The apparent distinction between these two mixes is the stabilized yet reactive available chlorine in the aforementioned invention compared with the reactive yet less stable compound ~2;~6~-~
containing all the available chlorine in an inorganic hypochlorite.
Example 8 To evaluate the stabilization effect of forming a solid detergent formed without the addition of a sulfonamide (as in Example 3), a comparative detergent solution was formed from the following components:
H20 19.9 10 ; Trisodium phosphate 8.84 Potassium Hydroxide (46%) 15.00 Sodium polyacrylate 0.2 Soda Ash 35.06 Nikolai%) 10.00 Sodium Tripolyphosphate 11.00 100 . 00 This formed a liquid suspension. The suspension was compared to the detergent composition formed according to Example 3 which was a solid formed without any sulfonamide. The results of the compare iron are shown in Fig. 3. This comparison clearly indicates that the solidification of the hypochlorite solution by the addition of hydra table detergent components acts to stabilize the chlorine content when stored at lower temperatures.
The remaining examples demonstrate alternate embodiments of the present invention.
~3~G~
Example 9 A slurries detergent was formulated from the following components:
Water 40.5 Sodium Hypochlorite (13.5 Solution) 10.3 Tulane Sulfonamide 1.7 Sodium Silicate (anhydrous)17.7 Sodium Hydroxide 13.0 Sodium Carbonate (an hydrous) 4.0 Sodium Tripolyphosphate (an hydrous) 12.0 ' Sodium Polyacrylate I
100 . O
The detergent was formulated by combining the water, Nikolai and Tulane sulfonamide. This formed an aqueous solution. The remaining components listed above were added to this solution to form a viscous plowable slurry. The slurry exhibited excel-lent chlorine stability.
Example 10 A slurries detergent was formulated from the following components:
Water 44.55 Sodium Hypochlorite (13.0 Sown) 5.2 Chloramine-T 2.75 Sodium Silicate (an hydrous) 17.7 Sodium Hydroxide 13.0 Sodium Carbonate (an hydrous) 4.0 Sodium Tripolyphosphate (an hydrous) 12.0 -23~ 2 Sodium Polyacrylate 0.8 The detergent was formulated by combining the water, Nikolai and chloramine-T. This formed an aqueous solution. The remaining components listed above were added to this solution to form a viscous plowable slurry. The slurry exhibited excellent chlorine stability.
Example 11 A solid detergent was formed from the following components:
Water 35.~
Trisodium Phosphate (an hydrous) 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 (an hydrous) 12.0 The detergent was formulated by combining the water chloramine-T and Nikolai to form an aqueous solution. The remaining components were mixed into the solution. The solution set to form a solid detergent which exhibited excellent chlorine stabile fly.
Example 12 Water 24.32 Trisodium Phosphate (an hydrous) 4.00 Sodium Hydroxide 9.68 ~23~
Sodium Tripolyphosphate 11.00 Sodium Carbonate (an hydrous) 21.00 Sodium Metasilicate (an hydrous) 11.00 Sodium Polyacrylate 1.00 Sodium Hypochlorite (13.5% Solution) 18.00 The detergent was formulated by combining the water and Nikolai to form an aqueous solution. The remaining components were mixed into the solution.
The solution set to form a solid detergent which ; exhibited excellent stability at moderate temperatures ` even in the absence of a sulfonamide.
Example 13 Water 29.1 Trisodium Phosphate (an hydrous) 8.84 Sodium Tripo]yphosphate (an hydrous) 11.00 Sodium Carbonate (anhydrous)25.06 Sodium Metasilicate (an hydrous) 15.00 Sodium Polyacrylate 1.00 Sodium Hypochlorite (13.5 solution) 10.00 The detergent was formulated by combining the water and Nikolai to form an aqueous solution. The remaining components were mixed into the solution.
The solution set to form a solid detergent which exhibited excellent chlorine stability.
These examples demonstrate that the present invention provides a stable, efficient halogen-containing detergent. Further, these examples I
demonstrate that the prior art fails to solve the problem of chlorine stability.
Accordingly, in light of the preceding disclosure and advantages of the present invention, we claim:
,.
Claims (14)
PRIVILEGE OR PROPERTY IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of stabilizing an active efficient halogen source comprising mixing free water, one or more sulfonamides, an active efficient halogen source and one or more hydratable detergent builders in an amount effective to form a solid detergent, wherein said sulfonamide includes a sulfonamide radical defined by the following formula:
wherein x and y are selected from the group consisting of H, halogen, alkyl, and an alkali or alkaline earth metal and at least x or y is H or a metal ion.
wherein x and y are selected from the group consisting of H, halogen, alkyl, and an alkali or alkaline earth metal and at least x or y is H or a metal ion.
2. A method of stabilizing an active efficient halogen source selected from the group consisting of water soluble hypochlorites, halogenated hydantoins, halogenated phosphates, chlorinated isocyanuric acids and salts thereof, comprising mixing free water, one or more sulfonamides selected from the group consisting of water soluble alkyl sulfonamides and water soluble aryl sulfonamides and an active efficient halogen source to form a solution of sulfonamide and halogen source and combining said solution with one or more hydratable detergent builders in an amount effective to form solid detergent, wherein said sulfonamide includes a sulfonamide radical defined by the following formula:
wherein x and y are selected from the group consisting of H, halogen, alkyl, and an alkali or alkaline earth metal ion and at least x or y is H or a metal ion.
wherein x and y are selected from the group consisting of H, halogen, alkyl, and an alkali or alkaline earth metal ion and at least x or y is H or a metal ion.
3. The method of stabilizing an active efficient halogen source claimed in claim 2, further comprising:
forming an aqueous solution of said active efficient halogen source;
mixing said aqueous solution with said sulfonamide; and adding said hydratable detergent builders to said solution.
forming an aqueous solution of said active efficient halogen source;
mixing said aqueous solution with said sulfonamide; and adding said hydratable detergent builders to said solution.
4. The method of claim 3 wherein said efficient halogen source is a source of chlorine.
5. The method of claim 4 wherein said source of chlorine is selected from the group consisting of water-soluble hypochlorites, chlorinated cyanuric acids, chlorinated isocyanurates, chlorinated hydantoins and chlorinated phosphates.
6. The method of claim 2 wherein said aryl sulfonamide is selected from the group consisting of p-toluene sulfonamide and N-sodium-N-chloro-p-toluene sulfonamide.
7. A stabilized active halogen composition formed by mixing a sulfonamide, an active halogen source, free water, and at least one hydratable detergent builder in at least an amount effective to form a solid, wherein said sulfonamide includes a sulfonamide radical defined by the following formula:
wherein x and y are selected from the group consisting of H, alkyl, halogen, and an alkali or alkaline earth metal ion and wherein x or y is H or a metal ion.
wherein x and y are selected from the group consisting of H, alkyl, halogen, and an alkali or alkaline earth metal ion and wherein x or y is H or a metal ion.
8. A stabilized active halogen composition formed by mixing a sulfonamide selected from the group consisting of water soluble alkyl sulfonamides, water soluble aryl sulfonamides and water soluble alkylaryl sulfonamides, an active halogen source selected from the group consisting of water-soluble hypochlorites, halogenated hydantoins, halogenated phosphates, chlorinated isocyanuric acids and salts thereof, free water to form a solution of said sulfonamide and said halogen, and further adding at least one hydratable detergent builder in at least an amount effective to form a solid, wherein said sulfonamide includes a sulfonamide radical defined by the following formula:
wherein x and y are selected from the group consisting of H, alkyl, halogen, and an alkali or alkaline earth metal ion and at least x or y is H or a metal ion.
wherein x and y are selected from the group consisting of H, alkyl, halogen, and an alkali or alkaline earth metal ion and at least x or y is H or a metal ion.
9. The composition of claim 7 wherein said active halogen source is selected from the group consisting of water-soluble hypochlorites, halogenated cyanuric acids, halogenated isocyanurates, halogenated hydantoins and halogenated phosphates.
10. The composition of claim 7 wherein said sulfonamide is selected from the group consisting of substituted and unsubstituted alkyl sulfonamides, substituted and unsubstituted aryl sulfonamides, and substituted and unsubstituted alkylaryl sulfonamides.
11. The composition of claim 8 or 10 wherein said alkylaryl sulfonamide is selected from the group consisting of p-toluene sulfonamide and N-sodium-N-chloro-p-toluene sulfonamide.
12. The composition of claim 8 wherein the molar ratio of sulfonamide to halogen source. is at least about 0.5 when both x and y are either H or an alkali or alkaline earth metal ion and at least about 1 when only x is H or a metal ion.
13. The composition of claim 12 comprising approx-imately 0.5 to 7% sulfonamide selected from the group consisting of p-toluene sulfonamide and N-sodium-N-chloro-p-toluene sulfonamide, 0.4 to 2.5% hypochlorite, 25 to 65%
water, 5 to 40% anhydrous phosphate, 0 to 25% anhydrous silicate, 0 to 10% polyelectrolyte, 0 to 35% sodium carbonate, and 0 to 5% defoamer.
water, 5 to 40% anhydrous phosphate, 0 to 25% anhydrous silicate, 0 to 10% polyelectrolyte, 0 to 35% sodium carbonate, and 0 to 5% defoamer.
14. The composition of claim 13 further comprising up to 40% metal hydroxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62219984A | 1984-06-19 | 1984-06-19 | |
| US622,199 | 1984-06-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1231612A true CA1231612A (en) | 1988-01-19 |
Family
ID=24493276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000474405A Expired CA1231612A (en) | 1984-06-19 | 1985-02-15 | Stabilized active halogen-containing detergent compositions and methods |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0165676A3 (en) |
| JP (1) | JPH0742480B2 (en) |
| CA (1) | CA1231612A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5066416A (en) * | 1987-08-31 | 1991-11-19 | Olin Corporation | Process for producing moldable detergents having a stable available chlorine concentration |
| SE465958B (en) * | 1988-09-26 | 1991-11-25 | Sandvik Ab | DOUBLE SIDE CUT |
| NZ237301A (en) * | 1990-03-13 | 1992-09-25 | Colgate Palmolive Co | Aqueous automatic dishwasher detergent compositions comprising potassium tripolyphosphate, cross-linked polycarboxylate-type thickener and sodium ions |
| WO1996027651A1 (en) * | 1995-03-03 | 1996-09-12 | The Procter & Gamble Company | Cleaning compositions with reduced skin malodor |
| JP2002060798A (en) * | 2000-08-17 | 2002-02-26 | Asahi Denka Kogyo Kk | Melt-type solid detergent composition and method for producing the same |
| BRPI0513876A (en) * | 2004-07-27 | 2008-05-20 | Unilever Nv | method for providing lasting antimicrobial activity on a hard surface, aqueous liquid bleach compositions, and toilet cleaning product |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE437383A (en) * | 1938-12-24 | |||
| BE544519A (en) * | 1955-01-18 | |||
| JPS5115038A (en) * | 1974-07-22 | 1976-02-06 | Hironori Hirai | OOPUNENDOSEI BOKI |
-
1985
- 1985-02-15 CA CA000474405A patent/CA1231612A/en not_active Expired
- 1985-04-26 EP EP85302981A patent/EP0165676A3/en not_active Withdrawn
- 1985-06-18 JP JP60132889A patent/JPH0742480B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6114299A (en) | 1986-01-22 |
| EP0165676A3 (en) | 1987-08-19 |
| JPH0742480B2 (en) | 1995-05-10 |
| EP0165676A2 (en) | 1985-12-27 |
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