CA1039610A - Method of washing textile materials - Google Patents
Method of washing textile materialsInfo
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- CA1039610A CA1039610A CA240,841A CA240841A CA1039610A CA 1039610 A CA1039610 A CA 1039610A CA 240841 A CA240841 A CA 240841A CA 1039610 A CA1039610 A CA 1039610A
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- catalyst
- alkali metal
- aqueous medium
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Abstract
Abstract of the Disclosure Textile materials are washed in water contain-ing a surface active agent and a catalytically effective amount of a novel catalyst. The catalyst is prepared by steps including admixing a water soluble alkali metal silicate with an aqueous medium containing carefully con-trolled amounts of dissolved water soluble substances which are sources of calcium ion and magnesium ion, reacting the same to produce an aqueous colloidal suspension of the reaction product, admixing a micelle-forming surfactant with the aqueous medium, and agitating the aqueous medium containing the colloidal particles and surfactant to form catalyst-containing micelles.
Description
~039610 ~BACKGROUND OF THE I~VE~TIO~
This invention relates to a novel method of removing dirt, grease, stains and foreign materials in general from soiled textile materials.
A wide variety of surface active agents have been used heretofore in washing soiled textile materials. Examples include the alkali metal soaps of long chain fatty acids, the - alkali metal soaps of rosin acids and the derivatives of rosin - acids, synthetic detergents of the anionic, cationic or non-ionic types, and mixtures of one or more of the foregoing surface active agents. It has also been common practice to use - inert diluents such as sodium sulfate, or builders such as polyphosphates, polysilicates or sodium carboxymethylcellulose in combination with one or more of the foregoing surface active ., agents. A number of nitrogen-containing sequestering agents, anti-bacterial agents and surface active agents, and enzymes ;- capable of removing certain stains from fabrics have also been added to laundry detergents heretofore.
Many of the commercially available surface active -~ compositions presently recommended for household and industrial uses are not entirely satisfactory for a number of reasons. -Laundry detergents often include a phosphorus or nitrogen-. . - :
containing compound which either directly or indirectly ~
.~, , results in a pollution problem. The phosphates and nitrogen-containing compounds promote the growth of microorganisms and ; alga in streams ` ~039610 and other bodies of water into which sewage is introduced and this results in an adverse change in the ecology.
The presence of a high concentration of sodium sulfate and other soluble fillers also is undesirable when the water is to be reused downstream for purposes which -~
require a low sodium or solubles content. In instances - _ where laundry detergents contain synthetic surfactants which are not destroyed by microrganisms at a sufficiently rapid rate, the surfactant concentration in streams ~ -tends to increase to an objectionable level. The enzymes presently added to laundry detergents are not effective for removing many stubborn stains and thus do not always produce the desired results. Additionally, all of the enzyme-producing microrganisms may not be killed prior to adding the enzyme to the laundry detergent. It has been reported that the live microrganisms are capable of causing lung infections when finely divided particles of the laundry detergent are inhaled.
As a result of the above mentioned and other disadvantages, the art has long sought an entirely satisfactory surface active composition for general household and industrial use which does not require the presence of phosphorus or nitrogen-containing compounds, inert fillers, enzymes and the like. However, prior to the present invention an entirely satisfactory ,: .. .. .
.:
. , . .. _ _ 11~396~ () heav~v duty surface active composition was not available which overcomes the pollution problems of the prior art and yet is capable of removing stubborn stains and deeply em~edded soil from textile materials.
Thus, the present invention relates to a method of washing soil from soiled textile material wherein the textile material is intimately contacted with water containing a surface active agent, and the improvement in combination therewith comprising washing the soil from the soiled textile material with water containing the said surface active agent and a catalyst, the catalyst being present in a catalytic-ally effective amount which increases the rate of re-moval of the soil from the textile material, the catalyst being prepared by a process comprising admixing : a water soluble alkali metal silicate with an '- aqueous medium containing a dissolved substan~e ~ :
. which is a source of calcium ion and a dissolved :
substance which is a source of magnesium ion, l 20 the aqueous medium containing said dissolved substances in amounts to provide between about 1 x 10 and : .:
. 1 x 10 mole per liter each of calcium ion and ; magnesium ion, the aqueous medium containing said dissolved substances -in amounts to provide a molar ratio of calcium ; ion to magnesium ion between about 2.0:1.0 and 1:0:2.0, the alkali metal silicate having an alkali metal oxide to silicon dioxide ratio between about 0.9:1.0 and : - 4 - B
,..... . . . . .. . . . .. . . . . . .. . .. . .. .
1~396~0 less than 2.0:1.0 and being admixed with the aqueous : medium in an amount of about 0.05-2 moles per liter, reacting the alkali metal silicate with said dissolved ; substances providing calcium ion and magnesium ; ion to produce an aqueous colloidal suspension of particles of the reaction product, admixing a micelle-forming surfactant with the aqueous medium in an amount to form catalyst micelles comprising said colloidal particles upon agitating the aqueous medium, and agitating the aqueous medium containing the colloidal particles and surfactant to form said catalyst . micelles. -; DETAILED DESCRIPTIO~ OF THE I~VE~TIO~
INCLUDI~G PREFERRED VARIA~TS THEREOF
. In accordance with the present invention, textile materials . are washed in water containing a surface active agent and a !' catalytic amount of a novel catalyst to be described more fully - :
: hereinafter. In practicing the method, the soiled textile - :
materials are intimately contacted with water containing the surface active agent and the , ., ' .
4~ ~ :
,.
",',. ~
1039610 `:
catalyst, and preferahly with agitation and/or _.
following the recommended prior art washing cycle.
Suitable surface active agents of the prior art may be used in washing the textile materials. Examples of surface active agents ~- include the alkali metal soaps of long chain fatty acids and especially the sodium and - potassium soaps of fatty acids containing about 14-25 carbon atoms and preferably - 10 about 16-18 carbon atoms. Other surface active agents include detergents which are not derived directly from fatty acids such as synthetic anionic, cationic and nonionic detergents. Specific examples of synthetic ; 15 anionic detergents include the alkali metal salts of organic sulfonates or organic sulfates, - and especially the alkali metal salts of high molecular weight alkyl and alkylaryl sulfonates such as sodium or potassium .. ;, ~ ,,.
, 20 dodecyl benzene sulfonate, and the sodium and potassium sulfates of straight chain primary alcohols such as sodium lauryl sulfate and other sodium and potassium sulfates of fatty alcohols or products of the Oxo process. Specific examples of cationic detergents include the quaternary "~ '~~
ammonium halides such as benzethonium chloride, and _ . . _ . _ , ., , . . _ _ _ . ~, 10;~9610 o~ten members of this group have outstanding germicidal activity as well as surface active properties. Specific examples of nonionic detergents include compounds having a polyoxyethylene or other oxygenated side chain and the remainder of the molecule may be derived from fatty acids, alcohols, ' phenols, amides or amines.
Further examples of surface active agents are dis-closed in the section on detergency appearing in the Kirk-Othmer Encyclopedia of Chemical Technology (2nd Edition), Volume 6, pages 853-895. Still additional specific examples of detergent compositions for industrial or household use are found in numerous United States patents, including the follow-ing:
:,, 3,031,510 3,119,848 3,222,287 3,382,177 `~
3,043,780 3,140,261 3,223,647 3,382,285 `~
` - 3,048,548 3,144,412 3,282,852 3,422,021 ` 3,053,771 3,156,655 3,314,891 3,424,689 3,061,551 3,173,877 3,320,172 3,429,822 ~ 3,067,143 3,203,955 3,326,807 3,437,697 `~ 20 3,082,172 3,208,949 3,337,463 3,444,242 3,095,381 3,101,374 3,349,038 3,499,841 3,101,297 3,213,028 3,359,205 3,507,798 3,118,000 3,215,633 3,382,176 , It is understood that the above surface active agents are given by way of example only, and that numerous ' ,~ - 6 -:' :' other suitable surface active agents may be used. A
mixture of one or more of the above surface active agents : may be used when desired. It is also common practice to admix therewith inert diluents such as sodium sulfate, .
or builders such as polyphosphates, polysilicates and ;~ sodium carboxymethyl cellulose. However, these substances are not essential and it is usually preferred that the textile materials be washed with a surface active agent or composition which is free of substances presenting a pollution problem, such as phosphorus and nitrogen-- containing compounds.
The surface active agent or composition ; selected for use in a given instance is often determined by the nature of the specific textile material to be washed, and may be in accordance with prior art practice.
The textile materials may be natural or synthetic, and in the form of fiber, roving, thread, woven fabric, unwoven fabric or articles prepared therefrom such as clothing. Examples of naturally ocurring textile ~; 20 materials include silk, cotton, flax, hemp and jute.
Examples of synthetic textile materials include regen-; erated cellulose such as rayon, polymeric amides such as Nylon, and polyesters such as Dacron.
The water used in washing the textile materials also may be in accordance with the prior art and in most , ' , .
~ - 7 ~" ' .
instanees is untreated or softened tap water derived from municipal water sources, wells or springs. A soft water usually gives better results and is preferred. The surfaee active composition may be added to the water in ~` 5 the quantity reeommended in aeeordanee with prior art , praetiee when desired, sueh as about 1/4-2 eups, and : preferably about 1/2-1 eup, for each 8-9 pounds of textile material. ~owever, the eatalyst of the invention inereases the effectiveness of a given quantity of surface aetive agent very markedly. Only about 1/8-1/2 as much surface aetive agent is required to obtain equally satisfactory results, and often about 1~4 as much is used in most household and industrial applications. The amount of water to be used may be in accordance with prior art practice and is ;
; 15 often about 5-20 gallons and preferably about 10-15 gallons for each 8-9 pounds of textile material.
The catalyst is present in the water that is intimately contacted with the textile material in a quantity providing suffieient catalytic activity to aid r 20 in removing stains and insoluble materials such as soil.
Usually the water contains about 0.00001-0.1 weight percent of the eatalyst, and preferably about 0.0004-0.001 weight pereent for many applications. Often about 0.00002 weight , percent of the eatalyst based upon the weight of the water - 25 gives very good results when washing clothing in household automatic washers, but it is understood that much larger or ; smaller quantities may be employed when desired.
It is not necessary to use special washing equipment and ordinary small automatic washing machines .-.~ l `` ~1039610 are preferred for household use and industrial washing machines for larger scale use such as in laundries. It also is not necessary to change the surface active agent, the amount of water and surface active agent, washing cycle, or other operating procedure with the exception of adding the catalyst or as otherwise noted herein. However, often it is preferred to allow the textile materials to soak in water contain-; ing the surface active agent and the catalyst prior to commencing the washing cycle. The Textile materials may be soaked, for - -` 10 example, for about five minutes to several hours and prefer-;
ably for about 15 minutes to 1 hour. The washing cycle may be, for example, over a period of about 5-60 minutes and preferably about 10-30 minutes.
A preformed laundry detergent composition for use in ~-practicing the invention may contain a major proportion by weight of a surface active agent and a catalytically effective amount - of the novel catalyst. The composition may contain, for example, the catalyst and one or more of the surface active agents previously mentioned for use in washing textile materials.
If desired, the catalyst may be added to commercially available solid or liquid surface active compositions such as Ivory Snow *, Tide-*, and Thrill ~, or the compositions disclosed in the patents listed herein. The catalyst is present in a quantity to provide a catalytic amount when the composition is admixed with *Trademarks . :
_ g _ B
. . .
1039610 ,,.
water in the recommen d ratio for washing clothing.
Usually the catalyst is present in an amount to provide about 0.00001-0.1 weight percent, and preferably - about 0.0004-0.0001 weight per cent in the water that is `~ 5 added thereto at the time of use. Often the catalyst is present in an amount of about 0.01-1 weight percent based ` upon the weight of the concentrated surface active composition.
Larger or smaller amounts may be present as it is only necessary to provide the catalyst in effective catalytic amounts in the wash water prepared by diluting the composition with water. Alternatively, the surface active agent may be admixed with the aqueous catalyst suspension produced in the catalyst preparation step discussed hereinafter.
For example, the aqueous catalyst suspension as 15 prepared may be diluted with 100-10,000 volumes of water, and for better results with about 250-2,000 volumes of water - and for best results with about 500-1,000 volumes of water, either before, during or after adding the surface active agent.
PREPARATION OF THE CATALYST
The catalyst used in practîcing the present invention may be prepared as described below. In the ~~~~~
presently preferred process for preparing an aqueous suspension of the catalyst, a water soluble alkali metal silicate is admixed and reacted with an aqueous solution of a water soluble dissolved substance which is a source of calcium ion and a water soluble dissolved substance which is a source of magnesium ion to produce a finely divided or colloidal suspension of the reaction product. The aqueous solution contains the dissolved substances initially in amounts to provide between about 1 x 10 ~ and 1 x 10 1 mole per liter each of calcium ion and magnesium ion, preferably between about 1 x 10 3 and 1 x 10 2 mole per liter, and for still better results between 1 x 10 3 and 6 x 10 3 mole per liter. The dissolved substances should also be present in amounts to provide a molar ratio of calcium ion to magnesium ion betwwen about 2.0:1.0 and 1.0:2.0, and preferably about 1.5:1.0 and 1.0:1.5. For best - results, the aqueous medium should contain the dissolved substances in amounts to provide between about 2.5 x 10 3 and 3.0 x 10 ~3 mole per liter each of calcium ion and magnesium ion, and the molar ratio of calcium ion to magnesium ion should be about 1.0:1.0, e. g., 2.9 x 10 3 mole per liter of calcium ion and 2.7 x 10 3 mole per liter of magnesium ion. The alkali metal silicate should have an alkali metal oxide to silicon ;- dioxide ratio between about 0.9:1.0 and less than
This invention relates to a novel method of removing dirt, grease, stains and foreign materials in general from soiled textile materials.
A wide variety of surface active agents have been used heretofore in washing soiled textile materials. Examples include the alkali metal soaps of long chain fatty acids, the - alkali metal soaps of rosin acids and the derivatives of rosin - acids, synthetic detergents of the anionic, cationic or non-ionic types, and mixtures of one or more of the foregoing surface active agents. It has also been common practice to use - inert diluents such as sodium sulfate, or builders such as polyphosphates, polysilicates or sodium carboxymethylcellulose in combination with one or more of the foregoing surface active ., agents. A number of nitrogen-containing sequestering agents, anti-bacterial agents and surface active agents, and enzymes ;- capable of removing certain stains from fabrics have also been added to laundry detergents heretofore.
Many of the commercially available surface active -~ compositions presently recommended for household and industrial uses are not entirely satisfactory for a number of reasons. -Laundry detergents often include a phosphorus or nitrogen-. . - :
containing compound which either directly or indirectly ~
.~, , results in a pollution problem. The phosphates and nitrogen-containing compounds promote the growth of microorganisms and ; alga in streams ` ~039610 and other bodies of water into which sewage is introduced and this results in an adverse change in the ecology.
The presence of a high concentration of sodium sulfate and other soluble fillers also is undesirable when the water is to be reused downstream for purposes which -~
require a low sodium or solubles content. In instances - _ where laundry detergents contain synthetic surfactants which are not destroyed by microrganisms at a sufficiently rapid rate, the surfactant concentration in streams ~ -tends to increase to an objectionable level. The enzymes presently added to laundry detergents are not effective for removing many stubborn stains and thus do not always produce the desired results. Additionally, all of the enzyme-producing microrganisms may not be killed prior to adding the enzyme to the laundry detergent. It has been reported that the live microrganisms are capable of causing lung infections when finely divided particles of the laundry detergent are inhaled.
As a result of the above mentioned and other disadvantages, the art has long sought an entirely satisfactory surface active composition for general household and industrial use which does not require the presence of phosphorus or nitrogen-containing compounds, inert fillers, enzymes and the like. However, prior to the present invention an entirely satisfactory ,: .. .. .
.:
. , . .. _ _ 11~396~ () heav~v duty surface active composition was not available which overcomes the pollution problems of the prior art and yet is capable of removing stubborn stains and deeply em~edded soil from textile materials.
Thus, the present invention relates to a method of washing soil from soiled textile material wherein the textile material is intimately contacted with water containing a surface active agent, and the improvement in combination therewith comprising washing the soil from the soiled textile material with water containing the said surface active agent and a catalyst, the catalyst being present in a catalytic-ally effective amount which increases the rate of re-moval of the soil from the textile material, the catalyst being prepared by a process comprising admixing : a water soluble alkali metal silicate with an '- aqueous medium containing a dissolved substan~e ~ :
. which is a source of calcium ion and a dissolved :
substance which is a source of magnesium ion, l 20 the aqueous medium containing said dissolved substances in amounts to provide between about 1 x 10 and : .:
. 1 x 10 mole per liter each of calcium ion and ; magnesium ion, the aqueous medium containing said dissolved substances -in amounts to provide a molar ratio of calcium ; ion to magnesium ion between about 2.0:1.0 and 1:0:2.0, the alkali metal silicate having an alkali metal oxide to silicon dioxide ratio between about 0.9:1.0 and : - 4 - B
,..... . . . . .. . . . .. . . . . . .. . .. . .. .
1~396~0 less than 2.0:1.0 and being admixed with the aqueous : medium in an amount of about 0.05-2 moles per liter, reacting the alkali metal silicate with said dissolved ; substances providing calcium ion and magnesium ; ion to produce an aqueous colloidal suspension of particles of the reaction product, admixing a micelle-forming surfactant with the aqueous medium in an amount to form catalyst micelles comprising said colloidal particles upon agitating the aqueous medium, and agitating the aqueous medium containing the colloidal particles and surfactant to form said catalyst . micelles. -; DETAILED DESCRIPTIO~ OF THE I~VE~TIO~
INCLUDI~G PREFERRED VARIA~TS THEREOF
. In accordance with the present invention, textile materials . are washed in water containing a surface active agent and a !' catalytic amount of a novel catalyst to be described more fully - :
: hereinafter. In practicing the method, the soiled textile - :
materials are intimately contacted with water containing the surface active agent and the , ., ' .
4~ ~ :
,.
",',. ~
1039610 `:
catalyst, and preferahly with agitation and/or _.
following the recommended prior art washing cycle.
Suitable surface active agents of the prior art may be used in washing the textile materials. Examples of surface active agents ~- include the alkali metal soaps of long chain fatty acids and especially the sodium and - potassium soaps of fatty acids containing about 14-25 carbon atoms and preferably - 10 about 16-18 carbon atoms. Other surface active agents include detergents which are not derived directly from fatty acids such as synthetic anionic, cationic and nonionic detergents. Specific examples of synthetic ; 15 anionic detergents include the alkali metal salts of organic sulfonates or organic sulfates, - and especially the alkali metal salts of high molecular weight alkyl and alkylaryl sulfonates such as sodium or potassium .. ;, ~ ,,.
, 20 dodecyl benzene sulfonate, and the sodium and potassium sulfates of straight chain primary alcohols such as sodium lauryl sulfate and other sodium and potassium sulfates of fatty alcohols or products of the Oxo process. Specific examples of cationic detergents include the quaternary "~ '~~
ammonium halides such as benzethonium chloride, and _ . . _ . _ , ., , . . _ _ _ . ~, 10;~9610 o~ten members of this group have outstanding germicidal activity as well as surface active properties. Specific examples of nonionic detergents include compounds having a polyoxyethylene or other oxygenated side chain and the remainder of the molecule may be derived from fatty acids, alcohols, ' phenols, amides or amines.
Further examples of surface active agents are dis-closed in the section on detergency appearing in the Kirk-Othmer Encyclopedia of Chemical Technology (2nd Edition), Volume 6, pages 853-895. Still additional specific examples of detergent compositions for industrial or household use are found in numerous United States patents, including the follow-ing:
:,, 3,031,510 3,119,848 3,222,287 3,382,177 `~
3,043,780 3,140,261 3,223,647 3,382,285 `~
` - 3,048,548 3,144,412 3,282,852 3,422,021 ` 3,053,771 3,156,655 3,314,891 3,424,689 3,061,551 3,173,877 3,320,172 3,429,822 ~ 3,067,143 3,203,955 3,326,807 3,437,697 `~ 20 3,082,172 3,208,949 3,337,463 3,444,242 3,095,381 3,101,374 3,349,038 3,499,841 3,101,297 3,213,028 3,359,205 3,507,798 3,118,000 3,215,633 3,382,176 , It is understood that the above surface active agents are given by way of example only, and that numerous ' ,~ - 6 -:' :' other suitable surface active agents may be used. A
mixture of one or more of the above surface active agents : may be used when desired. It is also common practice to admix therewith inert diluents such as sodium sulfate, .
or builders such as polyphosphates, polysilicates and ;~ sodium carboxymethyl cellulose. However, these substances are not essential and it is usually preferred that the textile materials be washed with a surface active agent or composition which is free of substances presenting a pollution problem, such as phosphorus and nitrogen-- containing compounds.
The surface active agent or composition ; selected for use in a given instance is often determined by the nature of the specific textile material to be washed, and may be in accordance with prior art practice.
The textile materials may be natural or synthetic, and in the form of fiber, roving, thread, woven fabric, unwoven fabric or articles prepared therefrom such as clothing. Examples of naturally ocurring textile ~; 20 materials include silk, cotton, flax, hemp and jute.
Examples of synthetic textile materials include regen-; erated cellulose such as rayon, polymeric amides such as Nylon, and polyesters such as Dacron.
The water used in washing the textile materials also may be in accordance with the prior art and in most , ' , .
~ - 7 ~" ' .
instanees is untreated or softened tap water derived from municipal water sources, wells or springs. A soft water usually gives better results and is preferred. The surfaee active composition may be added to the water in ~` 5 the quantity reeommended in aeeordanee with prior art , praetiee when desired, sueh as about 1/4-2 eups, and : preferably about 1/2-1 eup, for each 8-9 pounds of textile material. ~owever, the eatalyst of the invention inereases the effectiveness of a given quantity of surface aetive agent very markedly. Only about 1/8-1/2 as much surface aetive agent is required to obtain equally satisfactory results, and often about 1~4 as much is used in most household and industrial applications. The amount of water to be used may be in accordance with prior art practice and is ;
; 15 often about 5-20 gallons and preferably about 10-15 gallons for each 8-9 pounds of textile material.
The catalyst is present in the water that is intimately contacted with the textile material in a quantity providing suffieient catalytic activity to aid r 20 in removing stains and insoluble materials such as soil.
Usually the water contains about 0.00001-0.1 weight percent of the eatalyst, and preferably about 0.0004-0.001 weight pereent for many applications. Often about 0.00002 weight , percent of the eatalyst based upon the weight of the water - 25 gives very good results when washing clothing in household automatic washers, but it is understood that much larger or ; smaller quantities may be employed when desired.
It is not necessary to use special washing equipment and ordinary small automatic washing machines .-.~ l `` ~1039610 are preferred for household use and industrial washing machines for larger scale use such as in laundries. It also is not necessary to change the surface active agent, the amount of water and surface active agent, washing cycle, or other operating procedure with the exception of adding the catalyst or as otherwise noted herein. However, often it is preferred to allow the textile materials to soak in water contain-; ing the surface active agent and the catalyst prior to commencing the washing cycle. The Textile materials may be soaked, for - -` 10 example, for about five minutes to several hours and prefer-;
ably for about 15 minutes to 1 hour. The washing cycle may be, for example, over a period of about 5-60 minutes and preferably about 10-30 minutes.
A preformed laundry detergent composition for use in ~-practicing the invention may contain a major proportion by weight of a surface active agent and a catalytically effective amount - of the novel catalyst. The composition may contain, for example, the catalyst and one or more of the surface active agents previously mentioned for use in washing textile materials.
If desired, the catalyst may be added to commercially available solid or liquid surface active compositions such as Ivory Snow *, Tide-*, and Thrill ~, or the compositions disclosed in the patents listed herein. The catalyst is present in a quantity to provide a catalytic amount when the composition is admixed with *Trademarks . :
_ g _ B
. . .
1039610 ,,.
water in the recommen d ratio for washing clothing.
Usually the catalyst is present in an amount to provide about 0.00001-0.1 weight percent, and preferably - about 0.0004-0.0001 weight per cent in the water that is `~ 5 added thereto at the time of use. Often the catalyst is present in an amount of about 0.01-1 weight percent based ` upon the weight of the concentrated surface active composition.
Larger or smaller amounts may be present as it is only necessary to provide the catalyst in effective catalytic amounts in the wash water prepared by diluting the composition with water. Alternatively, the surface active agent may be admixed with the aqueous catalyst suspension produced in the catalyst preparation step discussed hereinafter.
For example, the aqueous catalyst suspension as 15 prepared may be diluted with 100-10,000 volumes of water, and for better results with about 250-2,000 volumes of water - and for best results with about 500-1,000 volumes of water, either before, during or after adding the surface active agent.
PREPARATION OF THE CATALYST
The catalyst used in practîcing the present invention may be prepared as described below. In the ~~~~~
presently preferred process for preparing an aqueous suspension of the catalyst, a water soluble alkali metal silicate is admixed and reacted with an aqueous solution of a water soluble dissolved substance which is a source of calcium ion and a water soluble dissolved substance which is a source of magnesium ion to produce a finely divided or colloidal suspension of the reaction product. The aqueous solution contains the dissolved substances initially in amounts to provide between about 1 x 10 ~ and 1 x 10 1 mole per liter each of calcium ion and magnesium ion, preferably between about 1 x 10 3 and 1 x 10 2 mole per liter, and for still better results between 1 x 10 3 and 6 x 10 3 mole per liter. The dissolved substances should also be present in amounts to provide a molar ratio of calcium ion to magnesium ion betwwen about 2.0:1.0 and 1.0:2.0, and preferably about 1.5:1.0 and 1.0:1.5. For best - results, the aqueous medium should contain the dissolved substances in amounts to provide between about 2.5 x 10 3 and 3.0 x 10 ~3 mole per liter each of calcium ion and magnesium ion, and the molar ratio of calcium ion to magnesium ion should be about 1.0:1.0, e. g., 2.9 x 10 3 mole per liter of calcium ion and 2.7 x 10 3 mole per liter of magnesium ion. The alkali metal silicate should have an alkali metal oxide to silicon ;- dioxide ratio between about 0.9:1.0 and less than
2.0:1.0, and preferably between about 0.9:1.0 and 1.2:
1Ø The alkali metal silicate should be admixed with the aqueous medium in an amount of about 0.05-2 moles per liter, preferably about 0.1-1 mole per liter, and for still better results about 0.2-0.5 mole per liter. For best results, the alkali metal silicate should be an . ~.. ...
1039610 !, ' alkali metal meta-silicate having an alkali metal oxide to silicon dioxide ratio of about 1:1, and it :` should be admixed with the aqueous medium in an amount to provide about 0.2-0.3 mole per liter, e.g., about ' 0.25 mole per li-ter.
Examples of sources of calcium ion and magnesium ion for use in preparing the aqueous solution ~ .
include mineral acid salts such as the halides, sulfates, bisulfates, nitrites, and nitrates of calcium and magnesium. The chlorides are usually the preferred halides, and both calcium and magnesium chloride are soluble and may be used. Magnesium sulfate and ; bisulfate are soluble and often are the preferred sources of magnesium ion. Calcium sulfate is only slightly soluble in water and usually is not a preferred source of calcium ion, but calcium bisulfate is somewhat more soluble. While calcium and magnesium nitrite or nitrate are soluble in water and may be used, these ,~ substances are not preferred in most instances. The sources of calcium ion and magnesium ion are dissolved , in the aqueous medium in amounts to provide calcium ion and magnesium ion within the above ranges. Complete - ionization is assumed when calculating the quantities `:
,~.
~ I
~039610 to be dissolved and any desired order of addition is satisfactory. For example, the source of calcium ion may be added to the aqueous medium before, during or after the source of magnesium ion.
The alkali metal silicate to be admixed with the aqueous medium is preferably a water soluble sodium ~~~~~
or potassium silicate having an alkali metal oxide (M20) to silicon dioxide (SiO2) mole ratio between about 0.9:1.0 and less than 2.0:1.0, and preferably between about 0.9:1.0 and 1.2:1Ø The best results are usually obtained with an alkali metal metasilicate having an alkali metal oxide to silicon dioxide ratio of about 1:1. Hydrated alkali metal silicates dissolve faster and should be used for best results when the alkali -- -metal silicate is added in solid form. In instances - where an anhydrous alkali metal silicate is used, it may be desirable to dissolve it in water and then add the solution to the aqueous medium. Sodium metasilicate is preferred and usually a hydrated sodium metasilicate . such as the pentahydrate gives the best results.
.~ i ;-~ Carbonate ion and/or bicarbonate ion should not be present in the aqueous medium in substantial concentrations as the calcium ion and magnesium ion are -~ precipitated in the form of their respective carbonates.
25 The free carbonate ion and/or bicarbonate ion concentra- -tions in~the aqueous medium should not exceed about 10 -~~~~
~:`
_ 13 ., , .
~03s6la ; ., parts per million by weight based upon the combined weight of the water and the ingredients added thereto and for this reason, the alkali metal silicates should be substantially free of carbonate ion and bicarbonate ion. A small amount of preciptated calcium carbonate and/or magnesium carbonate may be present in the aqueous medium provided additional calcium ion and magnesium ion are available to meet the above defined concentrations.
Distilled water and/or deionized water are usually preferred over a natural or untreated water when preparing the aqueous medium. In instances where water is used which contains substantial initial concentrations of alkaline earth metal ions, then this should be taken into consideration in calculating the amounts of the sources of calcium ion and magnesium ion which are " necessary to arrive at the final concentrations previously ; discussed.
An electrolyte which aids in the preparation of colloidal suspensions may be present in the aqueous medium at the time of admixing the alkali metal silicate therewith. Examples of electrolytes include those used in preparing prior art colloidal suspensions such as the alkali metal halides,sulfates and bisulfates.
Sodium chloride, sodium sulfate and sodium bisulfate are usually preferred. The electrolyte should be added in . .
. ~
" 1039610 small amounts such as, for example, about 0.00001-0.1 mole per liter, but often larger or smaller amounts may be present. ~ _ The conditions under which the alkali metal silicate is admixed with the aqueous medium and reacted ` with the sources of calcium ion and magnesium ion are ~; not critical provided the reaction mixture is maintained --in the liquid phase. The reaction temperature may be, for example, between the freezing point and boiling point of water under the existing pressure conditions. At atmospheric pressure, the temperature is usually about ~ _ 10-90C and often a more convenient temperature is about 20-50C. In many instances, ambient or normal room temperature is satisfactory.
The degree of agitation is not critical, and mild to vigorous agitation may be employed during addition of the alkali metal silicate. For the best results, the aqueous medium should be agitated sufficiently to assure ;
. .
rapid and uniform admixing of the alkali metal silicate.
After completing the addition of the alkali metal silicate, when desired the agitation may be continued for a sufficient period of time to assure complete reaction and aging of the resulting colloidal suspension, such ' _ ` as for approximately 1-5 minutes to one hour or longer.
Upon admixing the alkali metal silicate with ., - .
- the aqueous medium, it takes on a turbid appearance but in most instances no significant amount of visible ~ -precipitate is formed. The colloidal suspension of the reaction product thus produced should be strongly basic and may have a pl-l value of, for example, approximately ~ .. _._. . . .,.. . _ .. . . .. _ _ 103g610 10-14 and preferably about 11-13, and for hest results about 12. In view of this, the initial pH value of the aqueous medium containing the dissolved sources of calcium .
ion and magnesium ion is of importance and should be about 6-9 and preferably about 7-8. When necessary, it is possible to adjust the pH value of the aqueous medium to the foregoing levels either before during or after :_ - addition of the alkali metal silicate by adding bases such as sodium or potassium hydroxide, or mineral acids - 10 such as sulfuric or hydrochloric acid.
The colloidal suspension may be stored for .,.
;: several weeks or longer while awaiting the further .:
treatment described hereinafter. In instances where -~ the colloidal suspension is to be stored over a substantial period of time, the pH value should be maintained at the above described level and the storage vessel is preferably a tightly capped polyethylene bottle or other inert plastic container which prevents the contents from absorbing carbon dioxide from the atmosphere.
The colloidal suspension of the reaction product is not suitable for use as a catalyst as prepared and it should be agitated sufficiently in the presence of a micelle-forming surfactant to form catalyst-containing micelles. The degree of agitation, the length of the agitation period, and the amount of the micelle-forming surfactant that is present in the colloidal :. .
. . .
~039610 .
suspension are controlled at levels favorable to the formation of micelles. For example, the surfactant may be present in an amount of about 0.001-0.1 mole per liter and preferably about 0.03-0.07 mole per liter for most , 5 surfactants. Smaller or larger amounts may be effective -- with some surfactants such as 0.0001 mole per liter or less, or 0.2 mole per liter or more. About 0.05 mole per liter often gives the best results with many surfactants.
The minimum period of agitation and the minimum 10 degree of agitation that are required for micelle formation varies somewhat with temperature and the type and amount of surfactant. As is well understood in this art, gradually increasing these variants in the presence of an effective amount of the micelle-forming surfactant 15 will result in micelle formation when the proper levels are reached. As a general rule, longer periods of agitation and/or more vigorous agitation are required to form micelles at lower temperatures approaching the t freezing point of the colloidal suspension than at higher 20 temperatures approaching the boiling point. In instances where the aqueous suspension has a temperature of approximately 50-90C., then mild agitation over a perio~
of about 10-60 minutes is satisfactory. Often longer or shorter periods of mild to vigorous agitation may be 25 employed such as from about 1-5 minutes to several hours ~. ._ -"' ~03g610 at temperatures vaxying,respectively, between the boiling point and the freezing point. When desired, the agitation may be continued long after the catalyst containing micelles are formed as continued agitation does not seem to have an adverse effect.
As a general rule, the micelle-forming surfactants known in the prior art may be used in practicing the present invention. Micelle-forming surfactants used in the emulsion polymerization of monomeric organic compounds are discolsed in .:
the text Synthetic Rubber, by G. S. Whitby, et al, ~ohn Wiley & Sons Incorporated, New York (1954), and surface active agents ~k in general are disclosed on pages 418-424 of the text Organic ChemistrY, Fieser and Fieser, 2nd Edition, Reinhold Publishing Corporation, ~ew York, New York (1950). Examples of surfactants disclosed in the above texts include the alkali metal soaps of long chain fatty acids, and especially the sodium and potassium soaps of fatty acids containing about 14-25 carbon atoms and preferably about 16-18 carbon atoms, and the sodium and potassium soaps of the rosin acids, abietic acid and the derivatives thereof. Other micelle-forming surfactants include fats and oils such as corn oil, cotton seed oil, castor oil, soy bean oil and safflower oil which have been fully or part-ially saponified with alkali metal bases to . .
` ~ , , .
'," , .
:. V
~` ~039610 produce mixtures inclu ng saponified long chain fatty acids, the mono- or di-glycerides thereof, and glycerin.
Examples of synthetic micelle-forminy surfactants include the sulfonates of long chain alcohols prepared by hydrogenation of naturally ocurring fats and oils of the above types and especially sulfonated long chain alcohols containing about 10-20 and preferably about 12-14 carbon atoms, the alkali metal salts of the monosulfonates of monoglycerides such as sodium glyceryl monolaurate sulfonate, the sulfonates of succinic acid esters such as dioctyl sodium sulfcsuccinate and the alkylaryl alkali metal sulfonates. Specific examples of presently preferred micelle-forming surfactants include sodium and potassium sulforicinoleate, tetrahydronaphthalene sulfonate, octahydroanthracene sulfonic acid, butyl naphthalene sulfonic acid, sodium xylene sulfonate, alkyl benzene sulfonic acid and potassium benzene sulfonate.
Sulfated long chain hydroxycarboxylic acids containing about 14-25 carbon atoms and preferably about 16-18 carbon atoms, and sulfated fats and oils containing hydroxycarboxylic acids of this type produce exceptionally good micelle-forming surfactants. At least 25% of the hydroxyl groups and preferably at least 50% should be sulfated, and up to 95-100% may be sulfated. It is usually preferred that the sulfated oils and/or long chain - hydroxycarboxylic acids be neutralized with an alkali metal , .
. _ .:' ~, .
~039610 _ base, and that the corresponding alkali metal salts be added to the colloidal suspension in the form of an aqueous solution. The aqueous solution may contain at least 25%
of water and preferably at least 35-40% by weight. Much `~ 5 larger percentages of water may be present when desired --~ such as 75-80% or more by weight.
A very active catalyst is produced when using sulfated castor oil as the micelle-forming surfactant (Turkey Red oil.) Sulfated castor oil which has been purified sufficiently to be of U.S.P. or medicinal grade produces an exceptionally active catalyst. For the best results, the castor oil is reacted with about an equal - weight of concentrated sulfuric acid (e.g., 20% by weight) at a temperature of approximately 25-30C. The mixture may be reacted for about two hours with stirring and is then neutralized with sodium hydroxide solution. The reaction mixture separates into three layers, i.e., an upper layer which is a water solution, an intermediate or oily layer, and a white curdy precipitate. The intermediate oily layer is separated from the upper and lower layers, and b may ke added to the colloidal suspension as the micelle-forming surfactant in an amount, for example, of 0.001-0.1 mole per liter, and preferably about 0.005 mole per liter.
The activity of the catalyst may be increased very markedly by cooling the aqueous catalyst suspension to a temperature approaching the freezing point such as '"
;~' about 0-10C., and then warming over one or more cycles.
For best results, the aqueous catalyst suspension should : be frozen and thawed over one or more cycles. The reason for the increased catalytic activity is not fully ~~ ~
understood at the present time but cooling and then -warming the aqueous catalyst suspension seems to increase the concentration of the catalyst-containing micelles and/or increases the catalytic activity thereof. -~-~
The aqueous suspension of the catalyst contains lG a relatively small percentage by weight of the active - catalyst as produced. When desired, it may be concentrated by evaporating a portion of the water to produce a concentrated liquid catalyst suspension which may be stored and used more conveniently. It is also possible to prepare a dry catalyst concentrate by evaporating substantially - all of the water. The preferred method of producing the dry catalyst concentrate is by flash evaporation using a technique analogous to that employed in preparing powdered milk. The catalyst concentrates produced upon partial or complete evaporation of the water content of the intially prepared aqueous suspension may be reconstituted by addition of water with little or no .
loss of catalytic activity. Preferably, the water is added to the dry catalyst concentrate under sufficiently vigorous conditions of agitation to assure that the ~ ,~
, ' .
'1039610 catalyst micelles are resuspended and uniformly distributecd.
The aqueous catalyst suspension may be used as produced in practicing the invention, but preferably it is diluted with approximately lO0-lO,000 parts by weight of water and then used. For better results, the catalyst suspension should be diluted with about 250-2,000 parts `~
by weight of water before use, and for best results it should be diluted with about S00-l,000 parts by weight of water before use. The surface active agent may be added thereto when desired as previously discussed. Alternatively the dry catalyst or liquid catalyst concentrate may be admixed with water and/or the surface active agent to provide an effective catalyst concentration in the quantities previously discussed. The weight of the catalyst is calculated on a dry solids basis, i.e., the weight of --the catalyst ingredients in the aqueous suspension as produced after removal of the water.
- The invention is further illustrated by the following specific examples.
EX~PLE I
This example illustrates one presently preferred process for preparing the novel catalyst used in practicing the invention.
Anhydrous calcium chloride in an amount of 0.66 gram and magnesium sulfate heptahydrate in an amount of 1.32 grams were dissolved in two liters of cleionized water with stirring and warming until solution was complcte.
Then 95 grams of sodium silicate pentahydrate having a ~-~ ~
molecular ratio of sodium oxide to silicon dioxide of 1:1 were added to the solution with stirring and continued warming to produce a white colloidal suspension of the S reaction product.
After setting for 10 minutes, the colloidal - suspension was heated to 80C. and sulfated castor oil in an amount of 50 grams was added with stirring. The average molecular weight of the sulfated castor oil was 940 and it contained 50~ of water. The turbidity lessened somewhat as the colloidal suspension was heated at 80-90C. for one hour with vigorous stirring to produce catalyst micelles. The aqueous suspension of catalyst micelles thus prepared had a viscosity :
similar to that of water and it was used as the catalyst in certain Examples as noted hereinafter.
A dry or solid catalyst concentrate was prepared in a further run by evaporating water from the -~ r initially prepared aqueous catalyst suspension. The resulting dry catalyst concentrate was resuspended in water and there was no substantial loss of catalytic ; activity. In still other runs, the catalytic activity of the aqueous suspension of catalyst as initially ' prepared, the diluted aqueous suspension of catalyst, and the reconstituted aqueous catalyst suspension was enhanced by freezing and thawing.
EXAMPLE II.
This example illustrates the preparation of additional catalyst suspensions.
. ~;
~ 9610 Five suspensions of the catalyst were prepared from the same ingredients as used in Example I and following the general procedure of Example I. The ratios of ingredierlts were varied as follows:
Inqredient Amount of Ingredient Run 1 Run 2 Run 3 Run 4 Run 5 Deionized water 2 1 1.5 1 1.5 1 1.5 1 0.25 1 CaC12 0.66 g 0.5 g 0.5 g 1.0 g 0.5 g MgS04 . 7H20 1.32 g 1.0 g 1.0 g 2.0 g 1.0 g Na2 SiO3 5H20 165 g 132 g 71 g 185 g 71 g Sulfated Castor 100 ml 150 ml 150 ml 200 ml 150 ml oil (approximately 50% by weight H20) The catalyst suspensions prepared by the above five runs were used in certain examples as noted herein~fter.
-~ Example III
This example illustrates the use of the catalyst ,,, prepared in accordance with Example I in treating fabrics.
..
A standard household automatic washer (9 pounds .
capacity) was llsed in obtaining the data for this example.
The recommended washing cycle for the stained fabrics was also used.
; In one run, an attempt was made to remove chocolate stains from a cotton shirt using commercially available laundry ~' detergents (laundry detergents sold under the trademarks Biz* and Tide-XK*) and an oxidizing agent (Clorox*). The cocolate stains were not removed by this treatment. However, ` chocolate stains were *Trademarks .
~ ' . , . - , . , " 1039610 easily removed in a second run when washing with a catalytic amount of the diluted catalyst suspension prepared in accordance with Example I.
In subsequent runs, six fluid ounces of the catalyst suspension prepared in accordance with Example I were added to ;
the washer along with the recommended amount of cold water, laundry detergent and stained clothing. Blood, grape juice, catsup, grease and grass stains were easily removed. It was not possible to remove stains of this type when using only a laundry detergent and Clorox *.
The fabrics washed in water containing the catalyst suspension were softer and brighter. Thus, the catalyst suspension is useful as a fabric softener and brightner as ;~
- well as a stain remover.
Example IV
The general procedure of Example III was repeated in - a series of runs with the exception of reducing the amount of laundry detergent to between one half and one eighth of the recommended amount employed in Example III. It was found that only one-fourth as much laundry detergent was required when washing clothing in the presence of a catalytic amount of the catalyst.
Example V
The general procedures of Examples III and IV were repeated in a series of runs with the exception ' :-*Trademark -B
.. . . . . .
of using the catalysts prepared ~ln accordance with Example II
The catalysts of Example II were found to be active and produced comparable results.
Example VI
A catalyst suspension was prepared in accordance with the procedure of Example I~ The water content was removed by evaporation to produce a dried catalyst concentrate.
The dried catalyst concentrate and commercially available laundry detergent (Tide-XK *) are admixed in propor-tions to provide 1 weight percent of the catalyst in the re-sulting catalyzed surface active composition. A portion of the admixture is tested following the general washing procedure of Example III. The admixture is as effective in washing soiled clothing as separate additions of catalyst and detergent.
Example VII
A catalyst suspension was prepared following the general procedure of Example I and then diluted with 1,000 . . .
volumes of water.
,~ White cloth was treated in accordance with prior art practices to prepare a standard stained and soiled cloth for - use in testing the effectiveness of laundry detergents. The cloth was saturated with an admixture of soil, mustard, catsup, milk, grape juice, vegetable oil, mineral oil and bacon grease. -The ';'- ;:
*Trademark - 26 -.;
'.
: , .
admixture was dried and the initially white cloth took on a dark brown color.
A portion of the stained and soiled cloth was ; washed in the diluted catalyst suspension prepared above using the recommended amount of ordinary laundry soap.
A standard household automatic washer and the recommended washing cycle were used.
A second portion of the stained and soiled cloth was washed in soft tap water to which had been added the recommended amount of a commercially available heavy duty laundry deterqent. The manufacturer considered the laundry detergent to be the best formula available. The washer, washing cycle, and other variables were the same . . .
in the two runs with the exception of using laundry soap and catalyst in the first run, and the heavy duty laundry detergent without catalyst in the second run.
Following washing, the two test cloths were dried and examined in daylight. The cloth washed in the first run with ordinary laundry soap and diluted catalyst suspension was substantially the same color as the original white cloth. The cloth washed in the second run with heavy duty detergent without catalyst was somewhat lighter in color than the stained and soiled cloth, but markedly darker in color than the washed cloth from the first run. It was obvious that the stains and 10;~9610 soil were not removed effectively from the cloth washed in the second run, whereas they were in the cloth washed in the first run.
Example VIII
A catalyst suspension was prepared following the general procedure in Example I and then diluted with 1,000 volumes of water. The resulting dilute solution is referred to as "catalytic solution/1000" in this Example and in Example IX, and it was used in the following test:
A standard household automatic washer and the :
recommended washing cycle was used. A representative family wash was also used consisting o~ baby diapers, bibs, and other articles of clothing for a mechanics family. The housewife used 1/4 cup of Tide XK * and 1/2 cup of "catalytic solution/1000".
She used no bleach or fabric softener. The Tide XK~* and catalyst were added at the start of the washing cycle. The -;.. :
results were as good as in similar washes using 1 1/3 cups of Tide XK *, a chlorine bleach, and a fabric softener.
Example IX
.
A woman whose husband worked in the slaughter room of a meat packing plant, was unable-to clean her husband's work clothes of blood and slime stains when using the recommended amount of a commercial detergent and following the recommended ; washing cycle. In this test, she washed in her usual manner with the exception of using ': :
' * Trademarks ; - 28 -. . .
1039610 _ _ only 1/3 of the amount of detergent previously used, and 1/2 cup of "catalyst solution/1000". Surprisingly, even the dried in stains were removed and the washed clothing was free of all blood and slime stains.
~,.
. .
''' ` ' '' : `
,~ t .
_ ~9 _ . . . ,, ~
1Ø The alkali metal silicate should be admixed with the aqueous medium in an amount of about 0.05-2 moles per liter, preferably about 0.1-1 mole per liter, and for still better results about 0.2-0.5 mole per liter. For best results, the alkali metal silicate should be an . ~.. ...
1039610 !, ' alkali metal meta-silicate having an alkali metal oxide to silicon dioxide ratio of about 1:1, and it :` should be admixed with the aqueous medium in an amount to provide about 0.2-0.3 mole per liter, e.g., about ' 0.25 mole per li-ter.
Examples of sources of calcium ion and magnesium ion for use in preparing the aqueous solution ~ .
include mineral acid salts such as the halides, sulfates, bisulfates, nitrites, and nitrates of calcium and magnesium. The chlorides are usually the preferred halides, and both calcium and magnesium chloride are soluble and may be used. Magnesium sulfate and ; bisulfate are soluble and often are the preferred sources of magnesium ion. Calcium sulfate is only slightly soluble in water and usually is not a preferred source of calcium ion, but calcium bisulfate is somewhat more soluble. While calcium and magnesium nitrite or nitrate are soluble in water and may be used, these ,~ substances are not preferred in most instances. The sources of calcium ion and magnesium ion are dissolved , in the aqueous medium in amounts to provide calcium ion and magnesium ion within the above ranges. Complete - ionization is assumed when calculating the quantities `:
,~.
~ I
~039610 to be dissolved and any desired order of addition is satisfactory. For example, the source of calcium ion may be added to the aqueous medium before, during or after the source of magnesium ion.
The alkali metal silicate to be admixed with the aqueous medium is preferably a water soluble sodium ~~~~~
or potassium silicate having an alkali metal oxide (M20) to silicon dioxide (SiO2) mole ratio between about 0.9:1.0 and less than 2.0:1.0, and preferably between about 0.9:1.0 and 1.2:1Ø The best results are usually obtained with an alkali metal metasilicate having an alkali metal oxide to silicon dioxide ratio of about 1:1. Hydrated alkali metal silicates dissolve faster and should be used for best results when the alkali -- -metal silicate is added in solid form. In instances - where an anhydrous alkali metal silicate is used, it may be desirable to dissolve it in water and then add the solution to the aqueous medium. Sodium metasilicate is preferred and usually a hydrated sodium metasilicate . such as the pentahydrate gives the best results.
.~ i ;-~ Carbonate ion and/or bicarbonate ion should not be present in the aqueous medium in substantial concentrations as the calcium ion and magnesium ion are -~ precipitated in the form of their respective carbonates.
25 The free carbonate ion and/or bicarbonate ion concentra- -tions in~the aqueous medium should not exceed about 10 -~~~~
~:`
_ 13 ., , .
~03s6la ; ., parts per million by weight based upon the combined weight of the water and the ingredients added thereto and for this reason, the alkali metal silicates should be substantially free of carbonate ion and bicarbonate ion. A small amount of preciptated calcium carbonate and/or magnesium carbonate may be present in the aqueous medium provided additional calcium ion and magnesium ion are available to meet the above defined concentrations.
Distilled water and/or deionized water are usually preferred over a natural or untreated water when preparing the aqueous medium. In instances where water is used which contains substantial initial concentrations of alkaline earth metal ions, then this should be taken into consideration in calculating the amounts of the sources of calcium ion and magnesium ion which are " necessary to arrive at the final concentrations previously ; discussed.
An electrolyte which aids in the preparation of colloidal suspensions may be present in the aqueous medium at the time of admixing the alkali metal silicate therewith. Examples of electrolytes include those used in preparing prior art colloidal suspensions such as the alkali metal halides,sulfates and bisulfates.
Sodium chloride, sodium sulfate and sodium bisulfate are usually preferred. The electrolyte should be added in . .
. ~
" 1039610 small amounts such as, for example, about 0.00001-0.1 mole per liter, but often larger or smaller amounts may be present. ~ _ The conditions under which the alkali metal silicate is admixed with the aqueous medium and reacted ` with the sources of calcium ion and magnesium ion are ~; not critical provided the reaction mixture is maintained --in the liquid phase. The reaction temperature may be, for example, between the freezing point and boiling point of water under the existing pressure conditions. At atmospheric pressure, the temperature is usually about ~ _ 10-90C and often a more convenient temperature is about 20-50C. In many instances, ambient or normal room temperature is satisfactory.
The degree of agitation is not critical, and mild to vigorous agitation may be employed during addition of the alkali metal silicate. For the best results, the aqueous medium should be agitated sufficiently to assure ;
. .
rapid and uniform admixing of the alkali metal silicate.
After completing the addition of the alkali metal silicate, when desired the agitation may be continued for a sufficient period of time to assure complete reaction and aging of the resulting colloidal suspension, such ' _ ` as for approximately 1-5 minutes to one hour or longer.
Upon admixing the alkali metal silicate with ., - .
- the aqueous medium, it takes on a turbid appearance but in most instances no significant amount of visible ~ -precipitate is formed. The colloidal suspension of the reaction product thus produced should be strongly basic and may have a pl-l value of, for example, approximately ~ .. _._. . . .,.. . _ .. . . .. _ _ 103g610 10-14 and preferably about 11-13, and for hest results about 12. In view of this, the initial pH value of the aqueous medium containing the dissolved sources of calcium .
ion and magnesium ion is of importance and should be about 6-9 and preferably about 7-8. When necessary, it is possible to adjust the pH value of the aqueous medium to the foregoing levels either before during or after :_ - addition of the alkali metal silicate by adding bases such as sodium or potassium hydroxide, or mineral acids - 10 such as sulfuric or hydrochloric acid.
The colloidal suspension may be stored for .,.
;: several weeks or longer while awaiting the further .:
treatment described hereinafter. In instances where -~ the colloidal suspension is to be stored over a substantial period of time, the pH value should be maintained at the above described level and the storage vessel is preferably a tightly capped polyethylene bottle or other inert plastic container which prevents the contents from absorbing carbon dioxide from the atmosphere.
The colloidal suspension of the reaction product is not suitable for use as a catalyst as prepared and it should be agitated sufficiently in the presence of a micelle-forming surfactant to form catalyst-containing micelles. The degree of agitation, the length of the agitation period, and the amount of the micelle-forming surfactant that is present in the colloidal :. .
. . .
~039610 .
suspension are controlled at levels favorable to the formation of micelles. For example, the surfactant may be present in an amount of about 0.001-0.1 mole per liter and preferably about 0.03-0.07 mole per liter for most , 5 surfactants. Smaller or larger amounts may be effective -- with some surfactants such as 0.0001 mole per liter or less, or 0.2 mole per liter or more. About 0.05 mole per liter often gives the best results with many surfactants.
The minimum period of agitation and the minimum 10 degree of agitation that are required for micelle formation varies somewhat with temperature and the type and amount of surfactant. As is well understood in this art, gradually increasing these variants in the presence of an effective amount of the micelle-forming surfactant 15 will result in micelle formation when the proper levels are reached. As a general rule, longer periods of agitation and/or more vigorous agitation are required to form micelles at lower temperatures approaching the t freezing point of the colloidal suspension than at higher 20 temperatures approaching the boiling point. In instances where the aqueous suspension has a temperature of approximately 50-90C., then mild agitation over a perio~
of about 10-60 minutes is satisfactory. Often longer or shorter periods of mild to vigorous agitation may be 25 employed such as from about 1-5 minutes to several hours ~. ._ -"' ~03g610 at temperatures vaxying,respectively, between the boiling point and the freezing point. When desired, the agitation may be continued long after the catalyst containing micelles are formed as continued agitation does not seem to have an adverse effect.
As a general rule, the micelle-forming surfactants known in the prior art may be used in practicing the present invention. Micelle-forming surfactants used in the emulsion polymerization of monomeric organic compounds are discolsed in .:
the text Synthetic Rubber, by G. S. Whitby, et al, ~ohn Wiley & Sons Incorporated, New York (1954), and surface active agents ~k in general are disclosed on pages 418-424 of the text Organic ChemistrY, Fieser and Fieser, 2nd Edition, Reinhold Publishing Corporation, ~ew York, New York (1950). Examples of surfactants disclosed in the above texts include the alkali metal soaps of long chain fatty acids, and especially the sodium and potassium soaps of fatty acids containing about 14-25 carbon atoms and preferably about 16-18 carbon atoms, and the sodium and potassium soaps of the rosin acids, abietic acid and the derivatives thereof. Other micelle-forming surfactants include fats and oils such as corn oil, cotton seed oil, castor oil, soy bean oil and safflower oil which have been fully or part-ially saponified with alkali metal bases to . .
` ~ , , .
'," , .
:. V
~` ~039610 produce mixtures inclu ng saponified long chain fatty acids, the mono- or di-glycerides thereof, and glycerin.
Examples of synthetic micelle-forminy surfactants include the sulfonates of long chain alcohols prepared by hydrogenation of naturally ocurring fats and oils of the above types and especially sulfonated long chain alcohols containing about 10-20 and preferably about 12-14 carbon atoms, the alkali metal salts of the monosulfonates of monoglycerides such as sodium glyceryl monolaurate sulfonate, the sulfonates of succinic acid esters such as dioctyl sodium sulfcsuccinate and the alkylaryl alkali metal sulfonates. Specific examples of presently preferred micelle-forming surfactants include sodium and potassium sulforicinoleate, tetrahydronaphthalene sulfonate, octahydroanthracene sulfonic acid, butyl naphthalene sulfonic acid, sodium xylene sulfonate, alkyl benzene sulfonic acid and potassium benzene sulfonate.
Sulfated long chain hydroxycarboxylic acids containing about 14-25 carbon atoms and preferably about 16-18 carbon atoms, and sulfated fats and oils containing hydroxycarboxylic acids of this type produce exceptionally good micelle-forming surfactants. At least 25% of the hydroxyl groups and preferably at least 50% should be sulfated, and up to 95-100% may be sulfated. It is usually preferred that the sulfated oils and/or long chain - hydroxycarboxylic acids be neutralized with an alkali metal , .
. _ .:' ~, .
~039610 _ base, and that the corresponding alkali metal salts be added to the colloidal suspension in the form of an aqueous solution. The aqueous solution may contain at least 25%
of water and preferably at least 35-40% by weight. Much `~ 5 larger percentages of water may be present when desired --~ such as 75-80% or more by weight.
A very active catalyst is produced when using sulfated castor oil as the micelle-forming surfactant (Turkey Red oil.) Sulfated castor oil which has been purified sufficiently to be of U.S.P. or medicinal grade produces an exceptionally active catalyst. For the best results, the castor oil is reacted with about an equal - weight of concentrated sulfuric acid (e.g., 20% by weight) at a temperature of approximately 25-30C. The mixture may be reacted for about two hours with stirring and is then neutralized with sodium hydroxide solution. The reaction mixture separates into three layers, i.e., an upper layer which is a water solution, an intermediate or oily layer, and a white curdy precipitate. The intermediate oily layer is separated from the upper and lower layers, and b may ke added to the colloidal suspension as the micelle-forming surfactant in an amount, for example, of 0.001-0.1 mole per liter, and preferably about 0.005 mole per liter.
The activity of the catalyst may be increased very markedly by cooling the aqueous catalyst suspension to a temperature approaching the freezing point such as '"
;~' about 0-10C., and then warming over one or more cycles.
For best results, the aqueous catalyst suspension should : be frozen and thawed over one or more cycles. The reason for the increased catalytic activity is not fully ~~ ~
understood at the present time but cooling and then -warming the aqueous catalyst suspension seems to increase the concentration of the catalyst-containing micelles and/or increases the catalytic activity thereof. -~-~
The aqueous suspension of the catalyst contains lG a relatively small percentage by weight of the active - catalyst as produced. When desired, it may be concentrated by evaporating a portion of the water to produce a concentrated liquid catalyst suspension which may be stored and used more conveniently. It is also possible to prepare a dry catalyst concentrate by evaporating substantially - all of the water. The preferred method of producing the dry catalyst concentrate is by flash evaporation using a technique analogous to that employed in preparing powdered milk. The catalyst concentrates produced upon partial or complete evaporation of the water content of the intially prepared aqueous suspension may be reconstituted by addition of water with little or no .
loss of catalytic activity. Preferably, the water is added to the dry catalyst concentrate under sufficiently vigorous conditions of agitation to assure that the ~ ,~
, ' .
'1039610 catalyst micelles are resuspended and uniformly distributecd.
The aqueous catalyst suspension may be used as produced in practicing the invention, but preferably it is diluted with approximately lO0-lO,000 parts by weight of water and then used. For better results, the catalyst suspension should be diluted with about 250-2,000 parts `~
by weight of water before use, and for best results it should be diluted with about S00-l,000 parts by weight of water before use. The surface active agent may be added thereto when desired as previously discussed. Alternatively the dry catalyst or liquid catalyst concentrate may be admixed with water and/or the surface active agent to provide an effective catalyst concentration in the quantities previously discussed. The weight of the catalyst is calculated on a dry solids basis, i.e., the weight of --the catalyst ingredients in the aqueous suspension as produced after removal of the water.
- The invention is further illustrated by the following specific examples.
EX~PLE I
This example illustrates one presently preferred process for preparing the novel catalyst used in practicing the invention.
Anhydrous calcium chloride in an amount of 0.66 gram and magnesium sulfate heptahydrate in an amount of 1.32 grams were dissolved in two liters of cleionized water with stirring and warming until solution was complcte.
Then 95 grams of sodium silicate pentahydrate having a ~-~ ~
molecular ratio of sodium oxide to silicon dioxide of 1:1 were added to the solution with stirring and continued warming to produce a white colloidal suspension of the S reaction product.
After setting for 10 minutes, the colloidal - suspension was heated to 80C. and sulfated castor oil in an amount of 50 grams was added with stirring. The average molecular weight of the sulfated castor oil was 940 and it contained 50~ of water. The turbidity lessened somewhat as the colloidal suspension was heated at 80-90C. for one hour with vigorous stirring to produce catalyst micelles. The aqueous suspension of catalyst micelles thus prepared had a viscosity :
similar to that of water and it was used as the catalyst in certain Examples as noted hereinafter.
A dry or solid catalyst concentrate was prepared in a further run by evaporating water from the -~ r initially prepared aqueous catalyst suspension. The resulting dry catalyst concentrate was resuspended in water and there was no substantial loss of catalytic ; activity. In still other runs, the catalytic activity of the aqueous suspension of catalyst as initially ' prepared, the diluted aqueous suspension of catalyst, and the reconstituted aqueous catalyst suspension was enhanced by freezing and thawing.
EXAMPLE II.
This example illustrates the preparation of additional catalyst suspensions.
. ~;
~ 9610 Five suspensions of the catalyst were prepared from the same ingredients as used in Example I and following the general procedure of Example I. The ratios of ingredierlts were varied as follows:
Inqredient Amount of Ingredient Run 1 Run 2 Run 3 Run 4 Run 5 Deionized water 2 1 1.5 1 1.5 1 1.5 1 0.25 1 CaC12 0.66 g 0.5 g 0.5 g 1.0 g 0.5 g MgS04 . 7H20 1.32 g 1.0 g 1.0 g 2.0 g 1.0 g Na2 SiO3 5H20 165 g 132 g 71 g 185 g 71 g Sulfated Castor 100 ml 150 ml 150 ml 200 ml 150 ml oil (approximately 50% by weight H20) The catalyst suspensions prepared by the above five runs were used in certain examples as noted herein~fter.
-~ Example III
This example illustrates the use of the catalyst ,,, prepared in accordance with Example I in treating fabrics.
..
A standard household automatic washer (9 pounds .
capacity) was llsed in obtaining the data for this example.
The recommended washing cycle for the stained fabrics was also used.
; In one run, an attempt was made to remove chocolate stains from a cotton shirt using commercially available laundry ~' detergents (laundry detergents sold under the trademarks Biz* and Tide-XK*) and an oxidizing agent (Clorox*). The cocolate stains were not removed by this treatment. However, ` chocolate stains were *Trademarks .
~ ' . , . - , . , " 1039610 easily removed in a second run when washing with a catalytic amount of the diluted catalyst suspension prepared in accordance with Example I.
In subsequent runs, six fluid ounces of the catalyst suspension prepared in accordance with Example I were added to ;
the washer along with the recommended amount of cold water, laundry detergent and stained clothing. Blood, grape juice, catsup, grease and grass stains were easily removed. It was not possible to remove stains of this type when using only a laundry detergent and Clorox *.
The fabrics washed in water containing the catalyst suspension were softer and brighter. Thus, the catalyst suspension is useful as a fabric softener and brightner as ;~
- well as a stain remover.
Example IV
The general procedure of Example III was repeated in - a series of runs with the exception of reducing the amount of laundry detergent to between one half and one eighth of the recommended amount employed in Example III. It was found that only one-fourth as much laundry detergent was required when washing clothing in the presence of a catalytic amount of the catalyst.
Example V
The general procedures of Examples III and IV were repeated in a series of runs with the exception ' :-*Trademark -B
.. . . . . .
of using the catalysts prepared ~ln accordance with Example II
The catalysts of Example II were found to be active and produced comparable results.
Example VI
A catalyst suspension was prepared in accordance with the procedure of Example I~ The water content was removed by evaporation to produce a dried catalyst concentrate.
The dried catalyst concentrate and commercially available laundry detergent (Tide-XK *) are admixed in propor-tions to provide 1 weight percent of the catalyst in the re-sulting catalyzed surface active composition. A portion of the admixture is tested following the general washing procedure of Example III. The admixture is as effective in washing soiled clothing as separate additions of catalyst and detergent.
Example VII
A catalyst suspension was prepared following the general procedure of Example I and then diluted with 1,000 . . .
volumes of water.
,~ White cloth was treated in accordance with prior art practices to prepare a standard stained and soiled cloth for - use in testing the effectiveness of laundry detergents. The cloth was saturated with an admixture of soil, mustard, catsup, milk, grape juice, vegetable oil, mineral oil and bacon grease. -The ';'- ;:
*Trademark - 26 -.;
'.
: , .
admixture was dried and the initially white cloth took on a dark brown color.
A portion of the stained and soiled cloth was ; washed in the diluted catalyst suspension prepared above using the recommended amount of ordinary laundry soap.
A standard household automatic washer and the recommended washing cycle were used.
A second portion of the stained and soiled cloth was washed in soft tap water to which had been added the recommended amount of a commercially available heavy duty laundry deterqent. The manufacturer considered the laundry detergent to be the best formula available. The washer, washing cycle, and other variables were the same . . .
in the two runs with the exception of using laundry soap and catalyst in the first run, and the heavy duty laundry detergent without catalyst in the second run.
Following washing, the two test cloths were dried and examined in daylight. The cloth washed in the first run with ordinary laundry soap and diluted catalyst suspension was substantially the same color as the original white cloth. The cloth washed in the second run with heavy duty detergent without catalyst was somewhat lighter in color than the stained and soiled cloth, but markedly darker in color than the washed cloth from the first run. It was obvious that the stains and 10;~9610 soil were not removed effectively from the cloth washed in the second run, whereas they were in the cloth washed in the first run.
Example VIII
A catalyst suspension was prepared following the general procedure in Example I and then diluted with 1,000 volumes of water. The resulting dilute solution is referred to as "catalytic solution/1000" in this Example and in Example IX, and it was used in the following test:
A standard household automatic washer and the :
recommended washing cycle was used. A representative family wash was also used consisting o~ baby diapers, bibs, and other articles of clothing for a mechanics family. The housewife used 1/4 cup of Tide XK * and 1/2 cup of "catalytic solution/1000".
She used no bleach or fabric softener. The Tide XK~* and catalyst were added at the start of the washing cycle. The -;.. :
results were as good as in similar washes using 1 1/3 cups of Tide XK *, a chlorine bleach, and a fabric softener.
Example IX
.
A woman whose husband worked in the slaughter room of a meat packing plant, was unable-to clean her husband's work clothes of blood and slime stains when using the recommended amount of a commercial detergent and following the recommended ; washing cycle. In this test, she washed in her usual manner with the exception of using ': :
' * Trademarks ; - 28 -. . .
1039610 _ _ only 1/3 of the amount of detergent previously used, and 1/2 cup of "catalyst solution/1000". Surprisingly, even the dried in stains were removed and the washed clothing was free of all blood and slime stains.
~,.
. .
''' ` ' '' : `
,~ t .
_ ~9 _ . . . ,, ~
Claims (18)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a method of washing soil from soiled textile material wherein the textile material is intimately contacted with water containing a surface active agent, the improvement in combination therewith comprising washing the soil from the soiled textile material with water containing the said surface active agent and a catalyst, the catalyst being present in a catalytic-ally effective amount which increases the rate of re-moval of the soil from the textile material, the catalyst being prepared by a process comprising admixing a water soluble alkali metal silicate with an aqueous medium containing a dissolved substance which is a source of calcium ion and a dissolved substance which is a source of magnesium ion, the aqueous medium containing said dissolved substances in amounts to provide between about 1 x 10-4 and 1 x 10-1 mole per liter each of calcium ion and magnesium ion, the aqueous medium containing said dissolved substances in amounts to provide a molar ratio of calcium ion to magnesium ion between about 2.0:1.0 and 1.0:2.0, the alkali metal silicate having an alkali metal oxide to silicon dioxide ratio between about 0.9:1.0 and less than 2.0:1.0 and being admixed with the aqueous medium in an amount of about 0.05-2 moles per liter.
reacting the alkali metal silicate with said dissolved substances providing calcium ion and magnesium ion to produce an aqueous colloidal suspension of particles of the reaction product, admixing a micelle-forming surfactant with the aqueous medium in an amount to form catalyst micelles comprising said colloidal particles upon agitating the aqueous medium, and agitating the aqueous medium containing the colloidal particles and surfactant to form said catalyst micelles.
reacting the alkali metal silicate with said dissolved substances providing calcium ion and magnesium ion to produce an aqueous colloidal suspension of particles of the reaction product, admixing a micelle-forming surfactant with the aqueous medium in an amount to form catalyst micelles comprising said colloidal particles upon agitating the aqueous medium, and agitating the aqueous medium containing the colloidal particles and surfactant to form said catalyst micelles.
2. The method of Claim 1 wherein in the process for prepar-ing the catalyst said ratio of calcium ion to magnesium ion is between about 1.5:1.0 and 1.0:1.5.
3. The method of Claim 1 wherein in the process for prepar-ing the catalyst, said ratio of calcium ion to magnesium ion is about 1.0:1Ø
4. The method of Claim 1 wherein in the process for prepar-ing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 1 x 10-3 and 6 x 10-3 mole per liter each of calcium ion and magnesium ion.
5. The method of Claim 1 wherein in the process for prepar-ing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 2.5 x 10-3 and 3.0 x 10-3 mole per liter each of calcium ion and magnesium ion.
6. The method of Claim 1 wherein in the process for prepar-ing the catalyst, about 0.2-0.5 mole per liter of the alkali metal silicate is admixed with the aqueous medium.
7. The method of Claim 1 wherein in the process for prepar-ing the catalyst, the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio between about 0.9:1.0 and 1.2:1Ø
8. The method of Claim 1 wherein in the process for prepar-ing the catalyst, the alkali metal silicate is alkali metal meta-silicate having an alkali metal oxide to silicon dioxide ratio of about 1.0:1Ø
9. The method of Claim 1 wherein in the process for prepar-ing the catalyst, about 0.01-0.1 mole per liter of the surfactant is admixed with the aqueous medium.
10. The method of Claim 1 wherein in the process for prepar-ing the catalyst, the surfactant comprises sulfated castor oil.
11. The method of Claim 1 wherein in the process for prepar-ing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 1 x 10-3 and 6 x 10-3 mole per liter each of calcium ion and magnesium ion, the ratio of calcium ion to magnesium ion is between about 1.5:1.0 and 1.0:1.5, about 0.2-0.5 mole per liter of the alkali metal silicate is admixed with the aqueous medium, and the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio between about 0.9:1.0 and 1.2:1Ø
12. The method of Claim 1 wherein in the process for prepar-ing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 2.5 x 10-3 and 3.0 x 10-3 mole per liter each of calcium ion and magnesium ion, the aqueous medium con tains about equimolar amounts of calcium ion and magnesium ion, about 0.2-0.3 mole per liter of the alkali metal silicate is ad-mixed with the aqueous medium, and the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio of about 1.0:1Ø
13. The method of Claim 12 wherein in the process for prepar-ing the catalyst, the alkali metal metasilicate is sodium meta-silicate having an alkali metal oxide to silicon dioxide ratio of about 1.0:1Ø
14. The method of Claim 12 wherein in the process for prepar-ing the catalyst, about 0.01-0.1 mole per liter of the surfactant is admixed with the aqueous medium.
15. The method of Claim 14 wherein in the process for prepar-ing the catalyst, the surfactant comprises sulfated castor oil.
16. The method of Claim 15 wherein in the process for prepar-ing the catalyst, the alkali metal metasilicate is sodium meta-silicate having a sodium oxide to silicon dioxide ratio of about 1.0: 1Ø
17. The method of Claim 16 wherein in the process for prepar-ing the catalyst, at least 25 percent of the hydroxy groups of the castor oil are sulfated, and about 0.03-0.07 mole per liter of the sulfated castor oil is admixed with the aqueous medium.
18. The method of Claim 12 wherein in the process for prepar-ing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide about 2.9 x 10-3 mole per liter of calcium ion and about 2.7 x 10-3 mole per liter of magnesium ion, about 0.25 mole per liter of sodium metasilicate having a sodium oxide to silicon dioxide ratio of about 1.0:1.0 is admixed with the aqueous medium, the aqueous medium contains not more than 10 parts per million by weight of carbonate ion and bicarbonate ion, the surfactant comprises sulfated castor oil and at least 50 percent of the hydroxy groups of the castor oil are sulfated, and about 0.05 mole per liter of the sulfated castor oil is admixed with the aqueous medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA240,841A CA1039610A (en) | 1975-12-01 | 1975-12-01 | Method of washing textile materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA240,841A CA1039610A (en) | 1975-12-01 | 1975-12-01 | Method of washing textile materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1039610A true CA1039610A (en) | 1978-10-03 |
Family
ID=4104635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA240,841A Expired CA1039610A (en) | 1975-12-01 | 1975-12-01 | Method of washing textile materials |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1039610A (en) |
-
1975
- 1975-12-01 CA CA240,841A patent/CA1039610A/en not_active Expired
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