CA1190005A - Peroxygen bleaching composition - Google Patents
Peroxygen bleaching compositionInfo
- Publication number
- CA1190005A CA1190005A CA000417353A CA417353A CA1190005A CA 1190005 A CA1190005 A CA 1190005A CA 000417353 A CA000417353 A CA 000417353A CA 417353 A CA417353 A CA 417353A CA 1190005 A CA1190005 A CA 1190005A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- bleaching
- detergent
- water
- peroxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
Abstract
Abstract or The Disclosure A bleaching and laundering composition comprising a peroxygen compound, an activator comprising phthalic anhy-dride and diethylene triamine pentamethylene phosphonic acid and/or a water-soluble salt thereof. A method of bleaching and laundering soiled and/or stained materials with the afore-said bleaching composition is also described.
Description
~ 2301-1199 BA G OUND O rllF INvENrIoN
This invention relates, in general, to bleaching and laundering compositions and their applica-tion to laundering operations. More specific-ally, this invention relates to bleaching and ]aundering compositions con-taining a peroxygen compound, an organic activa-tor for said peroxygen COIII-pound comprising pht}lalic anhydride and a defined phosphonate compowld.
Bleaching compositions which release active oxygen in the laundry solution are extensively described in the prior art and commonly used in domestic laundering operations. In general, such bleaching conlpositions con-tain peroxygen compounds, such as, perborates, percarbonates, perphosphates and the like which promote the bleaching activity by forming hydrogen per-oxide in aqueous solution. A major drawback attendant to the use of such peroxygen compounds is that they are not optimally effective at the relatively low washing temperatures employed in most household washing machines in the United States, i.e., temperatures in the range of 80 to 130 F. By way of comparison, European wash temperatures are generally substantially higher extending over a range, typically, from 90 to 200 F. However, even in Europe and those other countries which generally presently employ near boil-ing washing temperatures, there is a move to lower temperature laundering.
In an effort to enhance the bleaching activity of peroxygen bleaches, the prior art has employed materials called activators in combina-tion with the peroxygen compounds. It is generally believed that the inter-action of the peroxygen compound and the activator results in the formation of peroxyacid which is the active species for bleaching. Numerous compounds have been proposed in the art as activators for peroxygen bleaches among which are included carboxylic acid anhydrides such as those disclosed in U.S.
Patent Nos. 3,298,775; 3,338,839 and 3,532,634; carboxylic esters such as disclosed in U.S. Patent No. 2,995,905; N-acyl compounds such as those des-cribed in U.S. Patent Nos. 3,912,648 and 3,919,102; cyanoamines such as des-cribed in U.S. Patent No. 4,199,466; and acyl sulfonamides such as disclosed in U.S. Patent No. 3,245,913.
U.S. No. 329,534 I.R. 3872 -2-Tlle use of chela-ting agents in bleachirlg compositions is descr:ibed in the patent l:iterature. U.S. Patent No. 3,2~3,378 to Stoltz discloses a b]eaching composition containing a hypoch:Lorite or peroxide type bleaching material and a chelating agent to sequestcr metal ca-tions. U.S. Patent No.
~,225,~52 to Leigh disclos0s the combinatlon of specified classes of chelat-ing agents (among which are phosphonate compounds) with peroxygerl compounds and an organic activator for the purpose of suppressing the decomposition of the peroxygen compound in the bleach composi-tion; specificallyl inhibiting the unwanted reaction of the peroxygen compound with a peroxyacid to form the corresponding carboxylic acid, oxygen and water. The paten-tee, however, states that the eEficacy of such chelating agents is restricted to certain peroxygen compound/activator systems. Specifically, at column 2, beginning at line 63, the patentee states that certain activators, such as phthalic anhydride, "which form with the percompound in solution a peracid having a double bond between the carbon atoms in the ~,~' position to the carbonyl groups of the corresponding anhydride ring", are excluded from use in the bleaching compositions described in the patent because of their instability.
Phthalic anhydride has, however, been disclosed in the art as an activator for peroxygen compounds, although it apparently was ineffective for such purpose. Specifically, U.S. Patent No. 3,338,839 is directed to a bleaching composition containing as an activator a mixed carboxylic acid anhydride. In Example I of the patent, phthalic anhydride was used as an activator in a comparative test run, the results of which illustrated the ineffectiveness of phthalic anhydride as an activator when used alone, as compared to the mixture of activators used in the bleaching composition of the patent.
SUMMARY OF TIIE INVENTION
The present invention provides a bleaching composition comprising a peroxygen compo~md, an ac-tivator for said peroxygen compound consisting essentially of phthalic anhydride, and diethylene triamine pentamethylene o~
phosphonic acid aIlcl/or a water-soluble salt thereo:~. Ihe detergent bleach-ing composition of the invention comprises the above-defined bleaching com-position in combination with a surEace active detergent, and preferably a detergency builder salt. In accordance with the process of the invention, bleaching of stained and/or soiled materials is effected by contacting such materials with an aqueous solution oE the above-defined compositions.
DETAILED DESCRIPTION 0~ ~-IE IN ENTION
The peroxygen compounds use:Eul in the present invention include hydrogen peroxide and compounds that release hydrogen peroxide in aqueous mediaJ such as, alkali metal perborates, e.g., sodium perborate and potas-sium perborate, alkali metal perphosphates, such as sodium perphosphate and potassium perphosphate, alkali metal persilicates, such as, sodium persili-cate and potassium persilicate, and alkali metal percarbonates, such as sodium percarbonate and potassium percarbonate. The alkali metal perborates are usually preferred because of their commercial availability and relatively low cost.
The peroxygen compound is generally present in the bleaching com-position relative to the activator in a molar ratio of peroxygen compound to phthalic anhydride of about 1:10 to about 10:1, the preferred ratio being from about 1:2 to about 3:1. It will be appreciated that the concentration of phthalic anhydride will depend on the concentration of the peroxygen com-pound, which in turn is governed by the degree of bleaching desired. The peroxygen compound is typically present in the bleaching composition in an amount ranging from about 1% to about 50%, by weight, preferably 3% to 25%, and most preferably, 5% to 20%, by weight of the bleaching composition.
The amount of bleaching composition added to the wash solution is generally selected to provide an amount of peroxygen compound within the range corresponding to about 3 to 100 parts of active oxygen per million parts o:E the wash solution. Thus, a bleach detergent composition intended for use at a concentration of 1.5g. per liter o:E wash solution and which con-tains, Eor example, 7% of sodium perborate tetrahydrate having an ac-tive oxygen (AØ) content of 10% will provide 10.5 ppm A.~.; similarly, a com-position containing 20% of such perborate compound will, under the same con-ditions of useJ provide 30 ppm AØ
Diethylene triamine pentamethylene phosphollic acid (conveniently referred to herein as "DTPMP") and/or one or more of its water-soluble salts may be employed in the bleaching composi-tions of the invent:ion. Among the salts of DTPMP, the sodium, potassium and ammonium salts are generally pre-ferred because of their relatively greater solubility and ease of prepara-tion. DTPMP is a known chelating agent but it is believed that its :Eunctionin the present bleaching composition is more than simply sequestering metal-lic impurities present in the aqueous media employed in the washing and/or bleaching operation. [t apparently increases bleaching efficacy by inhibit-ing the peroxyacid-consuming side reaction which result in deple*ion of the active bleaching species which would otherwise be available for useful pur-poses. In any event, regardless of the actual mechanism of its operation, the presence of DTPMP (or a salt thereof) in combination with the peroxygen compound/activator system of the present invention provides a bleaching solu-tion which consumes less active oxygen than solutions obtained from similar compositions without DTPMP, and yet provides comparable stain removal. The concentration of DTPMP and/or its salt derivatives in the bleaching composi-tion may vary from about 0.1% to about 10%, by weight, of the total composi-tion, but preferably is present in an amount from 0.5% to 2% by weight of the total composition.
The selected peroxygen compound, phthalic anhydride and DTPMP and/
OI' its water-soluble salt may be formulated as a separate bleach product, or alternatively, may be employed in a built detergent composition. Accordingly, the bleaching composition of the invention may include conventional additives used in the fabric washing art, such as, binders, fillers, builder salts, proteolytic enzymes, optical brighteners, fabric softeners, perfumes, dyes, corrosion inh:ibitors, ant:i-redeposi-tion agents, foam stabilizers and the like, all of wilich may be added in varying quantities depending on the de-sired properties of the bleaching composi-tion and their compatability with such composition. ~dditionally, the bleaching compositions of the invention may be incorporated into laundering detergent compositions containing sur-face active agents, such as, anionic, cationic, nonionic, ampholytic and zwitterionic detergents and mixtures thereof.
When the instan-t bleaching compositions are incorporated into a conventional laundering composition and are thus provided as a fully-formulated detergent bleachlng composition, the latter composition will com-prise the following: from about 5 to 50%, by weightJ of the instan-t bleach-ing composition, from about 5 to 50%, by weight, of a detergent surface active agent, and from about 1 to 60%, by weight, of a detergency builder which can also function as a buffer to provide the requisite p~l range when the laundering composition is added to water. The balance of the composl-tion will predominantly comprise filler salts~ such as, sodium sulfate and potassium sulfate, minor additives, such as, optical brighteners, perfumes, dyes, anti-redeposition agents and the like, and water.
The anionic surface active agents useful in the present invention include those surface active or detergent compounds which contain an organic hydrophobic group containing generally 8 to 26 carbon atoms and preferably 10 to 18 carbon atoms in their molecular structure and at least one water-solubilizing group selected from the group of sulfonate, sulfate, carboxylate, phosphonate and phosphate so as to form a water-soluble detergent.
Examples of suitable anionic detèrgents include, for example, the water-soluble salts (e.g., the sodium, ammonium and alkanolammonium salts) of higher fatty acids or resin salts containing from about 8 to 20 carbon atoms and preferably 10 to 18 carbon atoms. Suitable fatty acids can be ob-tained from oils and waxes of animal or vegetable origin, for example, tallow, grease, coconut oil and mixtures thereof. Particularly useful are the sodium cmd potassium salts of the Eatty acid mixtures derived from coconut oil and tallow, Eor example, sodium coconut soap and potassium tallow soap.
The anionic class of detergents also includes the water-soluble sulfated and sulfonated detergents having an alkyl radical containing from about 8 to 26, and preferably from about 12 to 22 carbon atoms. (The term "alkyl" includes the alkyl portion oE the higher acyl radicals). Examples of the sulfonated anionic detergents are the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from about 10 to 16 carbon atoms in the hi.gher alkyl group in a straight or branched chain, such as, for example, the sodium, potassium and ammonium salts of higher alkyl benzene sulfonates~ higher alkyl toluene sulfonates and higher alkyl phenol sulfonates.
Other suitable anionic detergents are the olefin sulfonates includ-ing long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mix-tures of alkene sulfonates and hydroxyalkane sulfonates. The olefin sulfon-ate detergents may be prepared in a conventional manner by the reaction of SO3 with long chain olefins containing from about 8 to 25, and preferably from about 12 to 21 carbon atoms, such olefins having, the formula R~l-~-IR
wherein R is a higher alkyl group of 6 to 23 carbons and Rl is an alkyl group containing from about 1 to 17 carbon atoms or hydrogen to form a mix-ture of sultones and alkene sulfonic acids which is then treated to convert the sultones to sulfonates. Other examples of sulfate or sulfonate deter-gents are paraffin sulfonates containing from about 10 to 20 carbon atoms, and preferably from about 15 to 20 carbon atoms. The primary paraffin sul-fonates are made by reacting long chain alpha olefins and bisulfites. Paraf-fin sulfonates having the sulfonate group distributed along the paraffin chain are shown in U.S. Patent Nos. 2,503,280; 2,507,088; 3,260,7~1;
3,372,188; and German Patent No. 735,096. Other useful sulfate and sulfon-ate detergents include sodium and potassium sulfates of higher alcohols con-taining from about 8 to 18 carbon atoms, such as, for example, sodium lauryl sulfate and sodlum taLlow alcollol sulfa-te, sodium and potassium sal-ts of alpha-sulfoEatty acid esters containing about 10 to 20 carbon atoms in the acyl group, Eor example, methyl alpha-sulEomyristate and methyl alpha-sulfotallowate, ammonillm sulEates of mono- or di- glycerides of higher (C10 -C18) fatty acids, for example, stearic monoglyceride monosulEate; sodium and alkylol ammonium salts of alkyl polyethenoxy ether sulfates produccd by con-densing 1 to 5 moles of ethylene oxide with 1 mole of higher (C8 - C18) alcohol; sodium higher al]cyl (C10 - Cl8) glyceryl ether sulfonates; and sodium or potassiwD alkyl phenol polyethenoxy ether sulfates with about l to 6 oxyethylene groups per molecule and in which the alkyl radicals contain about 8 to 12 carbon atoms.
The suitable anionic detergents also include the C8 to C18 acyl sarcosinates (for example, sodium lauroyl sarcosinates), sodium and potas-sium salts of the reaction product of higher fatty acids containing 8 to 18 carbon atoms in the molecule esterified with isethionic acid, and sodium and potassium salts of the C8 - Cl8 acyl N-methyl taurides, for example, sodium cocyl methyl taurate and potassium stearoyl methyl taurate.
Anionic phosphate surfactants in which the anionic solubilizing group attached to the hydrophobic group is an oxyacid of phosphorous are also useful in the detergent compositions. Suitable phosphate surfactants are the sodium, potassium and ammonium alkyl phosphate esters such as (R-0)2P02M and ROP03M2 in which R represents an alkyl chain containing from about 8 to 20 carbon atoms and M represents a soluble cation. The compounds formed by including from about l to 40 moles of ethylene oxide in the fore-going esters, for example, [R-O(C2l-l40)n]2 P02M are also useful-The most highly preferred water-soluble anionic detergent com-pounds are the ammonium and substituted ammonium (such as mono, di and tri-ethanolamine), alkali metal (such as, sodium and potassium) and alkaline earth metal (such as, calcium and magnesium) salts of the higher alkyl ben-zene sulfonates, olefin sulfonates and higher alkyl sulfates. Among the ~9~
above-listed aniollics, the mos-t pre:Eerred are the sodium linear alky:l ben-zene sulfona-tes ~LAS).
The nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature). Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a :Eree hydrogen attached to the ni-trogen can be condensed with ethylene oxicle or with the polyhydration product thereof, polyethylene glycol, to form a nonionic detergent. The lengt}l of the hydro-philic or polyoxyethylene chain can be readily adjusted to achieve the de-sired balance between the hydrophobic and hydrophilic groups.
The nonionic detergents incl.ude the polyethylene oxide condensate of 1 mole of alkyl phenol containing from about 6 to 12 carbon atoms in a straight or branched chain configuration with about 5 to 30 moles of ethylene oxide, for example, nonyl phenol condensed wi-th 9 moles of ethylene oxide; dodecyl phenol condensed wi.th 15 moles of ethylene oxide; and dinonyl phenol condensed with 15 moles of ethylene oxi.de. Condensation products of the corresponding alkyl thiophenols with 5 to 30 moles of e~hylene oxide are also suitable.
The polar nonionic detergents useful in -the present invention are those in which the hydrophilic group contains a semi-polar bond directly be-tween two atoms, for example N-~O, P ~ O, As-~O, and S-~O. Such polar non-iOlliC detergents include:
1. Open-chain aliphatic amine oxides of the general formula RlR2R3N-~O wherein Rl is an alkyl, alkenylJ or monohydroxy-alkyl group containing from about 10 to 18 carbon atoms, and R2 ancl R3 are each an alkyl or monohydroxyalkyl group contain-ing from 1 to 3 carbon atoms.
This invention relates, in general, to bleaching and laundering compositions and their applica-tion to laundering operations. More specific-ally, this invention relates to bleaching and ]aundering compositions con-taining a peroxygen compound, an organic activa-tor for said peroxygen COIII-pound comprising pht}lalic anhydride and a defined phosphonate compowld.
Bleaching compositions which release active oxygen in the laundry solution are extensively described in the prior art and commonly used in domestic laundering operations. In general, such bleaching conlpositions con-tain peroxygen compounds, such as, perborates, percarbonates, perphosphates and the like which promote the bleaching activity by forming hydrogen per-oxide in aqueous solution. A major drawback attendant to the use of such peroxygen compounds is that they are not optimally effective at the relatively low washing temperatures employed in most household washing machines in the United States, i.e., temperatures in the range of 80 to 130 F. By way of comparison, European wash temperatures are generally substantially higher extending over a range, typically, from 90 to 200 F. However, even in Europe and those other countries which generally presently employ near boil-ing washing temperatures, there is a move to lower temperature laundering.
In an effort to enhance the bleaching activity of peroxygen bleaches, the prior art has employed materials called activators in combina-tion with the peroxygen compounds. It is generally believed that the inter-action of the peroxygen compound and the activator results in the formation of peroxyacid which is the active species for bleaching. Numerous compounds have been proposed in the art as activators for peroxygen bleaches among which are included carboxylic acid anhydrides such as those disclosed in U.S.
Patent Nos. 3,298,775; 3,338,839 and 3,532,634; carboxylic esters such as disclosed in U.S. Patent No. 2,995,905; N-acyl compounds such as those des-cribed in U.S. Patent Nos. 3,912,648 and 3,919,102; cyanoamines such as des-cribed in U.S. Patent No. 4,199,466; and acyl sulfonamides such as disclosed in U.S. Patent No. 3,245,913.
U.S. No. 329,534 I.R. 3872 -2-Tlle use of chela-ting agents in bleachirlg compositions is descr:ibed in the patent l:iterature. U.S. Patent No. 3,2~3,378 to Stoltz discloses a b]eaching composition containing a hypoch:Lorite or peroxide type bleaching material and a chelating agent to sequestcr metal ca-tions. U.S. Patent No.
~,225,~52 to Leigh disclos0s the combinatlon of specified classes of chelat-ing agents (among which are phosphonate compounds) with peroxygerl compounds and an organic activator for the purpose of suppressing the decomposition of the peroxygen compound in the bleach composi-tion; specificallyl inhibiting the unwanted reaction of the peroxygen compound with a peroxyacid to form the corresponding carboxylic acid, oxygen and water. The paten-tee, however, states that the eEficacy of such chelating agents is restricted to certain peroxygen compound/activator systems. Specifically, at column 2, beginning at line 63, the patentee states that certain activators, such as phthalic anhydride, "which form with the percompound in solution a peracid having a double bond between the carbon atoms in the ~,~' position to the carbonyl groups of the corresponding anhydride ring", are excluded from use in the bleaching compositions described in the patent because of their instability.
Phthalic anhydride has, however, been disclosed in the art as an activator for peroxygen compounds, although it apparently was ineffective for such purpose. Specifically, U.S. Patent No. 3,338,839 is directed to a bleaching composition containing as an activator a mixed carboxylic acid anhydride. In Example I of the patent, phthalic anhydride was used as an activator in a comparative test run, the results of which illustrated the ineffectiveness of phthalic anhydride as an activator when used alone, as compared to the mixture of activators used in the bleaching composition of the patent.
SUMMARY OF TIIE INVENTION
The present invention provides a bleaching composition comprising a peroxygen compo~md, an ac-tivator for said peroxygen compound consisting essentially of phthalic anhydride, and diethylene triamine pentamethylene o~
phosphonic acid aIlcl/or a water-soluble salt thereo:~. Ihe detergent bleach-ing composition of the invention comprises the above-defined bleaching com-position in combination with a surEace active detergent, and preferably a detergency builder salt. In accordance with the process of the invention, bleaching of stained and/or soiled materials is effected by contacting such materials with an aqueous solution oE the above-defined compositions.
DETAILED DESCRIPTION 0~ ~-IE IN ENTION
The peroxygen compounds use:Eul in the present invention include hydrogen peroxide and compounds that release hydrogen peroxide in aqueous mediaJ such as, alkali metal perborates, e.g., sodium perborate and potas-sium perborate, alkali metal perphosphates, such as sodium perphosphate and potassium perphosphate, alkali metal persilicates, such as, sodium persili-cate and potassium persilicate, and alkali metal percarbonates, such as sodium percarbonate and potassium percarbonate. The alkali metal perborates are usually preferred because of their commercial availability and relatively low cost.
The peroxygen compound is generally present in the bleaching com-position relative to the activator in a molar ratio of peroxygen compound to phthalic anhydride of about 1:10 to about 10:1, the preferred ratio being from about 1:2 to about 3:1. It will be appreciated that the concentration of phthalic anhydride will depend on the concentration of the peroxygen com-pound, which in turn is governed by the degree of bleaching desired. The peroxygen compound is typically present in the bleaching composition in an amount ranging from about 1% to about 50%, by weight, preferably 3% to 25%, and most preferably, 5% to 20%, by weight of the bleaching composition.
The amount of bleaching composition added to the wash solution is generally selected to provide an amount of peroxygen compound within the range corresponding to about 3 to 100 parts of active oxygen per million parts o:E the wash solution. Thus, a bleach detergent composition intended for use at a concentration of 1.5g. per liter o:E wash solution and which con-tains, Eor example, 7% of sodium perborate tetrahydrate having an ac-tive oxygen (AØ) content of 10% will provide 10.5 ppm A.~.; similarly, a com-position containing 20% of such perborate compound will, under the same con-ditions of useJ provide 30 ppm AØ
Diethylene triamine pentamethylene phosphollic acid (conveniently referred to herein as "DTPMP") and/or one or more of its water-soluble salts may be employed in the bleaching composi-tions of the invent:ion. Among the salts of DTPMP, the sodium, potassium and ammonium salts are generally pre-ferred because of their relatively greater solubility and ease of prepara-tion. DTPMP is a known chelating agent but it is believed that its :Eunctionin the present bleaching composition is more than simply sequestering metal-lic impurities present in the aqueous media employed in the washing and/or bleaching operation. [t apparently increases bleaching efficacy by inhibit-ing the peroxyacid-consuming side reaction which result in deple*ion of the active bleaching species which would otherwise be available for useful pur-poses. In any event, regardless of the actual mechanism of its operation, the presence of DTPMP (or a salt thereof) in combination with the peroxygen compound/activator system of the present invention provides a bleaching solu-tion which consumes less active oxygen than solutions obtained from similar compositions without DTPMP, and yet provides comparable stain removal. The concentration of DTPMP and/or its salt derivatives in the bleaching composi-tion may vary from about 0.1% to about 10%, by weight, of the total composi-tion, but preferably is present in an amount from 0.5% to 2% by weight of the total composition.
The selected peroxygen compound, phthalic anhydride and DTPMP and/
OI' its water-soluble salt may be formulated as a separate bleach product, or alternatively, may be employed in a built detergent composition. Accordingly, the bleaching composition of the invention may include conventional additives used in the fabric washing art, such as, binders, fillers, builder salts, proteolytic enzymes, optical brighteners, fabric softeners, perfumes, dyes, corrosion inh:ibitors, ant:i-redeposi-tion agents, foam stabilizers and the like, all of wilich may be added in varying quantities depending on the de-sired properties of the bleaching composi-tion and their compatability with such composition. ~dditionally, the bleaching compositions of the invention may be incorporated into laundering detergent compositions containing sur-face active agents, such as, anionic, cationic, nonionic, ampholytic and zwitterionic detergents and mixtures thereof.
When the instan-t bleaching compositions are incorporated into a conventional laundering composition and are thus provided as a fully-formulated detergent bleachlng composition, the latter composition will com-prise the following: from about 5 to 50%, by weightJ of the instan-t bleach-ing composition, from about 5 to 50%, by weight, of a detergent surface active agent, and from about 1 to 60%, by weight, of a detergency builder which can also function as a buffer to provide the requisite p~l range when the laundering composition is added to water. The balance of the composl-tion will predominantly comprise filler salts~ such as, sodium sulfate and potassium sulfate, minor additives, such as, optical brighteners, perfumes, dyes, anti-redeposition agents and the like, and water.
The anionic surface active agents useful in the present invention include those surface active or detergent compounds which contain an organic hydrophobic group containing generally 8 to 26 carbon atoms and preferably 10 to 18 carbon atoms in their molecular structure and at least one water-solubilizing group selected from the group of sulfonate, sulfate, carboxylate, phosphonate and phosphate so as to form a water-soluble detergent.
Examples of suitable anionic detèrgents include, for example, the water-soluble salts (e.g., the sodium, ammonium and alkanolammonium salts) of higher fatty acids or resin salts containing from about 8 to 20 carbon atoms and preferably 10 to 18 carbon atoms. Suitable fatty acids can be ob-tained from oils and waxes of animal or vegetable origin, for example, tallow, grease, coconut oil and mixtures thereof. Particularly useful are the sodium cmd potassium salts of the Eatty acid mixtures derived from coconut oil and tallow, Eor example, sodium coconut soap and potassium tallow soap.
The anionic class of detergents also includes the water-soluble sulfated and sulfonated detergents having an alkyl radical containing from about 8 to 26, and preferably from about 12 to 22 carbon atoms. (The term "alkyl" includes the alkyl portion oE the higher acyl radicals). Examples of the sulfonated anionic detergents are the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from about 10 to 16 carbon atoms in the hi.gher alkyl group in a straight or branched chain, such as, for example, the sodium, potassium and ammonium salts of higher alkyl benzene sulfonates~ higher alkyl toluene sulfonates and higher alkyl phenol sulfonates.
Other suitable anionic detergents are the olefin sulfonates includ-ing long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mix-tures of alkene sulfonates and hydroxyalkane sulfonates. The olefin sulfon-ate detergents may be prepared in a conventional manner by the reaction of SO3 with long chain olefins containing from about 8 to 25, and preferably from about 12 to 21 carbon atoms, such olefins having, the formula R~l-~-IR
wherein R is a higher alkyl group of 6 to 23 carbons and Rl is an alkyl group containing from about 1 to 17 carbon atoms or hydrogen to form a mix-ture of sultones and alkene sulfonic acids which is then treated to convert the sultones to sulfonates. Other examples of sulfate or sulfonate deter-gents are paraffin sulfonates containing from about 10 to 20 carbon atoms, and preferably from about 15 to 20 carbon atoms. The primary paraffin sul-fonates are made by reacting long chain alpha olefins and bisulfites. Paraf-fin sulfonates having the sulfonate group distributed along the paraffin chain are shown in U.S. Patent Nos. 2,503,280; 2,507,088; 3,260,7~1;
3,372,188; and German Patent No. 735,096. Other useful sulfate and sulfon-ate detergents include sodium and potassium sulfates of higher alcohols con-taining from about 8 to 18 carbon atoms, such as, for example, sodium lauryl sulfate and sodlum taLlow alcollol sulfa-te, sodium and potassium sal-ts of alpha-sulfoEatty acid esters containing about 10 to 20 carbon atoms in the acyl group, Eor example, methyl alpha-sulEomyristate and methyl alpha-sulfotallowate, ammonillm sulEates of mono- or di- glycerides of higher (C10 -C18) fatty acids, for example, stearic monoglyceride monosulEate; sodium and alkylol ammonium salts of alkyl polyethenoxy ether sulfates produccd by con-densing 1 to 5 moles of ethylene oxide with 1 mole of higher (C8 - C18) alcohol; sodium higher al]cyl (C10 - Cl8) glyceryl ether sulfonates; and sodium or potassiwD alkyl phenol polyethenoxy ether sulfates with about l to 6 oxyethylene groups per molecule and in which the alkyl radicals contain about 8 to 12 carbon atoms.
The suitable anionic detergents also include the C8 to C18 acyl sarcosinates (for example, sodium lauroyl sarcosinates), sodium and potas-sium salts of the reaction product of higher fatty acids containing 8 to 18 carbon atoms in the molecule esterified with isethionic acid, and sodium and potassium salts of the C8 - Cl8 acyl N-methyl taurides, for example, sodium cocyl methyl taurate and potassium stearoyl methyl taurate.
Anionic phosphate surfactants in which the anionic solubilizing group attached to the hydrophobic group is an oxyacid of phosphorous are also useful in the detergent compositions. Suitable phosphate surfactants are the sodium, potassium and ammonium alkyl phosphate esters such as (R-0)2P02M and ROP03M2 in which R represents an alkyl chain containing from about 8 to 20 carbon atoms and M represents a soluble cation. The compounds formed by including from about l to 40 moles of ethylene oxide in the fore-going esters, for example, [R-O(C2l-l40)n]2 P02M are also useful-The most highly preferred water-soluble anionic detergent com-pounds are the ammonium and substituted ammonium (such as mono, di and tri-ethanolamine), alkali metal (such as, sodium and potassium) and alkaline earth metal (such as, calcium and magnesium) salts of the higher alkyl ben-zene sulfonates, olefin sulfonates and higher alkyl sulfates. Among the ~9~
above-listed aniollics, the mos-t pre:Eerred are the sodium linear alky:l ben-zene sulfona-tes ~LAS).
The nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature). Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a :Eree hydrogen attached to the ni-trogen can be condensed with ethylene oxicle or with the polyhydration product thereof, polyethylene glycol, to form a nonionic detergent. The lengt}l of the hydro-philic or polyoxyethylene chain can be readily adjusted to achieve the de-sired balance between the hydrophobic and hydrophilic groups.
The nonionic detergents incl.ude the polyethylene oxide condensate of 1 mole of alkyl phenol containing from about 6 to 12 carbon atoms in a straight or branched chain configuration with about 5 to 30 moles of ethylene oxide, for example, nonyl phenol condensed wi-th 9 moles of ethylene oxide; dodecyl phenol condensed wi.th 15 moles of ethylene oxide; and dinonyl phenol condensed with 15 moles of ethylene oxi.de. Condensation products of the corresponding alkyl thiophenols with 5 to 30 moles of e~hylene oxide are also suitable.
The polar nonionic detergents useful in -the present invention are those in which the hydrophilic group contains a semi-polar bond directly be-tween two atoms, for example N-~O, P ~ O, As-~O, and S-~O. Such polar non-iOlliC detergents include:
1. Open-chain aliphatic amine oxides of the general formula RlR2R3N-~O wherein Rl is an alkyl, alkenylJ or monohydroxy-alkyl group containing from about 10 to 18 carbon atoms, and R2 ancl R3 are each an alkyl or monohydroxyalkyl group contain-ing from 1 to 3 carbon atoms.
2. Open-chain ali.phatic phosphine oxides having the general tormula RlR~R3P ~O, whereln Rl is an alkyl, a]kenyl or mono-hydroxyalkyl group containing from about 10 to 18 carbon atoms, and R2 and R3 are each an a:Lkyl or monohydroxyalkyl group con-taining -Erom 1 -to 3 carbon atoms. O
3. Surfactants having the general formula Rl - S - R2 wherein Rl is an alkyl group containing from about 10 to 18 carbon a-toms, and R2 is an alkyl group containing from 1 to 3 carbon atoms and from 0 to 2 hydroxyl groups.
a:E ~he above-described types of nonionic surfactants, those of the ethoxylated alcohol type are preferred. Particularly preferred nonionic surfactants include the condensation product of coconut fatty alcohol with about 6 moles of ethylene oxide per mole of coconut fatty alcohol, the con-densation product of tallow fatty alcohol with about 11 moles of ethylene oxide per mole of tallow fatty alcohol, the condensation product of a second-ary fatty alcohol containing about 11-15 carbon atoms with about 9 moles of ethylene oxide per mole of fatty alcohol and condensation products of more or less branched primary alcohols, whose branching is predominantly 2-methyl, with from about 4 to 12 moles of ethylene oxide.
Zwitterionic detergents such as the betaines and sulfobetaines hav-ing the following formula are also useful:
R - O
wherein R is an alkyl group containing from about 8 to 18 carbon atoms, R2 and R3 are each an alkylene or hydroxyalkylene group containing about 1 to 4 carbon atoms, R4 is an alkylene or hydroxyalkylene group containing 1 to 4 atoms, and X is C or S:O. The alkyl group can contain one or more inter-mediate linkages such as arnido, ether, or polyether linkages or nonfunc-tional substituents such as hydroxyl or halogen which do not substantially affect the hydrophobic character of the group. When X is C, the detergent ls called a betaine; and when X is S:0, the detergent is called a sulfo-betaine or sultaine. Preferred betaine and sul-fobetaine detergents are l-(lauryl dimethylammonio) ace-tate, I-(myristyl d:imethylammonio) propane-3-sulfonate, and l-(myristyl dimethylammonio)-2-hydroxy-propane-3-sulfonate.
Cationic surface active agents may also be employed. They com-prise surface active detergent compounds which contain an organic hydro~
phobic group and a cationic solubilizing group. 'I'ypical cationic solubiliz-ing groups are amine and quaternary groups.
Examples of suitable synthetic cationic detergents include:
normal primary amines of the formula RN112 wherein R is an alkyl group con-taining from about 12 to 15 atoms; diamines having the formula RNHC2tl4NH2 wherein R is an alkyl group containing from about 12 to 22 carbon atoms, such as N-2-aminoethyl-stearyl amine and N-2-aminoethyl myristyl amine;
amide-linked amine such as those having the formula RlCONHC2H4NH2 wherein R
is an alkyl group containing about 8 to 20 carbon atoms, such as N-2-amino ethylstearyl amide and N-amino ethylmyristyl amide; quaternary ammonium com-pounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group containing about 8 to 22 carbon atoms and three of the groups linked to the nitrogen atom are alkyl groups which contain 1 to 3 carbon atoms, including alkyl groups bearing inert substituents, such as phenyl groups, and there is present an anion such as halogen, acetate, methosulfate, etc. ~le alkyl group may contain intermediate linkages such as amide which do not substantially affect the hydrophobic character of the group, for example, stearyl amido propyl quaternary ammonium chloride. Typical quater-nary ammonium detergents are ethyl-dimethyl-stearyl-ammonium ch:Loride, benzyl-dimethyl-stearyl-ammonium chloride, trimethyl-stearyl almmonium chloride, tri-methyl-cetyl ammonium bromideJ dimethyl-ethyl-lauryl ammonium chloride, dimethyl-propyl-myristyl ammonium chloride, and the corresponding metho-sulfates and acetates 3~ Ampholytic detergents are also suitable for the invention.
Ampholytic detergents are well known in the art and many operable de-tergents of thls class are disclosed by A. M. Schwartz, J. W. Perry and J. Birch in "Surface Active Agents and Detergents", Interscience Publishers, New York, 1958, vol. 2. Examples of suitable amphoteric detergents include: alkyl beta-ami.nodipropionates, RN(C2H4COOM)2; al:kyl beta-amino propionates, RN(il)C2114COOM; and long chain imida~ole derivatives having the general formula:
Cll N / ~ C~l ~ / \ 2 2 2 wherein in each of the above formulae R is an acyclic hydrophobic group con-taining from about 8 to 18 carbon atoms and M is a cation to neutrali~e the charge of the anion. Specific operable amphoteric detergents include the disodium salt of lauroycycloimidinium-l ethoxyethionic acid-2-ethionic acid, dodecyl beta alanine, and the inner salt of 2-trimethylamino lauric acid.
~ e bleaching and laundering compositions of ~he invention option-ally contain a detergency bui].der of the type commonly added to detergent formulations. Useful builders include any of the conventional i.norganic and organic water-soluble builder salts. Useful inorganic builder salts include, for example, water-soluble salts of phosphates, pyrophosphates, orthophos-phates, polyphosphates, silicates, carbonates, and the like. Organic builders include water-soluble phosphonates, polyphosphonates, polyhydroxysulfonates, polyacetates, carboxylates, polycarboxylatès, succina.tes and the like.
SpeciEic examples o:~ inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. The organic polyphosphonates specifically include, for example, the sodium and potassium salts of ethane l-hydroxy-l,l-disphosphonic acid and the sodium and potassium salts of ethane-l,l 2-triphosphonic acid. E~amples of these and 3( ~5 other phospllorous builder compounds are disclosed in U.S. Patent ~os.
3,213,030; 3,422~021; 3,422,137 and 3,400,176. Pentasodium tripolyphosphate and -tetrasodium pyropllosphate are especially preferred water-soluble inorganic builders.
SpeciEic examples of non-phosphorous inorganic builders include water~soluble inorganic carbonate, bicarbonate cmd silicate salts. The alkali metalg for example, sodium and potassium, carbonates, bicarbonates and silicates are particularly useEul herein.
Water-soluble organic builders are also useful. i:or example, the alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates are useful builders Eor the com-positions and processes of the invention. Specific examples of polyacetate and polycarboxylate builders include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diaminetetracetic acid, nitrilo-triacetic acid, benzene polycarboxylic ~i.e. penta- and tetra-) acids, carboxymethoxysuccinic acid and citric acid.
Water-insoluble builders may also be used, particularly, the com-plex silicates and more particularly, the complex sodium alumino silicates such as zeolites, e.g., zeolite 4A, a type of zeolite molecular sieve where-in the univalent cation is sodium and the pore size is about 4 Angstroms.The preparation of such type zeolite is described in U.S. Patent 3,114,603.
The zeolites may be amorphous or crystalline and ha-ve water of hydration as known in the art.
The use of inert, water-soluble filler salt is desirable in both the bleaching and laundering compositions of the invention. The filler salt employed should preferably be free of any halide anion, and not ionize in aqueous media to chloride or bromide anions because oE the possible deleteri-ous effects o-f such halide anion on the bleaching activi-ty of the bleach com-position. A preferred filler salt is an alkali metal sulfate, such as, pot-assium or sodium sulfate, the latter being especially preferred.
The bleach:ing compos.itions of the invention are prepared by admix-ing -the ingredients. When preparing laundering compositions containing the bleaching composition in combinati.on with a detergent and/or builder salts, the peroxygen compound and activator can be mixed either directly with the detergent compound, builder and the like, or the peroxygen compound and activator can be separately or collectively coated with a coating material to prevent premature activation o:E the bleaching agent. The coat:ing process is conducted in accordance with procedures well known in the art. Suitable coating material include compounds such as magnesium sulfate, polyvinyl alcohol lauric acid or its salts, and the like.
~gl~5 ll.SI` P~0v1`~)7J~E
~ achln~ tests ~Jere c;~l~riecl out on stand~ld stalncd test s~:atcles (descrihe(3 belo~/) using the Val`iO~lS bleachin~ alld launder-in~ compositlons dercribed in the Ri~amples in a Ter otol~el;er*vesscl manufactured by the U.S. Tes~in~ Company. The Ter~otome~er l:as maintainet3 at a constant tern~c~atuIe Or 120F and o~cr~ted t 100 r,)m.
E~ch of the tes-t compositions (e:cept wheIe spe~irically lndlcated to the contrar~j was added to one liter of tap water at 120i~ having a ~ater hardness of about 100 ppm, as calclum carbonate The test compositions were agitated for about one minute and then a mixed rabric load consisting of two swatches each (3" x 4") Or the stained fabrics described belo-" was added to each wash receptacle. After a 15 minute wash at 120F, the test fabrics were rinsed under 100F tap water and dried on a print dryer. The percent stain removal was measured by takin~
a reflectance reading for each test swatch prior to and after the bleaching test using a Gardner Color Difference Meter~ and the percent stain removal (~ S.R.) was calculated as follows:
(Rd after washing) - (Rd before washin~) S.R. =
90 - (Rd ~efore washing) A difference ~reater than ~ in the average of the five stained clo-ths tested is considered si~nificant.
At the end of each wash, the active o~ygen content Or the ash solution was determined by acldification wlth dilute sul-furic acid followed b~ treatment of the wash solutlon with * Trade Mark 1~
.
~t potassiwn ioclide and a minor amount of ammonium molybdate, and thereafter -titration with standardized sodium th:iosulfa-te using starch as the indica-tor.
The respective stains and test swatches were as follows:
Stain Test Cloth 1. Grape - 65 Dacron - 35 Cotton 2. Blueberry - Cotton 3. Sulfo Dye - EMPA 115 . Red Wine - EMPA 11~l 5. Coffee/Tea - Cotton Stained test cloths 1 and 2 are prepared by passing rolls of un-soiled fabric through a padding and drying apparatus (manufactured by Benz of Zurich, Switzerland) containing either grape or blueberry solutions at 90F. After drying at 2501:, the :Eabric is cut into 3" x 4" swatches.
Eighty of these swatches, impregnated with the same stain, are rinsed in 17 gallons of 85F water in an automatic home washer. They are then dried by a passage through a Beseler Print Dryer at a machine temperature setting of 6 and a speed of 10.
Stained fabrics 3 and L~ are purchased from Testfabrics Incorporated of Middlesex, New Jersey, and cut into 3" x ~" swatches.
Stained fabric 5 is prepared by agitating ancl soaking unsoiled cot-ton strips (18" x 36") in a washing machine filled with a solution of coffee/
tea (8:1 weight ratio) at 150F. The machine is allowed to rinse spin dry to remove the coffee/tea solution. The stained fabric is then machine washed twice with hot pyrophosphate-surfactant solution followed by two com-plete water wash cycles at 1~0F. The strips are then dried by two passes through an Ironrite machine set at 10 and then cut into 3" x ~" swatches.
EXAMPLE I
A granular detergent composition ~designatsd herei.n as "HDD'~) was prepared by conventional spray-drying and had the following approximate com--position:
3(~
CO~ L10n Weight Percent Sodium tridecylbeIl~enesulEonate 15 Ethoxylated C12 - C15 primary alcohol (7 moles EO/mole alcohol) Sodium tripolyphosphate 33 Sodium carbonate 5 Sodium silicate 7 Sodium carboxymethylcellulose 0.5 Optical brighteners 0.2 Perfume 0.2 Water 11 Sodium sulfate balance Detergent compositions A--E containing HDD were formulated as set forth below in Table I. To assure good dissolution of the phthalic anhy-dride in the aqueous wash solutionl the phthalic anhydride is finely ground to pass through a Number 20 U.S.A. Standard Sieve, and more preferably, through a Number 60 U.S.A. Sieve.
Table I
Component Composition A B C D E
Detergent, HDD 1.50g 1.50g 1.50g 1.50g 1.50g 1.50g Sodium perborate 0.10 0.10 0.10 0.10 0.10 0.10 (10.1% A.O.) DTPMP~ ) 0.02 ----- 0.02 ----- ----- -----Phthalic anhydride ----- 0.14 0.14 0.14 0.14 0.1 Sodium carbonate --~ 0.05 ----- ----- 0.05 EDTA(2) (disodium salt) ----- ----- ----- 0.02 ----- -----NTA(3) ____ ____ _ ___ ____ .020 .020 . .
(1) Sodium diethylene triamine pentamethylene phosphonate (2) Ethylene diamine tetraacetic acid, disodium salt (3) Nitrilotriacetic acid, trisodium salt - monohydra-te.
;~ -17-Compositions A througll r were tested in accordance Wit}l the proce-dure described above and the results of the bleaching tests are tabulated in Table II which sets forth the initi.al and :Einal values of the active oxygen (AØ) in the wash solution (expressed as "initial grams" and "residual grams", respectively) and the stai.n removal achieved for each of the 5 stains.
Table :~I
Comparative Bleaching Performcmce Composition A B C D E F
Initial grams 10.1 10.1 10.1 1Ø1 10.1 10.1 (AØ x 103) Residual grams 9.2 5.3 6.8 5.5 6.0 5.7 (AØ x 103) Stain removal: % % % % % %
Grape 52 72 69 68 72 62 Blueberry 45 48 50 51 52 48 Sulfodye (EMPA 115) 4 4 4 4 3 3 Red wine (EMPA 114) 30 40 36 39 38 35 Coffee/Tea 14 38 34 37 39 33 Avg. (%) 29 40 39 40 41 36 The resul-ts of Table II indicate that composition C, a composition in accordance with the invention, consumes less active oxygen while provid-ing about an equivalent level of stain removal relative to composition B~ acomposition essentially similar to composition C except -that it contains no DTPMP, and compositions D, E and F which differ from composition C in that they employ either EDTA or NTA as chelating agen-ts rather than DTPMP.
Example 2 Compositions B and C described in Table I above were tested in accordance with the test procedure of Example I except that the hardness of the wash water was 300 ppm, expressed as CaCo3, instead of 100 ppm. The wash water used was tap water to which 200 ppm of hardness derived from calcium and magnesium chloride was added. The results of the bleaching tests are shown in Table III.
Table TII
. ~ .
~ ching Performance __ B C
Initial grams ln. 1 lo. 1 (AØ x 103) Residual grams 5.0 5.8 ~AØ x 103) Stain Removal % %
_.
Grape 77 77 Blueberry 54 52 Sulfodye (EMPA 115) 2 2 Red Wine (EMPA 1]4) 40 ~0 Coffee/Tea 45 43 __ _ _ Avg. (%) 44 43 A comparison of the bleaching performance achieved with composi-tions B and C in this Example with the bleaching performance of Compositions B and C in Example l (Table II) indicates that a substantially improved stain removal efficiency was achieved in water having a 300 ppm hardness con-tent relative to the 100 ppm water of Example 1.
Example 3 Detergent compositions G and ll were formulated as sho~l below.
s Component _omposi.tion G H
Detergent IIDD 1.50g 1.50g Sodium perboratc 0.10 0.10 Phthalic anhydride ~P.A.)o~lo~
TAED~2) ___ _ 0.045~ ) DTPMP 0.02 0.02 ~1) Perbora-te : P.A. mole ratio - :L
~2) Tetraacetyl ethylenediamine ~3) Perborate : TAED mole ratio = 3 Compositions G and H were tested under the wash conditions of Example 1 (100 ppm water) and Example 2 (300 ppm water). The results are summarized in Table IV.
Table IV
Comparative Bleaching Performance In 100 And 300 ppm Water Hardness 100 ppm lardness 300 ppm llardness G H G H
Initial grams 10.1 10.1 10.1 10.1 (AØ x 103) Final Grams 7.7 8.0 6.g 7.4 (AØ x 103) Stain Removal % % % %
Grape 66 73 74 63 Blueberry 51 53 53 44 Red wine (EMPA 114) 34 33 36 28 Avg. (%) 50 53 54 45 As evident from Table IV, in water of 100 ppm hardness, the deter-gent composition of the invention ac-tivated with phthalic anhydride (composi-~ !., tion G) is nearly as e:Efective for bleaching as the de-tergent composition activated with T~EI) (composition ll). In water o:E 300 ppm hardness, the TAED
activated perborate composition is markedly less eEEective than composition G, the composition of the invention.
. ..
a:E ~he above-described types of nonionic surfactants, those of the ethoxylated alcohol type are preferred. Particularly preferred nonionic surfactants include the condensation product of coconut fatty alcohol with about 6 moles of ethylene oxide per mole of coconut fatty alcohol, the con-densation product of tallow fatty alcohol with about 11 moles of ethylene oxide per mole of tallow fatty alcohol, the condensation product of a second-ary fatty alcohol containing about 11-15 carbon atoms with about 9 moles of ethylene oxide per mole of fatty alcohol and condensation products of more or less branched primary alcohols, whose branching is predominantly 2-methyl, with from about 4 to 12 moles of ethylene oxide.
Zwitterionic detergents such as the betaines and sulfobetaines hav-ing the following formula are also useful:
R - O
wherein R is an alkyl group containing from about 8 to 18 carbon atoms, R2 and R3 are each an alkylene or hydroxyalkylene group containing about 1 to 4 carbon atoms, R4 is an alkylene or hydroxyalkylene group containing 1 to 4 atoms, and X is C or S:O. The alkyl group can contain one or more inter-mediate linkages such as arnido, ether, or polyether linkages or nonfunc-tional substituents such as hydroxyl or halogen which do not substantially affect the hydrophobic character of the group. When X is C, the detergent ls called a betaine; and when X is S:0, the detergent is called a sulfo-betaine or sultaine. Preferred betaine and sul-fobetaine detergents are l-(lauryl dimethylammonio) ace-tate, I-(myristyl d:imethylammonio) propane-3-sulfonate, and l-(myristyl dimethylammonio)-2-hydroxy-propane-3-sulfonate.
Cationic surface active agents may also be employed. They com-prise surface active detergent compounds which contain an organic hydro~
phobic group and a cationic solubilizing group. 'I'ypical cationic solubiliz-ing groups are amine and quaternary groups.
Examples of suitable synthetic cationic detergents include:
normal primary amines of the formula RN112 wherein R is an alkyl group con-taining from about 12 to 15 atoms; diamines having the formula RNHC2tl4NH2 wherein R is an alkyl group containing from about 12 to 22 carbon atoms, such as N-2-aminoethyl-stearyl amine and N-2-aminoethyl myristyl amine;
amide-linked amine such as those having the formula RlCONHC2H4NH2 wherein R
is an alkyl group containing about 8 to 20 carbon atoms, such as N-2-amino ethylstearyl amide and N-amino ethylmyristyl amide; quaternary ammonium com-pounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group containing about 8 to 22 carbon atoms and three of the groups linked to the nitrogen atom are alkyl groups which contain 1 to 3 carbon atoms, including alkyl groups bearing inert substituents, such as phenyl groups, and there is present an anion such as halogen, acetate, methosulfate, etc. ~le alkyl group may contain intermediate linkages such as amide which do not substantially affect the hydrophobic character of the group, for example, stearyl amido propyl quaternary ammonium chloride. Typical quater-nary ammonium detergents are ethyl-dimethyl-stearyl-ammonium ch:Loride, benzyl-dimethyl-stearyl-ammonium chloride, trimethyl-stearyl almmonium chloride, tri-methyl-cetyl ammonium bromideJ dimethyl-ethyl-lauryl ammonium chloride, dimethyl-propyl-myristyl ammonium chloride, and the corresponding metho-sulfates and acetates 3~ Ampholytic detergents are also suitable for the invention.
Ampholytic detergents are well known in the art and many operable de-tergents of thls class are disclosed by A. M. Schwartz, J. W. Perry and J. Birch in "Surface Active Agents and Detergents", Interscience Publishers, New York, 1958, vol. 2. Examples of suitable amphoteric detergents include: alkyl beta-ami.nodipropionates, RN(C2H4COOM)2; al:kyl beta-amino propionates, RN(il)C2114COOM; and long chain imida~ole derivatives having the general formula:
Cll N / ~ C~l ~ / \ 2 2 2 wherein in each of the above formulae R is an acyclic hydrophobic group con-taining from about 8 to 18 carbon atoms and M is a cation to neutrali~e the charge of the anion. Specific operable amphoteric detergents include the disodium salt of lauroycycloimidinium-l ethoxyethionic acid-2-ethionic acid, dodecyl beta alanine, and the inner salt of 2-trimethylamino lauric acid.
~ e bleaching and laundering compositions of ~he invention option-ally contain a detergency bui].der of the type commonly added to detergent formulations. Useful builders include any of the conventional i.norganic and organic water-soluble builder salts. Useful inorganic builder salts include, for example, water-soluble salts of phosphates, pyrophosphates, orthophos-phates, polyphosphates, silicates, carbonates, and the like. Organic builders include water-soluble phosphonates, polyphosphonates, polyhydroxysulfonates, polyacetates, carboxylates, polycarboxylatès, succina.tes and the like.
SpeciEic examples o:~ inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. The organic polyphosphonates specifically include, for example, the sodium and potassium salts of ethane l-hydroxy-l,l-disphosphonic acid and the sodium and potassium salts of ethane-l,l 2-triphosphonic acid. E~amples of these and 3( ~5 other phospllorous builder compounds are disclosed in U.S. Patent ~os.
3,213,030; 3,422~021; 3,422,137 and 3,400,176. Pentasodium tripolyphosphate and -tetrasodium pyropllosphate are especially preferred water-soluble inorganic builders.
SpeciEic examples of non-phosphorous inorganic builders include water~soluble inorganic carbonate, bicarbonate cmd silicate salts. The alkali metalg for example, sodium and potassium, carbonates, bicarbonates and silicates are particularly useEul herein.
Water-soluble organic builders are also useful. i:or example, the alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates are useful builders Eor the com-positions and processes of the invention. Specific examples of polyacetate and polycarboxylate builders include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diaminetetracetic acid, nitrilo-triacetic acid, benzene polycarboxylic ~i.e. penta- and tetra-) acids, carboxymethoxysuccinic acid and citric acid.
Water-insoluble builders may also be used, particularly, the com-plex silicates and more particularly, the complex sodium alumino silicates such as zeolites, e.g., zeolite 4A, a type of zeolite molecular sieve where-in the univalent cation is sodium and the pore size is about 4 Angstroms.The preparation of such type zeolite is described in U.S. Patent 3,114,603.
The zeolites may be amorphous or crystalline and ha-ve water of hydration as known in the art.
The use of inert, water-soluble filler salt is desirable in both the bleaching and laundering compositions of the invention. The filler salt employed should preferably be free of any halide anion, and not ionize in aqueous media to chloride or bromide anions because oE the possible deleteri-ous effects o-f such halide anion on the bleaching activi-ty of the bleach com-position. A preferred filler salt is an alkali metal sulfate, such as, pot-assium or sodium sulfate, the latter being especially preferred.
The bleach:ing compos.itions of the invention are prepared by admix-ing -the ingredients. When preparing laundering compositions containing the bleaching composition in combinati.on with a detergent and/or builder salts, the peroxygen compound and activator can be mixed either directly with the detergent compound, builder and the like, or the peroxygen compound and activator can be separately or collectively coated with a coating material to prevent premature activation o:E the bleaching agent. The coat:ing process is conducted in accordance with procedures well known in the art. Suitable coating material include compounds such as magnesium sulfate, polyvinyl alcohol lauric acid or its salts, and the like.
~gl~5 ll.SI` P~0v1`~)7J~E
~ achln~ tests ~Jere c;~l~riecl out on stand~ld stalncd test s~:atcles (descrihe(3 belo~/) using the Val`iO~lS bleachin~ alld launder-in~ compositlons dercribed in the Ri~amples in a Ter otol~el;er*vesscl manufactured by the U.S. Tes~in~ Company. The Ter~otome~er l:as maintainet3 at a constant tern~c~atuIe Or 120F and o~cr~ted t 100 r,)m.
E~ch of the tes-t compositions (e:cept wheIe spe~irically lndlcated to the contrar~j was added to one liter of tap water at 120i~ having a ~ater hardness of about 100 ppm, as calclum carbonate The test compositions were agitated for about one minute and then a mixed rabric load consisting of two swatches each (3" x 4") Or the stained fabrics described belo-" was added to each wash receptacle. After a 15 minute wash at 120F, the test fabrics were rinsed under 100F tap water and dried on a print dryer. The percent stain removal was measured by takin~
a reflectance reading for each test swatch prior to and after the bleaching test using a Gardner Color Difference Meter~ and the percent stain removal (~ S.R.) was calculated as follows:
(Rd after washing) - (Rd before washin~) S.R. =
90 - (Rd ~efore washing) A difference ~reater than ~ in the average of the five stained clo-ths tested is considered si~nificant.
At the end of each wash, the active o~ygen content Or the ash solution was determined by acldification wlth dilute sul-furic acid followed b~ treatment of the wash solutlon with * Trade Mark 1~
.
~t potassiwn ioclide and a minor amount of ammonium molybdate, and thereafter -titration with standardized sodium th:iosulfa-te using starch as the indica-tor.
The respective stains and test swatches were as follows:
Stain Test Cloth 1. Grape - 65 Dacron - 35 Cotton 2. Blueberry - Cotton 3. Sulfo Dye - EMPA 115 . Red Wine - EMPA 11~l 5. Coffee/Tea - Cotton Stained test cloths 1 and 2 are prepared by passing rolls of un-soiled fabric through a padding and drying apparatus (manufactured by Benz of Zurich, Switzerland) containing either grape or blueberry solutions at 90F. After drying at 2501:, the :Eabric is cut into 3" x 4" swatches.
Eighty of these swatches, impregnated with the same stain, are rinsed in 17 gallons of 85F water in an automatic home washer. They are then dried by a passage through a Beseler Print Dryer at a machine temperature setting of 6 and a speed of 10.
Stained fabrics 3 and L~ are purchased from Testfabrics Incorporated of Middlesex, New Jersey, and cut into 3" x ~" swatches.
Stained fabric 5 is prepared by agitating ancl soaking unsoiled cot-ton strips (18" x 36") in a washing machine filled with a solution of coffee/
tea (8:1 weight ratio) at 150F. The machine is allowed to rinse spin dry to remove the coffee/tea solution. The stained fabric is then machine washed twice with hot pyrophosphate-surfactant solution followed by two com-plete water wash cycles at 1~0F. The strips are then dried by two passes through an Ironrite machine set at 10 and then cut into 3" x ~" swatches.
EXAMPLE I
A granular detergent composition ~designatsd herei.n as "HDD'~) was prepared by conventional spray-drying and had the following approximate com--position:
3(~
CO~ L10n Weight Percent Sodium tridecylbeIl~enesulEonate 15 Ethoxylated C12 - C15 primary alcohol (7 moles EO/mole alcohol) Sodium tripolyphosphate 33 Sodium carbonate 5 Sodium silicate 7 Sodium carboxymethylcellulose 0.5 Optical brighteners 0.2 Perfume 0.2 Water 11 Sodium sulfate balance Detergent compositions A--E containing HDD were formulated as set forth below in Table I. To assure good dissolution of the phthalic anhy-dride in the aqueous wash solutionl the phthalic anhydride is finely ground to pass through a Number 20 U.S.A. Standard Sieve, and more preferably, through a Number 60 U.S.A. Sieve.
Table I
Component Composition A B C D E
Detergent, HDD 1.50g 1.50g 1.50g 1.50g 1.50g 1.50g Sodium perborate 0.10 0.10 0.10 0.10 0.10 0.10 (10.1% A.O.) DTPMP~ ) 0.02 ----- 0.02 ----- ----- -----Phthalic anhydride ----- 0.14 0.14 0.14 0.14 0.1 Sodium carbonate --~ 0.05 ----- ----- 0.05 EDTA(2) (disodium salt) ----- ----- ----- 0.02 ----- -----NTA(3) ____ ____ _ ___ ____ .020 .020 . .
(1) Sodium diethylene triamine pentamethylene phosphonate (2) Ethylene diamine tetraacetic acid, disodium salt (3) Nitrilotriacetic acid, trisodium salt - monohydra-te.
;~ -17-Compositions A througll r were tested in accordance Wit}l the proce-dure described above and the results of the bleaching tests are tabulated in Table II which sets forth the initi.al and :Einal values of the active oxygen (AØ) in the wash solution (expressed as "initial grams" and "residual grams", respectively) and the stai.n removal achieved for each of the 5 stains.
Table :~I
Comparative Bleaching Performcmce Composition A B C D E F
Initial grams 10.1 10.1 10.1 1Ø1 10.1 10.1 (AØ x 103) Residual grams 9.2 5.3 6.8 5.5 6.0 5.7 (AØ x 103) Stain removal: % % % % % %
Grape 52 72 69 68 72 62 Blueberry 45 48 50 51 52 48 Sulfodye (EMPA 115) 4 4 4 4 3 3 Red wine (EMPA 114) 30 40 36 39 38 35 Coffee/Tea 14 38 34 37 39 33 Avg. (%) 29 40 39 40 41 36 The resul-ts of Table II indicate that composition C, a composition in accordance with the invention, consumes less active oxygen while provid-ing about an equivalent level of stain removal relative to composition B~ acomposition essentially similar to composition C except -that it contains no DTPMP, and compositions D, E and F which differ from composition C in that they employ either EDTA or NTA as chelating agen-ts rather than DTPMP.
Example 2 Compositions B and C described in Table I above were tested in accordance with the test procedure of Example I except that the hardness of the wash water was 300 ppm, expressed as CaCo3, instead of 100 ppm. The wash water used was tap water to which 200 ppm of hardness derived from calcium and magnesium chloride was added. The results of the bleaching tests are shown in Table III.
Table TII
. ~ .
~ ching Performance __ B C
Initial grams ln. 1 lo. 1 (AØ x 103) Residual grams 5.0 5.8 ~AØ x 103) Stain Removal % %
_.
Grape 77 77 Blueberry 54 52 Sulfodye (EMPA 115) 2 2 Red Wine (EMPA 1]4) 40 ~0 Coffee/Tea 45 43 __ _ _ Avg. (%) 44 43 A comparison of the bleaching performance achieved with composi-tions B and C in this Example with the bleaching performance of Compositions B and C in Example l (Table II) indicates that a substantially improved stain removal efficiency was achieved in water having a 300 ppm hardness con-tent relative to the 100 ppm water of Example 1.
Example 3 Detergent compositions G and ll were formulated as sho~l below.
s Component _omposi.tion G H
Detergent IIDD 1.50g 1.50g Sodium perboratc 0.10 0.10 Phthalic anhydride ~P.A.)o~lo~
TAED~2) ___ _ 0.045~ ) DTPMP 0.02 0.02 ~1) Perbora-te : P.A. mole ratio - :L
~2) Tetraacetyl ethylenediamine ~3) Perborate : TAED mole ratio = 3 Compositions G and H were tested under the wash conditions of Example 1 (100 ppm water) and Example 2 (300 ppm water). The results are summarized in Table IV.
Table IV
Comparative Bleaching Performance In 100 And 300 ppm Water Hardness 100 ppm lardness 300 ppm llardness G H G H
Initial grams 10.1 10.1 10.1 10.1 (AØ x 103) Final Grams 7.7 8.0 6.g 7.4 (AØ x 103) Stain Removal % % % %
Grape 66 73 74 63 Blueberry 51 53 53 44 Red wine (EMPA 114) 34 33 36 28 Avg. (%) 50 53 54 45 As evident from Table IV, in water of 100 ppm hardness, the deter-gent composition of the invention ac-tivated with phthalic anhydride (composi-~ !., tion G) is nearly as e:Efective for bleaching as the de-tergent composition activated with T~EI) (composition ll). In water o:E 300 ppm hardness, the TAED
activated perborate composition is markedly less eEEective than composition G, the composition of the invention.
. ..
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A bleaching and laundering composition comprising a peroxygen com-pound, an activator for said peroxygen compound consisting essentially of phthalic anhydride, and diethylene triamine pentamethylene phosphonic acid and/or a water-soluble salt thereof.
2. A composition in accordance with claim 1 wherein the peroxygen com-pound is an alkali metal perborate.
3. A composition in accordance with claim 1 wherein the peroxygen com-pound is an alkali metal percarbonate.
4. A composition in accordance with claim 1 which additionally con-tains a surface active agent selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic detergents.
5. A bleaching detergent composition comprising:
(a) from about 5 to 50%, by weight, of a composition consisting essenti-ally of a peroxygen compound, phthalic anhydride as an activator therefor, and diethylene triamine pentamethylene phosphonic acid and/or a water-soluble salt thereof;
(b) from about 5 to 50%, by weight, of a detergent surface active agent;
(c) from about 1 to 60%, by weight, of a detergent builder salt; and, (d) the balance comprising water and optionally filler salts.
(a) from about 5 to 50%, by weight, of a composition consisting essenti-ally of a peroxygen compound, phthalic anhydride as an activator therefor, and diethylene triamine pentamethylene phosphonic acid and/or a water-soluble salt thereof;
(b) from about 5 to 50%, by weight, of a detergent surface active agent;
(c) from about 1 to 60%, by weight, of a detergent builder salt; and, (d) the balance comprising water and optionally filler salts.
6. A bleaching detergent composition in accordance with claim 5 where-in said peroxygen compound is an alkali metal perborate, and said surface active agent is selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic detergents.
7. A process for bleaching which comprises contacting the stained and/
or soiled material to be bleached with an aqueous solution of a composition comprising a peroxygen compound, an activator for said peroxygen compound consisting essentially of phthalic anhydride and diethylene triamine penta-methylene phosphonic acid and/or a water-soluble salt thereof.
or soiled material to be bleached with an aqueous solution of a composition comprising a peroxygen compound, an activator for said peroxygen compound consisting essentially of phthalic anhydride and diethylene triamine penta-methylene phosphonic acid and/or a water-soluble salt thereof.
8. The process of claim 7 wherein the peroxygen compound is an alkali metal perborate.
9. The process of claim 7 wherein the peroxygen compound is an alkali metal percarbonate.
10. The process of claim 7 wherein said composition additionally con-tains a surface active detergent selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic detergents.
11. A process for manufacturing the composition of claim 5 which com-prises:
(a) forming an aqueous slurry containing said detergent surface active agent and said detergent builder salt;
(b) spray-drying said aqueous slurry to form granular particles thereof;
and, (c) adding the composition consisting essentially of (i) a peroxygen compound, (ii) phthalic anhydride, and (iii) diethylene triamine pentamethylene phosphonic acid and/or a water-soluble salt thereof to the granular particles formed in step (b) to form the finished bleaching detergent composition.
(a) forming an aqueous slurry containing said detergent surface active agent and said detergent builder salt;
(b) spray-drying said aqueous slurry to form granular particles thereof;
and, (c) adding the composition consisting essentially of (i) a peroxygen compound, (ii) phthalic anhydride, and (iii) diethylene triamine pentamethylene phosphonic acid and/or a water-soluble salt thereof to the granular particles formed in step (b) to form the finished bleaching detergent composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US329,534 | 1981-12-10 | ||
| US06/329,534 US4378300A (en) | 1981-12-10 | 1981-12-10 | Peroxygen bleaching composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1190005A true CA1190005A (en) | 1985-07-09 |
Family
ID=23285861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000417353A Expired CA1190005A (en) | 1981-12-10 | 1982-12-09 | Peroxygen bleaching composition |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US4378300A (en) |
| AU (1) | AU555219B2 (en) |
| BE (1) | BE895307A (en) |
| CA (1) | CA1190005A (en) |
| CH (1) | CH654021A5 (en) |
| DE (1) | DE3245169A1 (en) |
| DK (1) | DK549782A (en) |
| ES (1) | ES518032A0 (en) |
| FR (1) | FR2518115B1 (en) |
| GB (1) | GB2112428B (en) |
| GR (1) | GR77844B (en) |
| IT (1) | IT1150399B (en) |
| MX (1) | MX159189A (en) |
| NZ (1) | NZ202662A (en) |
| PH (1) | PH18074A (en) |
| ZA (1) | ZA828774B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4529534A (en) * | 1982-08-19 | 1985-07-16 | The Procter & Gamble Company | Peroxyacid bleach compositions |
| US4664837A (en) * | 1982-10-04 | 1987-05-12 | Colgate Palmolive Co. | Bleaching and laundering composition containing magnesium monoperoxyphthalate a chelating agent, a peroxygen compound and phthalic anhydride |
| US4556975A (en) * | 1983-02-07 | 1985-12-03 | Westinghouse Electric Corp. | Programmable redundancy circuit |
| CS249980B1 (en) * | 1984-02-29 | 1987-04-16 | Jaroslav Simunek | Laundry agent with bleaching efficiency |
| US4717649A (en) * | 1986-04-18 | 1988-01-05 | Eastman Kodak Company | Photographic bleach-fixing compositions |
| US4737450A (en) * | 1986-04-18 | 1988-04-12 | Eastman Kodak Company | Method for bleach-fixing of photographic elements |
| US5130045A (en) * | 1987-10-30 | 1992-07-14 | The Clorox Company | Delayed onset active oxygen bleach composition |
| US5234616A (en) * | 1987-10-30 | 1993-08-10 | The Clorox Company | Method of laundering clothes using a delayed onset active oxygen bleach composition |
| GB8904007D0 (en) * | 1989-02-22 | 1989-04-05 | Procter & Gamble | Stabilized,bleach containing,liquid detergent compositions |
| US5663136A (en) * | 1992-06-15 | 1997-09-02 | The Procter & Gamble Company | Process for making compact detergent compositions |
| US6391839B1 (en) | 1992-08-01 | 2002-05-21 | The Procter & Gamble Company | Detergent bleach compositions containing layered silicate builder and percarbonate stabilized by EDDS |
| GB9216410D0 (en) * | 1992-08-01 | 1992-09-16 | Procter & Gamble | Detergent compositions |
| GB9216408D0 (en) * | 1992-08-01 | 1992-09-16 | Procter & Gamble | Stabilized bleaching compositions |
| GB9407535D0 (en) * | 1994-04-13 | 1994-06-08 | Procter & Gamble | Detergent compositions |
| GB9519094D0 (en) * | 1995-09-19 | 1995-11-22 | Warwick Int Group | Granulated active with controlled release |
| DE19651415A1 (en) * | 1996-12-11 | 1998-06-18 | Henkel Ecolab Gmbh & Co Ohg | Method of instrument disinfection |
| SE508954C2 (en) * | 1997-03-21 | 1998-11-16 | Eriksson Jan Olof | Detergent, free from surfactants |
| US5919745A (en) * | 1997-07-11 | 1999-07-06 | Church & Dwight Co., Inc | Liquid laundry detergent composition containing nonionic and amphoteric surfactants |
| EP0906950A1 (en) * | 1997-10-03 | 1999-04-07 | The Procter & Gamble Company | Peroxygen bleach-containing compositions comprising a particular chelating agent system |
| DE19847569A1 (en) * | 1998-10-15 | 2000-04-20 | Henkel Kgaa | Granules for use in detergents, especially detergents containing peroxide bleaches, comprise a phosphonate and a surfactant |
| KR100328267B1 (en) * | 2000-02-23 | 2002-03-16 | 성재갑 | liquid detergent composition |
| US7709437B2 (en) * | 2006-04-27 | 2010-05-04 | Oci Chemical Corp. | Co-granulates of bleach activator-peroxide compounds |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3243378A (en) * | 1962-04-11 | 1966-03-29 | Lestoil Products Inc | Bleaching composition |
| CA793720A (en) * | 1964-12-28 | 1968-09-03 | G. Mackellar Donald | Peroxygen compositions |
| LU61828A1 (en) * | 1970-10-07 | 1972-06-28 | ||
| US4009113A (en) * | 1971-04-30 | 1977-02-22 | Lever Brothers Company | Protection of materials |
| FI64639C (en) * | 1978-09-27 | 1983-12-12 | Unilever Nv | BLEKNINGS- OCH RENGOERINGSKOMPOSITION |
| US4259200A (en) * | 1979-04-06 | 1981-03-31 | Lever Brothers Company | Bleaching and cleaning compositions |
| FR2493294A1 (en) * | 1980-11-04 | 1982-05-07 | Air Liquide | STABILIZING COMPOSITIONS FOR PEROXIDE PRODUCTS |
-
1981
- 1981-12-10 US US06/329,534 patent/US4378300A/en not_active Expired - Fee Related
-
1982
- 1982-11-29 ZA ZA828774A patent/ZA828774B/en unknown
- 1982-11-30 NZ NZ202662A patent/NZ202662A/en unknown
- 1982-12-06 PH PH28231A patent/PH18074A/en unknown
- 1982-12-07 DE DE19823245169 patent/DE3245169A1/en not_active Withdrawn
- 1982-12-08 GR GR70019A patent/GR77844B/el unknown
- 1982-12-08 MX MX195499A patent/MX159189A/en unknown
- 1982-12-09 ES ES518032A patent/ES518032A0/en active Granted
- 1982-12-09 GB GB08235183A patent/GB2112428B/en not_active Expired
- 1982-12-09 BE BE0/209702A patent/BE895307A/en not_active IP Right Cessation
- 1982-12-09 AU AU91361/82A patent/AU555219B2/en not_active Ceased
- 1982-12-09 CA CA000417353A patent/CA1190005A/en not_active Expired
- 1982-12-09 FR FR8220649A patent/FR2518115B1/en not_active Expired
- 1982-12-10 CH CH7221/82A patent/CH654021A5/en not_active IP Right Cessation
- 1982-12-10 IT IT49654/82A patent/IT1150399B/en active
- 1982-12-10 DK DK549782A patent/DK549782A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| GR77844B (en) | 1984-09-25 |
| DE3245169A1 (en) | 1983-06-16 |
| NZ202662A (en) | 1985-04-30 |
| FR2518115B1 (en) | 1986-12-12 |
| IT1150399B (en) | 1986-12-10 |
| BE895307A (en) | 1983-06-09 |
| DK549782A (en) | 1983-06-11 |
| ZA828774B (en) | 1984-07-25 |
| MX159189A (en) | 1989-04-28 |
| GB2112428A (en) | 1983-07-20 |
| PH18074A (en) | 1985-03-18 |
| US4378300A (en) | 1983-03-29 |
| AU9136182A (en) | 1983-06-16 |
| FR2518115A1 (en) | 1983-06-17 |
| ES8402344A1 (en) | 1984-01-16 |
| GB2112428B (en) | 1985-09-04 |
| AU555219B2 (en) | 1986-09-18 |
| ES518032A0 (en) | 1984-01-16 |
| CH654021A5 (en) | 1986-01-31 |
| IT8249654A0 (en) | 1982-12-10 |
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