CA1207955A - Bleaching compositions - Google Patents
Bleaching compositionsInfo
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- CA1207955A CA1207955A CA000437910A CA437910A CA1207955A CA 1207955 A CA1207955 A CA 1207955A CA 000437910 A CA000437910 A CA 000437910A CA 437910 A CA437910 A CA 437910A CA 1207955 A CA1207955 A CA 1207955A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
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- Detergent Compositions (AREA)
Abstract
BLEACHING COMPOSITIONS This invention relates to bleaching compositions. More particularly, this invention relates to bleaching compositions that provide effective and efficient solution bleaching and/or surface bleaching performance on textiles. Such bleaching performance is obtained over an extremely wide class of stains and soils and a wide range of bleaching solution temperatures and pH. The bleaching compositions within the invention contain a carboxylic acid and an aromatic sulfonyl halide bleach activator. In a highly preferred embodiment the bleaching compositions within the invention are detergent compositions.
Description
s John C. Dyer -- BAC:KGROUND INFORMATION
This tnvention relates to bleaching compositions. More particularly, this invention relates to bleaching compositions that provide effective and efficient solution bleaching and/or surface 10 ~leaching performance on textiles. Solution bleaching is bleaching wherein the bleaching mechanism takes place in the bleaching solution itself, I.e., the bleaeh and water mixture, rather than the textile surface, and, thereby, modifies solls that are sus-pended in the bleaching solution. This prevents soils lFrom being 15 deposited on the textile surface and/or decolorizes soils which are then deposited on the textile surface, but are renclered less objectionable. Surface bleaching is bleaching wherein the bleach-ing mechanism takes place on the textile surface and, thereby, modifies stains that are on the textile surface. This results in 20 the removal andlor decoloration of such stains. Such bleaching per~ormance is obtained over an extremely wide class of stains and soils and wide range of bleaching solution temperatures and pH. The bleaching composttions within the Invention contain a peroxycarboxylic acid and an aromatic sul~onyl halide bteach acti-25 vator. In a highly preferred embodiment the bleaching composi-tions within t31e invention are detergent compositions.
It has long been known that peroxygen bleaches that yield hydrogen peroxide in an aqueous solution provide a desirable level of solution hleaching and/or surface bleaching performance, 3D but that they are also extremely temperature dependerlt. Such bleaches are essentially only practicable and/or effective in bleaching solutions wherein the solution temperature is above about 60C. At bleach solution temperatures of about 60C
peroxygen bleaches are only partially effective, due to their low 35 level of reactivity. Therefore, in order to obtain a desirabl~
~0'75~S5 level of bleaching performance extremely high levels of peroxygen bleach must be added to the system. As the bleach solution temperature is lowerecl below 60C, even higher levels of peroxy-gen bleach must be added to the system in order to obtain a desirable level of bleaching performance. The temperature depen-dence of peroxygen bleaches is significant because such bleaches are commonly used as a detergent adjuvant in textile wash pro-cesses that utilize an automatic household washing machine at wash water temperatures below 60C. Such wash temperatures are utilized because of textile care and energy considerations.
As a conse~uence of such wash processes, there has been much industrial research to develop substances, generally referred to as bleach activators, that render peroxygen bleaches effective at bleach solution temperatures below 60C. Numerous substances have been disclosed in the art as effective bleach activators.
Typically, the substances that have been utilized as bleach activators are substances that react with the perhydroxide anion of hydrogen peroxide, which is yielded by the peroxygen bleach in the bleaching solution, to form a peroxy acid. Peroxy acids are more reactive than the peroxygen bleach alone and, there-fore, can provide bleaching at bleach solution temperatures below about 60C. Many of the peroxy acids are peroxycarboxylic acids or persulfonic acids. The peroxycarboxylic acids are derived from bleach activators that contain a carbonyl carbon that reacts ~5 with the perhydroxide anion to form the peroxycarboxylic acid.
Examples of such bleach activators are disclosed in U.S. Patents 4,248,9~8, Spadini et al (February 3, 1981); 4,126,573, ~ohnston (November 21, 1978) and 4,100,095, Hutchins et al (July 1t ~
1978). The persulfonic acids are derived from bleach activators that contain a sulfonyl group that reacts with the perhydroxide anion to form the persulfonic acid. For example, U.S. Patent 4,292,19t, Gray (September 29, 1981) discloses bleaching composTtions containing a peroxygen bleach and a sulfonyl halide bleach activator, such as an all<oxybenzenesulfonyl halide. U.S.
Patent 4,107,065, Gray ~August 15, 1978) discloses bleaching , . ~ _ . _, ~2~'79SS
compositions containing a peroxygen bleach and a sulfonyl bleach activator, such as an aromatic sulfonyl halide.
SUMMARY OF TH~ INVENTION
The present invention comprises a bleaching composition 5 containing:
(a) a peroxycarboxylic acid or salt ther~of or precursors thereof; and (b) an aromatic sulfonyl halide bleach activator;
~Ivherein the molar ratio of each potential and actual 10 peroxycarboxyl group of (a~ to each sulfonyl group that can potentially generate an acyl persulfonate is from about 10 to about 0.05 .
DETAILED DESCPclPTlON OF THE tNVENTlON
This invention relates to bleaching compositions consisting of 15 a peroxycarboxylic acid and an aromatic sulfonyl halide bleach activator, both of which are defined hereinafter. The bleaching compositions provide very effective and e~ficient solution bleach-ing and/or surface bleaching performance on te~iles. Solueion bleaching is particularly beneficial when the ~leaching composi-20 tlons are detergent compositions. This is bec2use a detergentsystem may be effective for removing soils from lthe textiles and into the bleaching solution, but not for preventing such soils from being redeposited onto the textiles. Solution bleaching modifies the soils in the bleaching solution and, therebyO reduces 25 such soil redeposition and/or decolorizes the solls which renders soil redeposition less objectionable~ The surface bleaching pro-vided by the bleaching compositions not only provides effective and efficient removal and/or decoloration of stains on textiles, but also provides dingy soil removal. Dingy soils are soils that build 30 up on textiles after numerous cycles of usa~e and washing and, thus, result in a white textile having a gray tint. These soils tend to be a blend of body lipids and proteinaceous debris. The removal of this type of soil is sometimes referred to as "dingy fabric clean up". Furthermore, such solution bleaching andlor 35 surface bleaching performance is obtained with m;nimal damage to ~Z07955 $he textiles and with bleach solution temperatures as low as about 5C. Bleaching compositions consisting only of a peroxycarboxylic acid or a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus an aromatic s sulfonyl ha!ide bleach activator are also able to provide solu~ion bleaching andtor surface bleaching at temperatures below about 60C, i.e., the temperature wherein peroxygen bleaches are essentially ineffective; however, they provide neither the effectiveness nor the efficiency of the bleaching compositions 10 within the invention.
The bleaching compositions within the invention are extreme-ly effective. Such compositions provide a superior level of solution bleaching and/or surface bleaching per~ormance over a very wide class of stains. Bleaching compositions consisting of 15 only a peroxycarboxylic acid or, especially, a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus an aromatic sulfonyl halide bleach activator do not provide the superior level of bleaching performance over a very wide olass of stains. Bleaching compositions consisting only of a peroxycar-20 boxylic acid provide, at best, a superior level of bleaching per-~ormance for only a narrow class sf stains. Such performance is obtained primarily on beverage type stains, e.g., tea and wine.
This severely limits the practicability of such compositions because there are numerous other types of common stains. Without 25 being bound by theory, it is believed that this stain specificity is based upon the chemical structure of the stain. Beverage type stains consist essentially of aromatic type compounds. Other common stains, such as grass, ink and tomato, have structures which are very olefinic. This structural difFerence is believed to 30 be the cause of the stain specificity of such bleaching compo-sitions. Bleaching compositions consisting only of a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus an aromatic suifonyl halide bleach activator do not provide the superior level of bleaching performance, regardless of ~5 the type of stain. Surprisingly, only the compositions within the ~ 7955 invention provide the superior level of solution bleachin~ andlor surface bleaching performance over a very wide class of stains.
The bleaching compositions within the invention are very efficient. Extremely small quantities of such compositions provide 5 the superior level of solution bleaching and/or surface bleaching performance. Without being bound by theory, gt is believed that such efficiency is obtained because a substantial majority of active oxygen, defined below, is lJtilized for bleaching durin~3 the bleaching process. This can be explained as follows.
It is believed that the peroxycarboxylic acid reacts with the aromatic sulfonyl halide bleach actiYator to form an acyl persul-fonate. Since the acyl persulfonate contains an -O-O- group it contains a reactive oxygen atom, generalty referred to as an "active oxygen" atom. The active oxygen is the active bleaching 15 component which reacts with and, thereby, modifies stains on textiles and/or soils in the bleaching solution. The acyl persul-fonate is sufficiently reactive so that very little active oxygen is present after the bleaching process. However, and lust as important, the acyl persulfonate is not too reactive, based upon 20 the superior level of solution bleaching and/or surface bleachin~3 performance observed, so as to decompose rather than provide such bleaching performance. Therefore, the vast majority of the active oxygen is utilized for bleaching during the bleaching process. This enables one to obtain the superior ievel of bleach-25 ing performance with very small amounts of the Dleaching compo-sitions within the invention.
Bleaching compositions consisting only of a peroxycarboxylic acid or a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus an aromatic sulfonyl halide bleach 30 activator are extremely inefflcient and/or ine~fective. Bleaching compositions consisting only of a peroxycarboxylic acid are very inefficient because a substantial amount of the active oxygen of the peroxycarboxylic acid remains in the bleaching solution after the bleaching process is carried out. This unreacted peroxycar-35 boxylic acid is essentially wasted. Thus, in order to achieve the ., . ~
L
~z~
superior level of bleaching performance very large amounts of such compositions, as compared to th~ bleaching compositions within the invention, are required. However, it should be noted that regardless of the amount of peroxycarboxylic acid added to S the bleaching sols~tion, within practicable limits, the desired superior level of bleaching performance is obtain~d primarily on beverage type stains. E~leaching compositions consisting of a peroxygen bleach capable of yieiding hydrogen peroxide in an aqueous solution plus an aromatic sulfonyl halide bleach activator are very efficient in that very little active oxygen is present after the bleaching process. However, such bleaching compo-sitions do not provide the desired superior level of solution bleaching per~ormance and provide essentially no surface bleach-ing. Without being bound by theory, it is believed that the persulfonic acid ~ormed is so reactive that it decompos~s before it even oomes into contact with the textiles. Only the bleaching rompositions within the invention are both efficient and provide r the superior level of solution bleaching andlor surface t)leaching performance over a very wide class of stains.
Another major advantage of the bleaching compositions within the invention is that they provide the superior level of solution bleaching and/or surface bleaching performance over a very wide range of pH's of the bleaching solution. Therefore, ~or example, when the bleaching compositions are detergent compositions one can adiust the pH of the bleaching solution so as to optimize detergency performance without sacrificing bleaching performance.
Typical activated bleaching compositions, i.e., those consisting only of a peroxygen bleach capable of yielding hydrogen peroxids in an aqueous solution and a bleach activator which react in the bleaching solution to form a peroxy acid, are very pH dependent.
It is believed that such p~ dependence is due to the fact that the active oxygen of the peroxy acid reacts with stains and/or soils via the formation of a dimer by the peroxy acid with its anion. Thus, in order to maximize the amount of the dimer ~ormed it is essential that the PKa of the peroxy acid be similar to the pH of the ~L2~7~55 bleaching solution. This ensures that there will be similar levels of the peroxy acid and its anion present in the bleaching solution and, therefore maximizes the amount of dimer formef:l. Otherwise, there will be an excess of peroxy acid as compared to its anion or 5 vice versa; either of such excess is not utilized and, thus, as indicated by experimental eYidence, bleaching performance deciines. It should be noted that even if the pH of the bleaching solution is similar to the PKa of the peroxy acid the vast maiority of the active oxygen is still present after the bleaching process.
10 It is theorized that the bleaching compositions within the inven-tion do not operate via the formation of a reactive climer and, therefore, as indicated by experimental evidence, provide the superior level of bleaching performance over a wide range of pH's.
The initial pH of the bleaching solution containing the bleaching compositions within the invention is from about 6 to about 12, preferably from about 7 to about 11 and most prefer-ably from about 8.5 to about 10.
In the compositions within the invention the ratio of the 20 peroxycarboxylic acid to aromatic sulfonyl halide is such that the molar ratio of each actual and potential peroxycarboxyl group of the peroxycarboxylic acid to each sulfonyl group of the aromatic sulfonyl halide that can potentially generate acyl persulfonate is from about 10 to about 0.05, preferably from about 1 to about .3 25 and most preferably from about 1 to about 0.7. Molar ratios of such components of from about 1 to about O . 7 a re most preferred because vast excesses of either component will result in such excess not interacting with the other component and, therefore, won't provide the superior îevel of bleaching performance that is 30 obtained by such components that interact with each other. The terlT "potential peroxycarboxyl group" is meant to define the level of peroxycarboxylic acid that can be present in the bleaching compositions within the invention when the peroxycarboxylic acid is generated in situ, as discussed hereinafter. It should be 3i noted that the ratio is found to vary considerably as a function )7~S5 of pH. For example, if the initial pH of the bieaching solution is greater than 10, then excess aromatic sulfonyl halide would be preferred to make up for the amount lost clue to alkaline hydrolysis.
The following is a detailed description of the essential and the optional components of the bleaching compositions within the invention. All percentages, parts 01' ratios are by weight unless otherwise indicated.
THE PEROXYCARBOXYLIC ACID
Essentially any peroxycarboxylic aoid or salt thereof is suitable lFor use herein. Albeit some peroxycarboxylic acids are more preferred than others, it is believed that the effectiveness and efficiency of solution bleaching and/or surface bleaching perforn~ance of essentially any peroxycarboxytic acid will be enhanced by utilizing it in the bleaching compositions within the invention .
The preferred peroxycarboxytic acids and sal~s thereof have the general formula:
~: . . _ _ R- jC-O-OM
~ _ r wherein R is selected from the group consisting ~lF H, a linear or branched alkyl or alkylene group containing from t to about 18 carbon atoms, a cyciic alkyl, or alkylene group containing from about 3 to about 18 carbon atoms, an aryl group, an aromatic heterocyclic group, a polyarylene group consisting of two or more annelated benzenoid rings and groups in which two or more aryl or arylene substituents are covalently attach~d, M is H or a cation which provides water-solubility or dis~ersibility to the peroxycarboxylic acid and r is from l to the total number of hydrogen atoms on R. Preferably, M is H or an alkali metal or an alkaline earth metal, with H, magnesium, sodium and potassium being the most preferred. R can be substituted with essentially any group or groups, including an alkyl group when R is aryl and an aryl group when R i5 alkyl, so long as they do not lZ(~79~iS
interfere with the function of the peroxycarboxylic aeidO The preferred alkyl or alkylene group substituents are -SO3M and -COOM and the preferred aryl and arylene substituents are selected from the group consisting of halogens (fluorine, chlorine, or bromine), ~N02, -OCH3 and -COOM wherein l~A is as defined above. Suitable aromatic heterocyclic groups include furan, thiophene and pyridine. Examples of polyarylene groups consist-li-g of two or more annelated benzenoid rings are the naph~hyl, phenanthryl and anthraceny3 moietiès.
The more preferred peroxycarboxylic acids and salts thereof have the general formula:
~ -~-O-OM or T E ~-O-O-M~
wherein A is a halogen (fluorine or chlorine) or -NO2, M is as defined above, T is an alkyl group containing from about 5 to about 18 carbon atoms ar;d r is one or two.
The most preferred peroxycarboxylic acids ~nd salts thereof have the general ~ormula:
A O
~> -C-O-OM
wherein A i5 a halogen (chlorine or fluorine), preferably Cl, and M is H or magnesium. Surprisingly, when halogen substituted peroxybenzoic acids or salts thereof are utilized within the compositions of the invention, solution bleaching and, especially, surface bleaching perforrnance are exceptional.
Formation of the Peroxycarboxylic Acid In Situ by l.ltilizing Specific Peroxygen Bleaches and Bleach Activators As an alternative to directly adding the peroxycarboxylic acid to the bleaching solution, the peroxycarboxylic acid can be formed in situ lFrom its precursors. For example, a two -component peroxycarboxylic acid source consistin~ of a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution and a bleach activator that contains a carbonyO carbon that can pot~ntially react with the hydrogen peroxide to form a ~r1~ ' ~'7~5 peroxycarboxylic acid can be utilized. The use of this system within the compositions of the invention provides essentially the sarne leYel of effectiveness and efficiency of solution bleaching and/or surface bleaching performance as is obtained by directly 5 utilizing a peroxycarboxylic acid within the compositions of the invention . - -An ~dditional advantage of such two component peroxycar- -boxylic acid source with respect to bleaching compositions con-sisting solely of such two components is based upon pH As 10 discussed above, for bleaching compositions that consist solely of such peroxygen bleach and bieach activator, it is believed that the pH of the bleaching solution must be adjusted to be similar to the PKa of the peroxycarboxylic acid formed in order So maximize the formation of the reactive dimer. However, the pl~ of the 15 bleaching solution must also be adjusted to ensure that the hy-drogen peroxide, yielded by the peroxygen bleach, is to an appreciable extent in the perhydroxide anion form~ This maxi-mizes the rate of formation of the peroxycarboxylic acid. There-fore, since there are two pH dependent chemical reactions that 20 must take place, neither one can be maximized. However, when utilizing the two component peroxycarboxylic acid source within the compositions of the snvention the pH of the bleaching solution need not be similar to the PKa of the peroxycarboxylic acid.
Therefore, one can adjust the pH of the bleaching solution to 25 maximize the formation of the perhydroxide anion and, thus, maximize the formation of the peroxycarboxylic acid.
The Peroxygen Bleach The peroxygen bleaches useful herein are those capable of yielding hydrogen peroxide in an aqueous solution. These 30 bleaches are well known in the art and includa hydrogen peroxide and the alkali metal peroxides, organic peroxide bleaching com-pounds such as urea peroxide, and inorganic persalt bleaches, such as the alkali metal perborates, percarbonates, perphos-phates, and the like. hlixtures of two or more such bleaches can 35 also be used, if desired.
~!LZ(~75~S~
Preferred peroxygen bleaches include sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhy-drate, urea peroxyhydrate, and sodium peroxide. Particularly preferred are sodium perborate monohydrate and sodium perborate tetrahydrate and mixtures thereof.
The Bleach Activator The bleach activators that can be utilized for such a purpose are ones capable of generating peroxycarboxylic acids and have the general formula: -O
R - ~ - L
wherein R is as defined above and L is a leaving group, wherein the conjugate acid of the anion formed on L has a PKa in the range of from about 4 to about 13.
L can be essentially any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophi!ic attack on the bleach activator [ by ths perhydroxide anion. This, as discussed hereinabove, is the perhydrolysis reaction. Leaving groups that exhibit such behavior are those in which their conjugate acid has a PKa in the range of from about 4 to about 13, preferably from about 7 to about 11 and most preferably from about 8 to about 11.
It should be noted that, as an option, R or L can be a group that contains an aromatic sulfonyl halide. Such a system can be utilized in combination with a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution and provides the desired level of solution bleaching and/or surface bleaching performance .
3~ Preferred bleach activators are those of the above general formula wherein R is as defined above and L is selected from the group consisting of:
_o~ , -o{~ , - O ~, -N-C-R, lZ~S~
O ~ -0~
-0-C-R, -N H, -Q,~_ -0-CH = C - CH = CH2, -N ,N
~.2 -0-C = CHR, wherein R is as defined above, ~2 is an alkyl chain containing from about 1 to about 8 carbon atoms, R3 is H or R2, and Z is H
or a solubilizing group. The preferred solubilizing groups are -503M, -C00 M, -S04M, (-N R34)X and O+NR2 and most preferably -S03M and -C00 M wherein R is an alkyl chain containing from about 1 to about 4 carbon atoms, 1~/1 is as defined above and X is an anion which provides solubility to the bleach activator. Preferably, X is a halide (fluorine, chlorine or 2û bromine), hydroxide, methylsulfate or acetate anion. It should be noted that bleach activators with a leaving group that does not contain a solubilizing group should be well dispersed in the bleaching solution in order to assist in their dissolution.
The molar ratio of hydrogen peroxide yielded by the peroxy-25 gen bleach to such peroxycarboxylic acid generating bleach activator is from about 20 to about 0.1, preferably lFrom about 3 to about 1 and most preferably from about 2 to about 1.
However, it should be noted that the preferred ratio is found to vary considerably if the initial pH of the bleaching solution ;s 30 below about 9. Under such conditions a higher molar ratio of hydrogen peroxide yielded by the peroxygen bleach to peroxycarboxylic acid generating bleach activator is desirable.
Preferably, such molar ratio is from about 4 to 20.
9S~
Formation of The Peroxycarboxylic Acid In Situ Utilizing an Organic Peroxide Compound Another precursor that can be utilized to ~orm the perox-ycarboxylic acid in situ is an organic peroxide compound. It is 5 believed that such a compound undergoes hydrolysis in the bleach-ing solution to form the peroxycarboxylic acid. This system is not preferred because the peroxycarboxylic acid formation is often slow and, therefore, it is theorized that during this time some of the aromatic sulfonyl halide bleach activator undergoes hydrolysis 10 to form an inactive sulfonic acid.
The organic peroxide compounds have the general formula:
O O
R - C - O - O - C - R
wherein each R is as defined above.
As an option, a peroxygen bleach, such as those described above, can also be added to the bleaching solution with the organic peroxide compound. This results in the potential forma-tion of two moles of peroxycarboxylic acid per mole of organic peroxide and, therefore, only half of the level of organic peroxide is required as would otherwise be necessary without such peroxygen bleach. The molar ratio of such or~anic peroxide compounds to such peroxygen bleach is from about 0.1 to about 10, preferabiy from about 0.~5 to about ~ and most preferably from about 1 to about 0.3.
The level of peroxycarboxylic acid within compositions of the invention is from about 0.1% to about 8096, preferably from about 5% to about 60% and most preferably from about 30% to about 60%.
It should be noted that when a two component peroxycarboxylic acid source is utilized, e.g., a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus a peroxycarboxylic acid generating bleach activator or such peroxygen bleach plus an organic peroxide compound, the level of each component should be such that it can theoretically produce the levels of peroxycarboxylic acid within the compositions of the 35 invention. When the bleaching compositions within the invention ~ . lZ~7~55 . . .
are also detergent compositions i$ is preferred that the level of peroxycarboxylic acid is from about 0.1% to about 10% and more preferably from about 196 to about 3%.
l HE AROMATIC SULFONYL HALIDE
Essentially any aromatic sulfonyl halide bleach activator is suitable for use herein. l he aromatic group can contain one or more substituents so long as they do not inter~ere with the function of the bleach activator.
The preferred aromatic sulfonyl halide bleach activators within the compositions of the invention have the general ~ormula:
Y 3E {~
wherein each Y is selected from the group consisting of:
H, -C N tC 2H 2 ) 2, -OC 2H 2 n 2n +1 n 2n +1 n2 2n2+1 O O
( N+(C 11 )3), -OC CnH2n~1 ~ ~5CnH2n+l ~ n 2n~1 o halogens and any group which provides an anionic moiety in aqueous solution wherein each n is from O to about 12 and each n is lFrom 0 to about 1~, E is selected from the group consisting 25 of an aryl arylene group, an aromatic heterocyclic group, a polyarylene group consisting of two or Inore annelated benzenoid rings and groups in which two or more aryl arylene substituents are covalently attached, Q is a halogen (fluorine, chlorine, or bromine] preferably chlorine, and each n is from 11 to about 3.
30 Suitable aromatic heterocyclic groups include furan, thiophene, quinoline and pyridine. Examples of polyarylene groups consist-lng of two or more annelated groups are the naphthyl, ph~nanthryl and anthracenyl moieties.
The preferred aromatic sulfonyl halide bleach activators are 35 selected from the group consisting of:
~.
I
~L2~5 , -- 15 -- .
O O O
1 13 C ~S - C l, H3C~S F~
O COOH O
Cl 5{~s Cl ~ - Cl S - Cl O O
10The most preferred aromatic sulfonyl halide bl~ach activator has the formula:
~ ~ - C I
15(~O
S - Cl The level of aromatic sulfonyl halide within the compositions of the invention is from about .1% to about 70%, preferably from 20about 5~ ~o about 70% and most preferably from about ~0% to about 709~. When the bleaching cornpositions within the invention are also detergent compositions it is preferred that the level of aromatic sulfonyl halide is from about 0.1% to about 10% and more preferably from about 19~ to about 3~.
25OPTiONAL COMPONENTS
As a preferred embodiment, the bleaching compositions of the invention can be detergent compositions. T51us, the bleaching compositions can contain typical detergent composition components such as detergency surfactants and detergency builders. In such 30preferred embodiments the bleaching compositions are particularly effective. The bleaching compositions of this invention can contain all of the usual cornponents of detergent compositions Including the ingrediants set forth in U~S. Patent 3~fl36,537, Baskerville et al, Such com-35ponents include color speckles, suds boosters, suds suppressors, .
7~35S
antitarnish and/or anticorrosion agents, soil-suspendin~ agents, soil-release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, perfumes, etc.
The detergent surfactants can be any one or more surface active agents selected from anionic, nonionic, zwitterionic, ampho-teric and cationie classes and compatible mixt~res thereof.
Detergent surfactants useful herein are listed in U . S. Patent 3,664,961, Norris, issued May 23, 1972, and In U.S. Patent 3,919,678, I aughlin et al, issued Decamber 30, 1975,~
Useful cationic surfactants also include those described in U.S. Patent l~,222,gOS, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980, t5 The ~ollowing are representative examples of deter-gent surfactants useful in the present compositions.
Water soluble salts of the higher fatty acids, i.e., soaps, are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammon-ium, and alkylammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. sGaps can be made by direc saponification of fats and oils or by the neutralizatiorl of ~ree fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oii and tallow, i.e., sodium or potassium tallow and coconut soap.
Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylammonium salts, of organic sulfuric reaction products having in their mole-cular structure an alkyl group containing from a~out 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
(Included in the term alkyl is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sul-fating the higher alcohols (C8-C18 carbon atoms) such 3S those ~7~i produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383. Espec-ially valuable are linear straight chain alkylbenzene sulfonates in which the average number of c~rbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11 13LAS.
Other anionic surfactants herein are the sodium alkyl gly-ceryl ether sulfonates, especially those ethers of higher alcohois derived from tallow and coconut oil; sodium coconut oil fatty acid monoglycerlde sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the est r group; water-soluble salts of 2-acytoxyalkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 tu about 23 carbon atoms in the alkane moiety; water-solubie satts of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Water-soluble nonionic surfactants are also useful in the compositions of the invention. Such nonionic rnaterials include compounds produced by the condensation of alkyl or alkylene oxlde groups thydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
- ~2~ 5 The length of the polyoxyalkytene group which is condensed with any particular hydrophobic group can be readily adiusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Suitable nonionic surfactants Include the pl~lyethylene oxide condensatés of alkyl phenols, e.g., the condensation products o~
alkyl phenols having an alkyl group containing from about 6 to 15 carbon atoms, in either a straight chain or branched chain con-figuration, with from about 3 to 12 moles of ethylene oxide per mole of alkyl phenol.
Preferred nonionics are the water-soluble and water-disper-sible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched config-uration, with from 2 to 12 moles of ethylene oxide per mole of a!cohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to 8 moles of ethy~ene oxide per mole of alcohol.
Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and two moleties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms;
water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups con-taining from about 1 to 3 carbon atoms; and water-soluble sulfox-ides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group c~sisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
Ampholytic surfactants includs derivatives of alipha~ic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains ~rom about 8 to 18 carbon atoms and at least one aliphatic substituent con-tains an anionic water-solubilizing group.
~,,fz~
;
2witterionic surfactants include derivatives of aliphatic, quaternary~ ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
The level of detergent surfactant that can be employed is from 0% to about 50%, preferably from about 1% to about 30~ and most preferably from about 10% to about 25~ by ~reîght of the total composition.
In addition to detergent surfactants, detergency builders can l O be employed in the bleaching compositions. Water-soluble inor-ganic or organic elec~rolytes are suitable builders. The builder can also be water-insoluble calcium lon exchange materials; non-limiting examples of suitable water-soluble, inorganlc detergent builders include: alkali metal carbonates, borates, phosphates, bicarbonates and silicates, Specific examples of such salts include sodium and potasslum tetraborates, bicarbonates, carbonates, orthophosphates, pyrophosphates, tripolyphosphates and meta-phosphates.
Examples of suitable organic alkaline detergency builders include: (1 ) water-soluble amino carboxylates and aminopolyace-tates, for example, nitrilotriacetates, glycTnates, ethylenediamine tetraacetates, N-~2-hydroxyethyl)nitrilo diacetates and diethy3-enetriamine pentaacetates; (2) water-soluble salts of phytic acid, for example, sodium and potassium ,ohytates; t3) water-soluble polyphosphonates, including sodiurn, potassium, and lithium salts of ethane-l-hydroxy-1, 1-diphosphonic acid; sodium, potassium, and lithium salts of cthyiene diphosphonic acid; and the like; (43 water-soluble polycarboxylates such as the sal~s olF lactlc acid, succinic acid, malonic acid, maleic acid, citric acid~ carboxy-3a methyloxysuccinic acid, 2-oxa-l ~1 ,3-propane tricarboxylic acid, 1,1 ,2,2-ethane tetracarboxylic acid, mellitic acid and pyromellitic acid; l5) water-soluble polyacetals as disclosed in U.S. Patents 4,144,266 and 4,246,495~ and 16) water-soluble polyacrylates.
75~iS
.
.
-- 2~ --Another type ~f detergency builder material use~ul in the present compositions comprises a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which 5 is capable of providing growth sites for said reaction product.
Such "seeded builder" compositions are fully disclosed in British Patent Specification No. 1,424,406.
A further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particu-10 lariy those described in U.S. Patent 4,303,556 issued December 1, 1981, This patent discloses and claims detergent compositions containing sodium aluminosili-cates having the formula:
Naz(A102) Z~S jO2)yXH20 15 wherein z and y are integers equal to at least 6, the molar ratio of z to y is in the ran~e of from 1.0:1 to about 0.5:1, and X is an integer from about 15 to about 264, said aluminosilicates hav-ing a alcium ion exchange capacity of at least 200 milligrams equivalent/gram and a calcium ion exchange rate of at least about 20 2 grains/gallon/minutetgram. A preferred material is Zeolite A
which is:
Nal 2 ~ STO2AlO2 ) 1227 H2O
The level of detergency builder of the bleaching compositisns is from 0% to about 70%, preferably from about 10~ to about 60~6 25 and most preferably from about 20% to about 60~.
Buffering agents can be utilized to maintain ~he desired alkaline pH of the bleaching solutions. Buffering agents include, but are not limited to many of the detergency builder compounds disclosed hereinbefore. Buffering ayents suitable for use herein 30 are those well known in the detergency art.
Preferred optional ingredients include suds modifiers parti-cularly those of suds suppressing types, exemplified by silicones, and silica-silicone mixtures. U.S. Patents 3,933,672, issued January 20, 1976 to Bartolotta et al, and 4,136,045, issued January 23, 1979 to Gault e~ al, disclose silicone suds controlling agents. Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in U.S. Patent 4,073,1t8, Gault et al, issued February 21, 1 978 , An example of such a compound is DB-544, commerciatly available from Dow Corning, which is a siloxanelglycol copolym~r. Suds modifiers as described above are used at levels of up to approxi-mately 2~, preferably from about 0.1 to about ~ by weight o~
10 the surfactant.
Microcrystalline waxes having a melting point in the rang~
from 35C-115~C and a saponiflcation value of less than 100 represent additional examples of preferred suds control compon-ents ~or use in the subject compositions, and are described in 15 detail in U.S. Patent 4,056,481, Tate, issued November 1, t977, The microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfactants. Preferred microcrystalline waxes have a melting point from about 65C to 100C, a molecular weight 20 Tn the range from 400-1, 000; and a penetration value of at least 6, measured at 77F by ASTM-D1321. Suitable examples o~ the above waxes include: microcrystalline and oxidized microcrystal-line petroleum waxes; Fischer-Tropsch and oxidizecl Fischer-Tropsch waxes; ozokerite; ceresin; montan wax; beeswax; cande-25 lilla wax; and camauba wax.
Alkyl phosphate esters represent an additional preferred suds control agent for use herein. These pre~erred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain Bi- and tristearyl phosphates and monooleyl 30 phosphate, which can contain di- and trioleyl phosphate.
Other suds control agents useful in the practlce of the invention are the soap or the 50ap and nonionic mixtures as disclosed in U.S. Patents 2,954,347 and 2,954,348, * l~ad~nark ,.~
,. . ., ~.~, . _ _ . ~ _ . _ _ _ _ _ , _ _ . . ~ _ .. _ ... . . ... ~ . _ . . . . , _ ... _ . _ . . _ ~Z0~7~
~ 22 -Fluorescent or optical brighteners can be utilized within the bleaching compositions of the invention. Surprisingly, such brighteners exhibit acceptable compatibility with such composi-tions. Suitable anionic brighteners are disclosed in U.S. Patents 3,537,993 Coward et al (November 3, 1~70) and 3,953,380 Sundby (April 27, 1976), Nonionic brighteners can also be utilized within the compositions of the invention .
The following examples are given to illustrate the parameters o of and compositions within the invention. All percentages, parts and ratios are by weight unless otherwise indicated.
EXAMPL~ I
The following granular detergent composition was prepared:
m C16_18 alkyl sulfate 5o5 Sodium C12 linear alkylbenzene sulfonate 3~5 C14_l6 alkyl polyethoxylate2 25 5.5 Sodium tripolyphosphate 2~
Zeolite A 17.6 20 Sodium carbonate 10~5 Sodium silicate (2.0r) 1.9 Sodium sulfate 2t.0 Water IB.g Mi scel laneous 1 . 2 Two sets of six 5"x5" swatches consisting of fiYe polycotton swatches each stained with one of the following stains - chili, RAGU spaghetti sauce, mustard, ink and tea - and one denim swatch stained with grass were prepared.
A laundry load consisting of one set of the six swatches, 30 four clean terry cloth towels and one terry cloth towel soiled with 1.5 grams o~ a mlxture of artificial body soil and vacuum cleaner soil was placed in a mini-wash system. This laundry load was ~hen washed with S.5 grams of the above granular detergent composition in 5 . 5 liters of water . This mTni-wash system with 35 such a load and granular detergent concentration simulates a * Trad~nark __ :~.zu7~
.
conventional automatic wash process. The wash water tempera-ture was 37C and the wash water contained 8 grains/gallon water hardness. The initial pH of the wash water was about 9.7.
After drying, each of the swatches was visually graded by 5 comparing it to its unwashed counterpart. A grading scale of 0 to 5 was used, with 0 indicating no stain removal and 5 indicating 100% stain removal. Each swatch was graded by three graders and then the average grade for each swatch was calculated. This average was then scaled from 0 to 100, with 100 being 100% stain 10 removal. Also, the mean for the set of swatches was calculated.
The entire procedure was repeated numerous times, but each time a different bleaching system was added to the mini-wash system one minute after the start of the wash process.
The results were as follows:
9~ Stain Removal Bleachin~ SystemChili Spa~hetti Mustard 1. None 62 60 64
This tnvention relates to bleaching compositions. More particularly, this invention relates to bleaching compositions that provide effective and efficient solution bleaching and/or surface 10 ~leaching performance on textiles. Solution bleaching is bleaching wherein the bleaching mechanism takes place in the bleaching solution itself, I.e., the bleaeh and water mixture, rather than the textile surface, and, thereby, modifies solls that are sus-pended in the bleaching solution. This prevents soils lFrom being 15 deposited on the textile surface and/or decolorizes soils which are then deposited on the textile surface, but are renclered less objectionable. Surface bleaching is bleaching wherein the bleach-ing mechanism takes place on the textile surface and, thereby, modifies stains that are on the textile surface. This results in 20 the removal andlor decoloration of such stains. Such bleaching per~ormance is obtained over an extremely wide class of stains and soils and wide range of bleaching solution temperatures and pH. The bleaching composttions within the Invention contain a peroxycarboxylic acid and an aromatic sul~onyl halide bteach acti-25 vator. In a highly preferred embodiment the bleaching composi-tions within t31e invention are detergent compositions.
It has long been known that peroxygen bleaches that yield hydrogen peroxide in an aqueous solution provide a desirable level of solution hleaching and/or surface bleaching performance, 3D but that they are also extremely temperature dependerlt. Such bleaches are essentially only practicable and/or effective in bleaching solutions wherein the solution temperature is above about 60C. At bleach solution temperatures of about 60C
peroxygen bleaches are only partially effective, due to their low 35 level of reactivity. Therefore, in order to obtain a desirabl~
~0'75~S5 level of bleaching performance extremely high levels of peroxygen bleach must be added to the system. As the bleach solution temperature is lowerecl below 60C, even higher levels of peroxy-gen bleach must be added to the system in order to obtain a desirable level of bleaching performance. The temperature depen-dence of peroxygen bleaches is significant because such bleaches are commonly used as a detergent adjuvant in textile wash pro-cesses that utilize an automatic household washing machine at wash water temperatures below 60C. Such wash temperatures are utilized because of textile care and energy considerations.
As a conse~uence of such wash processes, there has been much industrial research to develop substances, generally referred to as bleach activators, that render peroxygen bleaches effective at bleach solution temperatures below 60C. Numerous substances have been disclosed in the art as effective bleach activators.
Typically, the substances that have been utilized as bleach activators are substances that react with the perhydroxide anion of hydrogen peroxide, which is yielded by the peroxygen bleach in the bleaching solution, to form a peroxy acid. Peroxy acids are more reactive than the peroxygen bleach alone and, there-fore, can provide bleaching at bleach solution temperatures below about 60C. Many of the peroxy acids are peroxycarboxylic acids or persulfonic acids. The peroxycarboxylic acids are derived from bleach activators that contain a carbonyl carbon that reacts ~5 with the perhydroxide anion to form the peroxycarboxylic acid.
Examples of such bleach activators are disclosed in U.S. Patents 4,248,9~8, Spadini et al (February 3, 1981); 4,126,573, ~ohnston (November 21, 1978) and 4,100,095, Hutchins et al (July 1t ~
1978). The persulfonic acids are derived from bleach activators that contain a sulfonyl group that reacts with the perhydroxide anion to form the persulfonic acid. For example, U.S. Patent 4,292,19t, Gray (September 29, 1981) discloses bleaching composTtions containing a peroxygen bleach and a sulfonyl halide bleach activator, such as an all<oxybenzenesulfonyl halide. U.S.
Patent 4,107,065, Gray ~August 15, 1978) discloses bleaching , . ~ _ . _, ~2~'79SS
compositions containing a peroxygen bleach and a sulfonyl bleach activator, such as an aromatic sulfonyl halide.
SUMMARY OF TH~ INVENTION
The present invention comprises a bleaching composition 5 containing:
(a) a peroxycarboxylic acid or salt ther~of or precursors thereof; and (b) an aromatic sulfonyl halide bleach activator;
~Ivherein the molar ratio of each potential and actual 10 peroxycarboxyl group of (a~ to each sulfonyl group that can potentially generate an acyl persulfonate is from about 10 to about 0.05 .
DETAILED DESCPclPTlON OF THE tNVENTlON
This invention relates to bleaching compositions consisting of 15 a peroxycarboxylic acid and an aromatic sulfonyl halide bleach activator, both of which are defined hereinafter. The bleaching compositions provide very effective and e~ficient solution bleach-ing and/or surface bleaching performance on te~iles. Solueion bleaching is particularly beneficial when the ~leaching composi-20 tlons are detergent compositions. This is bec2use a detergentsystem may be effective for removing soils from lthe textiles and into the bleaching solution, but not for preventing such soils from being redeposited onto the textiles. Solution bleaching modifies the soils in the bleaching solution and, therebyO reduces 25 such soil redeposition and/or decolorizes the solls which renders soil redeposition less objectionable~ The surface bleaching pro-vided by the bleaching compositions not only provides effective and efficient removal and/or decoloration of stains on textiles, but also provides dingy soil removal. Dingy soils are soils that build 30 up on textiles after numerous cycles of usa~e and washing and, thus, result in a white textile having a gray tint. These soils tend to be a blend of body lipids and proteinaceous debris. The removal of this type of soil is sometimes referred to as "dingy fabric clean up". Furthermore, such solution bleaching andlor 35 surface bleaching performance is obtained with m;nimal damage to ~Z07955 $he textiles and with bleach solution temperatures as low as about 5C. Bleaching compositions consisting only of a peroxycarboxylic acid or a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus an aromatic s sulfonyl ha!ide bleach activator are also able to provide solu~ion bleaching andtor surface bleaching at temperatures below about 60C, i.e., the temperature wherein peroxygen bleaches are essentially ineffective; however, they provide neither the effectiveness nor the efficiency of the bleaching compositions 10 within the invention.
The bleaching compositions within the invention are extreme-ly effective. Such compositions provide a superior level of solution bleaching and/or surface bleaching per~ormance over a very wide class of stains. Bleaching compositions consisting of 15 only a peroxycarboxylic acid or, especially, a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus an aromatic sulfonyl halide bleach activator do not provide the superior level of bleaching performance over a very wide olass of stains. Bleaching compositions consisting only of a peroxycar-20 boxylic acid provide, at best, a superior level of bleaching per-~ormance for only a narrow class sf stains. Such performance is obtained primarily on beverage type stains, e.g., tea and wine.
This severely limits the practicability of such compositions because there are numerous other types of common stains. Without 25 being bound by theory, it is believed that this stain specificity is based upon the chemical structure of the stain. Beverage type stains consist essentially of aromatic type compounds. Other common stains, such as grass, ink and tomato, have structures which are very olefinic. This structural difFerence is believed to 30 be the cause of the stain specificity of such bleaching compo-sitions. Bleaching compositions consisting only of a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus an aromatic suifonyl halide bleach activator do not provide the superior level of bleaching performance, regardless of ~5 the type of stain. Surprisingly, only the compositions within the ~ 7955 invention provide the superior level of solution bleachin~ andlor surface bleaching performance over a very wide class of stains.
The bleaching compositions within the invention are very efficient. Extremely small quantities of such compositions provide 5 the superior level of solution bleaching and/or surface bleaching performance. Without being bound by theory, gt is believed that such efficiency is obtained because a substantial majority of active oxygen, defined below, is lJtilized for bleaching durin~3 the bleaching process. This can be explained as follows.
It is believed that the peroxycarboxylic acid reacts with the aromatic sulfonyl halide bleach actiYator to form an acyl persul-fonate. Since the acyl persulfonate contains an -O-O- group it contains a reactive oxygen atom, generalty referred to as an "active oxygen" atom. The active oxygen is the active bleaching 15 component which reacts with and, thereby, modifies stains on textiles and/or soils in the bleaching solution. The acyl persul-fonate is sufficiently reactive so that very little active oxygen is present after the bleaching process. However, and lust as important, the acyl persulfonate is not too reactive, based upon 20 the superior level of solution bleaching and/or surface bleachin~3 performance observed, so as to decompose rather than provide such bleaching performance. Therefore, the vast majority of the active oxygen is utilized for bleaching during the bleaching process. This enables one to obtain the superior ievel of bleach-25 ing performance with very small amounts of the Dleaching compo-sitions within the invention.
Bleaching compositions consisting only of a peroxycarboxylic acid or a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus an aromatic sulfonyl halide bleach 30 activator are extremely inefflcient and/or ine~fective. Bleaching compositions consisting only of a peroxycarboxylic acid are very inefficient because a substantial amount of the active oxygen of the peroxycarboxylic acid remains in the bleaching solution after the bleaching process is carried out. This unreacted peroxycar-35 boxylic acid is essentially wasted. Thus, in order to achieve the ., . ~
L
~z~
superior level of bleaching performance very large amounts of such compositions, as compared to th~ bleaching compositions within the invention, are required. However, it should be noted that regardless of the amount of peroxycarboxylic acid added to S the bleaching sols~tion, within practicable limits, the desired superior level of bleaching performance is obtain~d primarily on beverage type stains. E~leaching compositions consisting of a peroxygen bleach capable of yieiding hydrogen peroxide in an aqueous solution plus an aromatic sulfonyl halide bleach activator are very efficient in that very little active oxygen is present after the bleaching process. However, such bleaching compo-sitions do not provide the desired superior level of solution bleaching per~ormance and provide essentially no surface bleach-ing. Without being bound by theory, it is believed that the persulfonic acid ~ormed is so reactive that it decompos~s before it even oomes into contact with the textiles. Only the bleaching rompositions within the invention are both efficient and provide r the superior level of solution bleaching andlor surface t)leaching performance over a very wide class of stains.
Another major advantage of the bleaching compositions within the invention is that they provide the superior level of solution bleaching and/or surface bleaching performance over a very wide range of pH's of the bleaching solution. Therefore, ~or example, when the bleaching compositions are detergent compositions one can adiust the pH of the bleaching solution so as to optimize detergency performance without sacrificing bleaching performance.
Typical activated bleaching compositions, i.e., those consisting only of a peroxygen bleach capable of yielding hydrogen peroxids in an aqueous solution and a bleach activator which react in the bleaching solution to form a peroxy acid, are very pH dependent.
It is believed that such p~ dependence is due to the fact that the active oxygen of the peroxy acid reacts with stains and/or soils via the formation of a dimer by the peroxy acid with its anion. Thus, in order to maximize the amount of the dimer ~ormed it is essential that the PKa of the peroxy acid be similar to the pH of the ~L2~7~55 bleaching solution. This ensures that there will be similar levels of the peroxy acid and its anion present in the bleaching solution and, therefore maximizes the amount of dimer formef:l. Otherwise, there will be an excess of peroxy acid as compared to its anion or 5 vice versa; either of such excess is not utilized and, thus, as indicated by experimental eYidence, bleaching performance deciines. It should be noted that even if the pH of the bleaching solution is similar to the PKa of the peroxy acid the vast maiority of the active oxygen is still present after the bleaching process.
10 It is theorized that the bleaching compositions within the inven-tion do not operate via the formation of a reactive climer and, therefore, as indicated by experimental evidence, provide the superior level of bleaching performance over a wide range of pH's.
The initial pH of the bleaching solution containing the bleaching compositions within the invention is from about 6 to about 12, preferably from about 7 to about 11 and most prefer-ably from about 8.5 to about 10.
In the compositions within the invention the ratio of the 20 peroxycarboxylic acid to aromatic sulfonyl halide is such that the molar ratio of each actual and potential peroxycarboxyl group of the peroxycarboxylic acid to each sulfonyl group of the aromatic sulfonyl halide that can potentially generate acyl persulfonate is from about 10 to about 0.05, preferably from about 1 to about .3 25 and most preferably from about 1 to about 0.7. Molar ratios of such components of from about 1 to about O . 7 a re most preferred because vast excesses of either component will result in such excess not interacting with the other component and, therefore, won't provide the superior îevel of bleaching performance that is 30 obtained by such components that interact with each other. The terlT "potential peroxycarboxyl group" is meant to define the level of peroxycarboxylic acid that can be present in the bleaching compositions within the invention when the peroxycarboxylic acid is generated in situ, as discussed hereinafter. It should be 3i noted that the ratio is found to vary considerably as a function )7~S5 of pH. For example, if the initial pH of the bieaching solution is greater than 10, then excess aromatic sulfonyl halide would be preferred to make up for the amount lost clue to alkaline hydrolysis.
The following is a detailed description of the essential and the optional components of the bleaching compositions within the invention. All percentages, parts 01' ratios are by weight unless otherwise indicated.
THE PEROXYCARBOXYLIC ACID
Essentially any peroxycarboxylic aoid or salt thereof is suitable lFor use herein. Albeit some peroxycarboxylic acids are more preferred than others, it is believed that the effectiveness and efficiency of solution bleaching and/or surface bleaching perforn~ance of essentially any peroxycarboxytic acid will be enhanced by utilizing it in the bleaching compositions within the invention .
The preferred peroxycarboxytic acids and sal~s thereof have the general formula:
~: . . _ _ R- jC-O-OM
~ _ r wherein R is selected from the group consisting ~lF H, a linear or branched alkyl or alkylene group containing from t to about 18 carbon atoms, a cyciic alkyl, or alkylene group containing from about 3 to about 18 carbon atoms, an aryl group, an aromatic heterocyclic group, a polyarylene group consisting of two or more annelated benzenoid rings and groups in which two or more aryl or arylene substituents are covalently attach~d, M is H or a cation which provides water-solubility or dis~ersibility to the peroxycarboxylic acid and r is from l to the total number of hydrogen atoms on R. Preferably, M is H or an alkali metal or an alkaline earth metal, with H, magnesium, sodium and potassium being the most preferred. R can be substituted with essentially any group or groups, including an alkyl group when R is aryl and an aryl group when R i5 alkyl, so long as they do not lZ(~79~iS
interfere with the function of the peroxycarboxylic aeidO The preferred alkyl or alkylene group substituents are -SO3M and -COOM and the preferred aryl and arylene substituents are selected from the group consisting of halogens (fluorine, chlorine, or bromine), ~N02, -OCH3 and -COOM wherein l~A is as defined above. Suitable aromatic heterocyclic groups include furan, thiophene and pyridine. Examples of polyarylene groups consist-li-g of two or more annelated benzenoid rings are the naph~hyl, phenanthryl and anthraceny3 moietiès.
The more preferred peroxycarboxylic acids and salts thereof have the general formula:
~ -~-O-OM or T E ~-O-O-M~
wherein A is a halogen (fluorine or chlorine) or -NO2, M is as defined above, T is an alkyl group containing from about 5 to about 18 carbon atoms ar;d r is one or two.
The most preferred peroxycarboxylic acids ~nd salts thereof have the general ~ormula:
A O
~> -C-O-OM
wherein A i5 a halogen (chlorine or fluorine), preferably Cl, and M is H or magnesium. Surprisingly, when halogen substituted peroxybenzoic acids or salts thereof are utilized within the compositions of the invention, solution bleaching and, especially, surface bleaching perforrnance are exceptional.
Formation of the Peroxycarboxylic Acid In Situ by l.ltilizing Specific Peroxygen Bleaches and Bleach Activators As an alternative to directly adding the peroxycarboxylic acid to the bleaching solution, the peroxycarboxylic acid can be formed in situ lFrom its precursors. For example, a two -component peroxycarboxylic acid source consistin~ of a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution and a bleach activator that contains a carbonyO carbon that can pot~ntially react with the hydrogen peroxide to form a ~r1~ ' ~'7~5 peroxycarboxylic acid can be utilized. The use of this system within the compositions of the invention provides essentially the sarne leYel of effectiveness and efficiency of solution bleaching and/or surface bleaching performance as is obtained by directly 5 utilizing a peroxycarboxylic acid within the compositions of the invention . - -An ~dditional advantage of such two component peroxycar- -boxylic acid source with respect to bleaching compositions con-sisting solely of such two components is based upon pH As 10 discussed above, for bleaching compositions that consist solely of such peroxygen bleach and bieach activator, it is believed that the pH of the bleaching solution must be adjusted to be similar to the PKa of the peroxycarboxylic acid formed in order So maximize the formation of the reactive dimer. However, the pl~ of the 15 bleaching solution must also be adjusted to ensure that the hy-drogen peroxide, yielded by the peroxygen bleach, is to an appreciable extent in the perhydroxide anion form~ This maxi-mizes the rate of formation of the peroxycarboxylic acid. There-fore, since there are two pH dependent chemical reactions that 20 must take place, neither one can be maximized. However, when utilizing the two component peroxycarboxylic acid source within the compositions of the snvention the pH of the bleaching solution need not be similar to the PKa of the peroxycarboxylic acid.
Therefore, one can adjust the pH of the bleaching solution to 25 maximize the formation of the perhydroxide anion and, thus, maximize the formation of the peroxycarboxylic acid.
The Peroxygen Bleach The peroxygen bleaches useful herein are those capable of yielding hydrogen peroxide in an aqueous solution. These 30 bleaches are well known in the art and includa hydrogen peroxide and the alkali metal peroxides, organic peroxide bleaching com-pounds such as urea peroxide, and inorganic persalt bleaches, such as the alkali metal perborates, percarbonates, perphos-phates, and the like. hlixtures of two or more such bleaches can 35 also be used, if desired.
~!LZ(~75~S~
Preferred peroxygen bleaches include sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhy-drate, urea peroxyhydrate, and sodium peroxide. Particularly preferred are sodium perborate monohydrate and sodium perborate tetrahydrate and mixtures thereof.
The Bleach Activator The bleach activators that can be utilized for such a purpose are ones capable of generating peroxycarboxylic acids and have the general formula: -O
R - ~ - L
wherein R is as defined above and L is a leaving group, wherein the conjugate acid of the anion formed on L has a PKa in the range of from about 4 to about 13.
L can be essentially any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophi!ic attack on the bleach activator [ by ths perhydroxide anion. This, as discussed hereinabove, is the perhydrolysis reaction. Leaving groups that exhibit such behavior are those in which their conjugate acid has a PKa in the range of from about 4 to about 13, preferably from about 7 to about 11 and most preferably from about 8 to about 11.
It should be noted that, as an option, R or L can be a group that contains an aromatic sulfonyl halide. Such a system can be utilized in combination with a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution and provides the desired level of solution bleaching and/or surface bleaching performance .
3~ Preferred bleach activators are those of the above general formula wherein R is as defined above and L is selected from the group consisting of:
_o~ , -o{~ , - O ~, -N-C-R, lZ~S~
O ~ -0~
-0-C-R, -N H, -Q,~_ -0-CH = C - CH = CH2, -N ,N
~.2 -0-C = CHR, wherein R is as defined above, ~2 is an alkyl chain containing from about 1 to about 8 carbon atoms, R3 is H or R2, and Z is H
or a solubilizing group. The preferred solubilizing groups are -503M, -C00 M, -S04M, (-N R34)X and O+NR2 and most preferably -S03M and -C00 M wherein R is an alkyl chain containing from about 1 to about 4 carbon atoms, 1~/1 is as defined above and X is an anion which provides solubility to the bleach activator. Preferably, X is a halide (fluorine, chlorine or 2û bromine), hydroxide, methylsulfate or acetate anion. It should be noted that bleach activators with a leaving group that does not contain a solubilizing group should be well dispersed in the bleaching solution in order to assist in their dissolution.
The molar ratio of hydrogen peroxide yielded by the peroxy-25 gen bleach to such peroxycarboxylic acid generating bleach activator is from about 20 to about 0.1, preferably lFrom about 3 to about 1 and most preferably from about 2 to about 1.
However, it should be noted that the preferred ratio is found to vary considerably if the initial pH of the bleaching solution ;s 30 below about 9. Under such conditions a higher molar ratio of hydrogen peroxide yielded by the peroxygen bleach to peroxycarboxylic acid generating bleach activator is desirable.
Preferably, such molar ratio is from about 4 to 20.
9S~
Formation of The Peroxycarboxylic Acid In Situ Utilizing an Organic Peroxide Compound Another precursor that can be utilized to ~orm the perox-ycarboxylic acid in situ is an organic peroxide compound. It is 5 believed that such a compound undergoes hydrolysis in the bleach-ing solution to form the peroxycarboxylic acid. This system is not preferred because the peroxycarboxylic acid formation is often slow and, therefore, it is theorized that during this time some of the aromatic sulfonyl halide bleach activator undergoes hydrolysis 10 to form an inactive sulfonic acid.
The organic peroxide compounds have the general formula:
O O
R - C - O - O - C - R
wherein each R is as defined above.
As an option, a peroxygen bleach, such as those described above, can also be added to the bleaching solution with the organic peroxide compound. This results in the potential forma-tion of two moles of peroxycarboxylic acid per mole of organic peroxide and, therefore, only half of the level of organic peroxide is required as would otherwise be necessary without such peroxygen bleach. The molar ratio of such or~anic peroxide compounds to such peroxygen bleach is from about 0.1 to about 10, preferabiy from about 0.~5 to about ~ and most preferably from about 1 to about 0.3.
The level of peroxycarboxylic acid within compositions of the invention is from about 0.1% to about 8096, preferably from about 5% to about 60% and most preferably from about 30% to about 60%.
It should be noted that when a two component peroxycarboxylic acid source is utilized, e.g., a peroxygen bleach capable of yielding hydrogen peroxide in an aqueous solution plus a peroxycarboxylic acid generating bleach activator or such peroxygen bleach plus an organic peroxide compound, the level of each component should be such that it can theoretically produce the levels of peroxycarboxylic acid within the compositions of the 35 invention. When the bleaching compositions within the invention ~ . lZ~7~55 . . .
are also detergent compositions i$ is preferred that the level of peroxycarboxylic acid is from about 0.1% to about 10% and more preferably from about 196 to about 3%.
l HE AROMATIC SULFONYL HALIDE
Essentially any aromatic sulfonyl halide bleach activator is suitable for use herein. l he aromatic group can contain one or more substituents so long as they do not inter~ere with the function of the bleach activator.
The preferred aromatic sulfonyl halide bleach activators within the compositions of the invention have the general ~ormula:
Y 3E {~
wherein each Y is selected from the group consisting of:
H, -C N tC 2H 2 ) 2, -OC 2H 2 n 2n +1 n 2n +1 n2 2n2+1 O O
( N+(C 11 )3), -OC CnH2n~1 ~ ~5CnH2n+l ~ n 2n~1 o halogens and any group which provides an anionic moiety in aqueous solution wherein each n is from O to about 12 and each n is lFrom 0 to about 1~, E is selected from the group consisting 25 of an aryl arylene group, an aromatic heterocyclic group, a polyarylene group consisting of two or Inore annelated benzenoid rings and groups in which two or more aryl arylene substituents are covalently attached, Q is a halogen (fluorine, chlorine, or bromine] preferably chlorine, and each n is from 11 to about 3.
30 Suitable aromatic heterocyclic groups include furan, thiophene, quinoline and pyridine. Examples of polyarylene groups consist-lng of two or more annelated groups are the naphthyl, ph~nanthryl and anthracenyl moieties.
The preferred aromatic sulfonyl halide bleach activators are 35 selected from the group consisting of:
~.
I
~L2~5 , -- 15 -- .
O O O
1 13 C ~S - C l, H3C~S F~
O COOH O
Cl 5{~s Cl ~ - Cl S - Cl O O
10The most preferred aromatic sulfonyl halide bl~ach activator has the formula:
~ ~ - C I
15(~O
S - Cl The level of aromatic sulfonyl halide within the compositions of the invention is from about .1% to about 70%, preferably from 20about 5~ ~o about 70% and most preferably from about ~0% to about 709~. When the bleaching cornpositions within the invention are also detergent compositions it is preferred that the level of aromatic sulfonyl halide is from about 0.1% to about 10% and more preferably from about 19~ to about 3~.
25OPTiONAL COMPONENTS
As a preferred embodiment, the bleaching compositions of the invention can be detergent compositions. T51us, the bleaching compositions can contain typical detergent composition components such as detergency surfactants and detergency builders. In such 30preferred embodiments the bleaching compositions are particularly effective. The bleaching compositions of this invention can contain all of the usual cornponents of detergent compositions Including the ingrediants set forth in U~S. Patent 3~fl36,537, Baskerville et al, Such com-35ponents include color speckles, suds boosters, suds suppressors, .
7~35S
antitarnish and/or anticorrosion agents, soil-suspendin~ agents, soil-release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, perfumes, etc.
The detergent surfactants can be any one or more surface active agents selected from anionic, nonionic, zwitterionic, ampho-teric and cationie classes and compatible mixt~res thereof.
Detergent surfactants useful herein are listed in U . S. Patent 3,664,961, Norris, issued May 23, 1972, and In U.S. Patent 3,919,678, I aughlin et al, issued Decamber 30, 1975,~
Useful cationic surfactants also include those described in U.S. Patent l~,222,gOS, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980, t5 The ~ollowing are representative examples of deter-gent surfactants useful in the present compositions.
Water soluble salts of the higher fatty acids, i.e., soaps, are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammon-ium, and alkylammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. sGaps can be made by direc saponification of fats and oils or by the neutralizatiorl of ~ree fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oii and tallow, i.e., sodium or potassium tallow and coconut soap.
Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylammonium salts, of organic sulfuric reaction products having in their mole-cular structure an alkyl group containing from a~out 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
(Included in the term alkyl is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sul-fating the higher alcohols (C8-C18 carbon atoms) such 3S those ~7~i produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383. Espec-ially valuable are linear straight chain alkylbenzene sulfonates in which the average number of c~rbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11 13LAS.
Other anionic surfactants herein are the sodium alkyl gly-ceryl ether sulfonates, especially those ethers of higher alcohois derived from tallow and coconut oil; sodium coconut oil fatty acid monoglycerlde sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the est r group; water-soluble salts of 2-acytoxyalkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 tu about 23 carbon atoms in the alkane moiety; water-solubie satts of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Water-soluble nonionic surfactants are also useful in the compositions of the invention. Such nonionic rnaterials include compounds produced by the condensation of alkyl or alkylene oxlde groups thydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
- ~2~ 5 The length of the polyoxyalkytene group which is condensed with any particular hydrophobic group can be readily adiusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Suitable nonionic surfactants Include the pl~lyethylene oxide condensatés of alkyl phenols, e.g., the condensation products o~
alkyl phenols having an alkyl group containing from about 6 to 15 carbon atoms, in either a straight chain or branched chain con-figuration, with from about 3 to 12 moles of ethylene oxide per mole of alkyl phenol.
Preferred nonionics are the water-soluble and water-disper-sible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched config-uration, with from 2 to 12 moles of ethylene oxide per mole of a!cohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to 8 moles of ethy~ene oxide per mole of alcohol.
Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and two moleties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms;
water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups con-taining from about 1 to 3 carbon atoms; and water-soluble sulfox-ides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group c~sisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
Ampholytic surfactants includs derivatives of alipha~ic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains ~rom about 8 to 18 carbon atoms and at least one aliphatic substituent con-tains an anionic water-solubilizing group.
~,,fz~
;
2witterionic surfactants include derivatives of aliphatic, quaternary~ ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
The level of detergent surfactant that can be employed is from 0% to about 50%, preferably from about 1% to about 30~ and most preferably from about 10% to about 25~ by ~reîght of the total composition.
In addition to detergent surfactants, detergency builders can l O be employed in the bleaching compositions. Water-soluble inor-ganic or organic elec~rolytes are suitable builders. The builder can also be water-insoluble calcium lon exchange materials; non-limiting examples of suitable water-soluble, inorganlc detergent builders include: alkali metal carbonates, borates, phosphates, bicarbonates and silicates, Specific examples of such salts include sodium and potasslum tetraborates, bicarbonates, carbonates, orthophosphates, pyrophosphates, tripolyphosphates and meta-phosphates.
Examples of suitable organic alkaline detergency builders include: (1 ) water-soluble amino carboxylates and aminopolyace-tates, for example, nitrilotriacetates, glycTnates, ethylenediamine tetraacetates, N-~2-hydroxyethyl)nitrilo diacetates and diethy3-enetriamine pentaacetates; (2) water-soluble salts of phytic acid, for example, sodium and potassium ,ohytates; t3) water-soluble polyphosphonates, including sodiurn, potassium, and lithium salts of ethane-l-hydroxy-1, 1-diphosphonic acid; sodium, potassium, and lithium salts of cthyiene diphosphonic acid; and the like; (43 water-soluble polycarboxylates such as the sal~s olF lactlc acid, succinic acid, malonic acid, maleic acid, citric acid~ carboxy-3a methyloxysuccinic acid, 2-oxa-l ~1 ,3-propane tricarboxylic acid, 1,1 ,2,2-ethane tetracarboxylic acid, mellitic acid and pyromellitic acid; l5) water-soluble polyacetals as disclosed in U.S. Patents 4,144,266 and 4,246,495~ and 16) water-soluble polyacrylates.
75~iS
.
.
-- 2~ --Another type ~f detergency builder material use~ul in the present compositions comprises a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which 5 is capable of providing growth sites for said reaction product.
Such "seeded builder" compositions are fully disclosed in British Patent Specification No. 1,424,406.
A further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particu-10 lariy those described in U.S. Patent 4,303,556 issued December 1, 1981, This patent discloses and claims detergent compositions containing sodium aluminosili-cates having the formula:
Naz(A102) Z~S jO2)yXH20 15 wherein z and y are integers equal to at least 6, the molar ratio of z to y is in the ran~e of from 1.0:1 to about 0.5:1, and X is an integer from about 15 to about 264, said aluminosilicates hav-ing a alcium ion exchange capacity of at least 200 milligrams equivalent/gram and a calcium ion exchange rate of at least about 20 2 grains/gallon/minutetgram. A preferred material is Zeolite A
which is:
Nal 2 ~ STO2AlO2 ) 1227 H2O
The level of detergency builder of the bleaching compositisns is from 0% to about 70%, preferably from about 10~ to about 60~6 25 and most preferably from about 20% to about 60~.
Buffering agents can be utilized to maintain ~he desired alkaline pH of the bleaching solutions. Buffering agents include, but are not limited to many of the detergency builder compounds disclosed hereinbefore. Buffering ayents suitable for use herein 30 are those well known in the detergency art.
Preferred optional ingredients include suds modifiers parti-cularly those of suds suppressing types, exemplified by silicones, and silica-silicone mixtures. U.S. Patents 3,933,672, issued January 20, 1976 to Bartolotta et al, and 4,136,045, issued January 23, 1979 to Gault e~ al, disclose silicone suds controlling agents. Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in U.S. Patent 4,073,1t8, Gault et al, issued February 21, 1 978 , An example of such a compound is DB-544, commerciatly available from Dow Corning, which is a siloxanelglycol copolym~r. Suds modifiers as described above are used at levels of up to approxi-mately 2~, preferably from about 0.1 to about ~ by weight o~
10 the surfactant.
Microcrystalline waxes having a melting point in the rang~
from 35C-115~C and a saponiflcation value of less than 100 represent additional examples of preferred suds control compon-ents ~or use in the subject compositions, and are described in 15 detail in U.S. Patent 4,056,481, Tate, issued November 1, t977, The microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfactants. Preferred microcrystalline waxes have a melting point from about 65C to 100C, a molecular weight 20 Tn the range from 400-1, 000; and a penetration value of at least 6, measured at 77F by ASTM-D1321. Suitable examples o~ the above waxes include: microcrystalline and oxidized microcrystal-line petroleum waxes; Fischer-Tropsch and oxidizecl Fischer-Tropsch waxes; ozokerite; ceresin; montan wax; beeswax; cande-25 lilla wax; and camauba wax.
Alkyl phosphate esters represent an additional preferred suds control agent for use herein. These pre~erred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain Bi- and tristearyl phosphates and monooleyl 30 phosphate, which can contain di- and trioleyl phosphate.
Other suds control agents useful in the practlce of the invention are the soap or the 50ap and nonionic mixtures as disclosed in U.S. Patents 2,954,347 and 2,954,348, * l~ad~nark ,.~
,. . ., ~.~, . _ _ . ~ _ . _ _ _ _ _ , _ _ . . ~ _ .. _ ... . . ... ~ . _ . . . . , _ ... _ . _ . . _ ~Z0~7~
~ 22 -Fluorescent or optical brighteners can be utilized within the bleaching compositions of the invention. Surprisingly, such brighteners exhibit acceptable compatibility with such composi-tions. Suitable anionic brighteners are disclosed in U.S. Patents 3,537,993 Coward et al (November 3, 1~70) and 3,953,380 Sundby (April 27, 1976), Nonionic brighteners can also be utilized within the compositions of the invention .
The following examples are given to illustrate the parameters o of and compositions within the invention. All percentages, parts and ratios are by weight unless otherwise indicated.
EXAMPL~ I
The following granular detergent composition was prepared:
m C16_18 alkyl sulfate 5o5 Sodium C12 linear alkylbenzene sulfonate 3~5 C14_l6 alkyl polyethoxylate2 25 5.5 Sodium tripolyphosphate 2~
Zeolite A 17.6 20 Sodium carbonate 10~5 Sodium silicate (2.0r) 1.9 Sodium sulfate 2t.0 Water IB.g Mi scel laneous 1 . 2 Two sets of six 5"x5" swatches consisting of fiYe polycotton swatches each stained with one of the following stains - chili, RAGU spaghetti sauce, mustard, ink and tea - and one denim swatch stained with grass were prepared.
A laundry load consisting of one set of the six swatches, 30 four clean terry cloth towels and one terry cloth towel soiled with 1.5 grams o~ a mlxture of artificial body soil and vacuum cleaner soil was placed in a mini-wash system. This laundry load was ~hen washed with S.5 grams of the above granular detergent composition in 5 . 5 liters of water . This mTni-wash system with 35 such a load and granular detergent concentration simulates a * Trad~nark __ :~.zu7~
.
conventional automatic wash process. The wash water tempera-ture was 37C and the wash water contained 8 grains/gallon water hardness. The initial pH of the wash water was about 9.7.
After drying, each of the swatches was visually graded by 5 comparing it to its unwashed counterpart. A grading scale of 0 to 5 was used, with 0 indicating no stain removal and 5 indicating 100% stain removal. Each swatch was graded by three graders and then the average grade for each swatch was calculated. This average was then scaled from 0 to 100, with 100 being 100% stain 10 removal. Also, the mean for the set of swatches was calculated.
The entire procedure was repeated numerous times, but each time a different bleaching system was added to the mini-wash system one minute after the start of the wash process.
The results were as follows:
9~ Stain Removal Bleachin~ SystemChili Spa~hetti Mustard 1. None 62 60 64
2. m-chloroperoxybenzoic acid (3 ) I 60 50 63 20 3. p-chloroperoxybenzoic acid ~ 3 ) 63 53 63 4. p-nitroperoxybenzoic acid (3) 63 57 63 5. m chloroperoxybenzoic acid (3) + 1,3-benzene disulfonyl chloride (6)ii 83 83 63 6. p-chloroperoxybenzoic acid t3) + 1,3-benzenedisulfonyl chloride (6) go 90 77 7. p-nitroperoxybenzoic acid (3 + 1,3-benzenedisulfonyl chloride (6) 77 57 67 *8. p-fluoroperoxybenzoic 35 acid (3) 73 60 50 *
5~
9. p-fluoroperoxybenzoic acid (3 + 1 ,3-benzenedisulfonyl chloride (3~ 80 73 60 % Stain Removal _ _ Bleachin~3 System Ink Tea Grass Mean 1. None 61 62 5~ 61 ~-2. m-chloroperoxybenzoic acid t3)' 60 77 67 63
5~
9. p-fluoroperoxybenzoic acid (3 + 1 ,3-benzenedisulfonyl chloride (3~ 80 73 60 % Stain Removal _ _ Bleachin~3 System Ink Tea Grass Mean 1. None 61 62 5~ 61 ~-2. m-chloroperoxybenzoic acid t3)' 60 77 67 63
3. p~ehloroperoxybenzoic acid (33 60 0 50 62
4. p-nitroperoxybenzoic acid (3) 57 83 60 64
5. m-chloroperoxybenzoic acid (3) ~ 1,3-benzenedisulfonyl chloride t6)ii 70 73 67 73
6. p-chloroperoxybenzoic acid (3~ + 1,3-ben~enedisulfonyl chloride (6) 73 83 57 78 207. p-nitroperoxybenzoic acid t3) 1 ,3-benzene disulfonyl chloride (6) 60 87 53 67 *8. p-fluoroperoxybenzoic acid ( 3 ) 57 73 60 62 25 *9. p-fluoroperoxybenzoic acid (3 ~ l ,3-benzenedisulfonyl chloride (3) 67 67 7~ 70 ' - indicates the parts per million of active oxygen availab1e in the wash water from m-chloroperoxybenzoic aeld. This same denotation is utilized in all the examples.
ii_ indicates the potential parts per million of active oxygen in the wash water available as an acyl persulfonate.
* - The initial pH of the wash water was about 10.
Bleaching systems 5-7 and 9 which are within the composi-tions of the invention, provided significantly more stain removat ~2()7~
and, thçrefore, surface bleaching than bleaching systems 2~4 and 8 which are outside the compositions of the invention because they did not contain an aromatic sulfonyl halide bleach activator.
The above procedure was carried out with other bleaching 5 systems consisting only of a peroxycarboxylic acid, which are not within the compositions of the invention, and bleaching systems consisting of such peroxycarboxylic acids plus 1,3-benzenedi-sulfonyl chloride, which are within the compositions of the in-vention. The data indicate that the surface bleaching perform-10 ance obtained with each peroxycarboxylic acid plus 1 ,3-benzene-disulfonyl chioride bleaching system was improved on some of the above stains as compared to the same bleaching system, but containin~ only the peroxycarboxylic acid. However, it is be-lieved that solution bleaching performance of all the bleaching 15 systems consisting solely of the peroxycarboxylic acid is improved by the addition of 1,3-benzenedisulfonyl chloride.
EXAMPLE I I
Surface bleaching performance capabilities were determined as in EXAMPLE I with various bleaching systems. The results 20 were as follows:
% Stain Removal Bleaching SystemChili Spaghetti Mustard l. None 57 63 63 2. m-chloroperoxybenzoic acid (3) 60 50 63 *3. m-chloroperoxybenzoic acid (3) 1 ,3-benzenedisulfonyl chloride (3) 83 70 90 *4~ m-chloroperoxybenzoic acid t3) ~ 1 ,3,5-benzenetrisulfonyl chloride l3) 73 53 9o *5. m-chloroperoxybenzoic acid (3) + p-acetaminobenzene-sulfonyl chloride (3) 63 63 83 35 *
~2(~ SS
6.m chloroperoxybenzoic acid (3) ~ p-toluenesulfonyl chloride ~3) 77 60 90 *7.m-chloroperoxybenzoic acid (3) 5~ m-chlorosulfonyl-benzoic acid (3) 87 80 80 *8. m-chloroperoxybenzoic acid (3) p-toluenesulfonyl fluoride (3~ 80 70 80 9. m-chloroperoxybenzoic acid (3) 8-quinolinesulfonyl chloride (3) 90 90 73 10. m-chloroperoxybenzoic acid (3) + d-camphorsulfonyl 15chloride (3) 70 53 57 11. m-chloroperoxybenzoic acid 133 dodecanesulfonyl chloride (3) 60 S0 63 % Stain Removal Bleachin~ System Ink GrassTea Mean 1. None 57 73 60 62 2. m-chloroperoxybenzoic acid (3~ 60 77 67 63 *3. m-chloroperoxybenzoic acid (3) + 1,3-benzenedisulfonyl chloride (3) 67 77 73 n *4. m-chloroperoxybenzoic acid t3) ~ 1 ,3,5-benzenetrisulfonyl chloride (3) 57 70 77 70 30 *5. m-chloroperoxybenzoic acid (3) + p-acetaminobenzene-sulfonyl chloride (3) 57 63 60 65 *6. m-chloroperoxybenzoic acid [3) ~ p-toluenesul~onyl chloride (3) 67 73 73 73 1~0~7955 *7. m-chloroperoxybenzoic acid (3) m-chlorosulfonyl-benzoic acid t3) 70 77 77 79 *8~ m-chloroperoxybenzoic acid (3) - 5 + p-toluenesulfonyl fluoride 13) 7û 60 67 71 ..
9. m-chloroperoxybenzoic acid (3) 8-quinolinesulfonyl chloride 13) 70 73 73 73 lO 10. m-chloroperoxybenzoic acid (3) + d-camphorsulfonyl chloride 13) 63 70 70 64 11. m-chloroperoxybenzoic acid (3) + dodecanesul~onyl chloride (3) 63 70 60 61 * - 2.0 grams of sodium carbonate was added to the granular detergent composition and, therefore, the initial pH of the wash water was about 10.5.
. I E~leaching systems 3-9, which are within the compositions of 20 the invention, provided significantly more surface bleaching than bleaching systems 2, 10 and 11 which are outside the compositions of the invention because each did not contain an aromatic sulfonyl halide bleach activator.
EXAMPLE l l I
Surface bleaching per~ormance capabilities were determined as in Example I with various bleaching systems. The results were as follows:
% Stain Remova!
E~leaching System Chili Spa3hetti Mustard 30 1. N~ne 62 60 64 2. Sodium perborate t13.5) 70 50 63 3 . Sodium s~erborate l 13 . 5 ) 1 ,3-benzenedisulfonyl chloride (13.5) 63 50 60 79~5 4. Sodium perborate ~13.5) +
4-sulfophenyloctanoate, sodium salt (4.5) 67 67 57 5. Sodium perborate (13.5) +
4-sulfophenyloctanoate, sodium salt (4.5) + _`
1 ,3 benzenedisulfonyl chloride (1305) 87 77 63 6. Sodium perborate tl3.5) +
l O tetracetylethylenediamine tTAE~) (4.5~ 67 63 57
ii_ indicates the potential parts per million of active oxygen in the wash water available as an acyl persulfonate.
* - The initial pH of the wash water was about 10.
Bleaching systems 5-7 and 9 which are within the composi-tions of the invention, provided significantly more stain removat ~2()7~
and, thçrefore, surface bleaching than bleaching systems 2~4 and 8 which are outside the compositions of the invention because they did not contain an aromatic sulfonyl halide bleach activator.
The above procedure was carried out with other bleaching 5 systems consisting only of a peroxycarboxylic acid, which are not within the compositions of the invention, and bleaching systems consisting of such peroxycarboxylic acids plus 1,3-benzenedi-sulfonyl chloride, which are within the compositions of the in-vention. The data indicate that the surface bleaching perform-10 ance obtained with each peroxycarboxylic acid plus 1 ,3-benzene-disulfonyl chioride bleaching system was improved on some of the above stains as compared to the same bleaching system, but containin~ only the peroxycarboxylic acid. However, it is be-lieved that solution bleaching performance of all the bleaching 15 systems consisting solely of the peroxycarboxylic acid is improved by the addition of 1,3-benzenedisulfonyl chloride.
EXAMPLE I I
Surface bleaching performance capabilities were determined as in EXAMPLE I with various bleaching systems. The results 20 were as follows:
% Stain Removal Bleaching SystemChili Spaghetti Mustard l. None 57 63 63 2. m-chloroperoxybenzoic acid (3) 60 50 63 *3. m-chloroperoxybenzoic acid (3) 1 ,3-benzenedisulfonyl chloride (3) 83 70 90 *4~ m-chloroperoxybenzoic acid t3) ~ 1 ,3,5-benzenetrisulfonyl chloride l3) 73 53 9o *5. m-chloroperoxybenzoic acid (3) + p-acetaminobenzene-sulfonyl chloride (3) 63 63 83 35 *
~2(~ SS
6.m chloroperoxybenzoic acid (3) ~ p-toluenesulfonyl chloride ~3) 77 60 90 *7.m-chloroperoxybenzoic acid (3) 5~ m-chlorosulfonyl-benzoic acid (3) 87 80 80 *8. m-chloroperoxybenzoic acid (3) p-toluenesulfonyl fluoride (3~ 80 70 80 9. m-chloroperoxybenzoic acid (3) 8-quinolinesulfonyl chloride (3) 90 90 73 10. m-chloroperoxybenzoic acid (3) + d-camphorsulfonyl 15chloride (3) 70 53 57 11. m-chloroperoxybenzoic acid 133 dodecanesulfonyl chloride (3) 60 S0 63 % Stain Removal Bleachin~ System Ink GrassTea Mean 1. None 57 73 60 62 2. m-chloroperoxybenzoic acid (3~ 60 77 67 63 *3. m-chloroperoxybenzoic acid (3) + 1,3-benzenedisulfonyl chloride (3) 67 77 73 n *4. m-chloroperoxybenzoic acid t3) ~ 1 ,3,5-benzenetrisulfonyl chloride (3) 57 70 77 70 30 *5. m-chloroperoxybenzoic acid (3) + p-acetaminobenzene-sulfonyl chloride (3) 57 63 60 65 *6. m-chloroperoxybenzoic acid [3) ~ p-toluenesul~onyl chloride (3) 67 73 73 73 1~0~7955 *7. m-chloroperoxybenzoic acid (3) m-chlorosulfonyl-benzoic acid t3) 70 77 77 79 *8~ m-chloroperoxybenzoic acid (3) - 5 + p-toluenesulfonyl fluoride 13) 7û 60 67 71 ..
9. m-chloroperoxybenzoic acid (3) 8-quinolinesulfonyl chloride 13) 70 73 73 73 lO 10. m-chloroperoxybenzoic acid (3) + d-camphorsulfonyl chloride 13) 63 70 70 64 11. m-chloroperoxybenzoic acid (3) + dodecanesul~onyl chloride (3) 63 70 60 61 * - 2.0 grams of sodium carbonate was added to the granular detergent composition and, therefore, the initial pH of the wash water was about 10.5.
. I E~leaching systems 3-9, which are within the compositions of 20 the invention, provided significantly more surface bleaching than bleaching systems 2, 10 and 11 which are outside the compositions of the invention because each did not contain an aromatic sulfonyl halide bleach activator.
EXAMPLE l l I
Surface bleaching per~ormance capabilities were determined as in Example I with various bleaching systems. The results were as follows:
% Stain Remova!
E~leaching System Chili Spa3hetti Mustard 30 1. N~ne 62 60 64 2. Sodium perborate t13.5) 70 50 63 3 . Sodium s~erborate l 13 . 5 ) 1 ,3-benzenedisulfonyl chloride (13.5) 63 50 60 79~5 4. Sodium perborate ~13.5) +
4-sulfophenyloctanoate, sodium salt (4.5) 67 67 57 5. Sodium perborate (13.5) +
4-sulfophenyloctanoate, sodium salt (4.5) + _`
1 ,3 benzenedisulfonyl chloride (1305) 87 77 63 6. Sodium perborate tl3.5) +
l O tetracetylethylenediamine tTAE~) (4.5~ 67 63 57
7. Sodi~m perborate (13.5) + TAED
(4.5) ~ 1 ,3-benzenedisulfonyl chloride ( 13 . 5 ) 77 63 60 lS 8. Sodium perborate ~13,5) +
tetracetylglycoluril (TAGU) (4.5) 67 67 57 9, Sodium perborate (13,5) + TAGU
(4.5) + 1,3-benzenedisul-fonyl chloride ~13.5) 77 60 60 96 Stain Removal Bleachin~3 System Ink Tea Grass Mean 1. None 61 62 58 61 2. Sodium perborate (13.5) 60 63 60 61 3. Sodium perborate (13.5) +
1 ,3-benzenedisulfonyl chloride (13.5) 60 67 60 60 4. Sodium perborate (13.5) +
4-sulfophenyloctanoate, sodium salt (4.5) 63 77 60 65 5. Sodium perborate (13.5) +
4-sulfophenyloctanoate, sodium salt ~4.5) +
1 ,3 benzenedisulfonyl chloride (13.5) 77 77 73 76 ~2~ SS
-- 2~ --Sodium perborate (13.5) ~ tetra-cetylethylenediamine lTAED) (4.5) 60 70 S0 63 7. Sodium perborate 113.5) ~ TAED
(4.5) + 1,3-benzenedisul~onyl chloride ~13.5) 67 73 70 68 --
(4.5) ~ 1 ,3-benzenedisulfonyl chloride ( 13 . 5 ) 77 63 60 lS 8. Sodium perborate ~13,5) +
tetracetylglycoluril (TAGU) (4.5) 67 67 57 9, Sodium perborate (13,5) + TAGU
(4.5) + 1,3-benzenedisul-fonyl chloride ~13.5) 77 60 60 96 Stain Removal Bleachin~3 System Ink Tea Grass Mean 1. None 61 62 58 61 2. Sodium perborate (13.5) 60 63 60 61 3. Sodium perborate (13.5) +
1 ,3-benzenedisulfonyl chloride (13.5) 60 67 60 60 4. Sodium perborate (13.5) +
4-sulfophenyloctanoate, sodium salt (4.5) 63 77 60 65 5. Sodium perborate (13.5) +
4-sulfophenyloctanoate, sodium salt ~4.5) +
1 ,3 benzenedisulfonyl chloride (13.5) 77 77 73 76 ~2~ SS
-- 2~ --Sodium perborate (13.5) ~ tetra-cetylethylenediamine lTAED) (4.5) 60 70 S0 63 7. Sodium perborate 113.5) ~ TAED
(4.5) + 1,3-benzenedisul~onyl chloride ~13.5) 67 73 70 68 --
8 . Sodium perborate t 13 . S ) +
tetracetylglycoluril (TA(iU) ~4.5) 60 70 60 64 10 9. Sodium perborate (13.5) ~ TAGU
t4.5) + 1,3-benzenedisul-fonyl chloride (13.5) 60 77 70 67 Bleaching systems 5, 7 and 9, which are within the composi-tions of the invention, generaily provided signific~ntly more 15 surface bleaching than bleaching systems 2-4, 6 and 8d which are without the compositions of the invention. Bleaching system 2 contained neither a peroxycarboxylic acid source nor an aromatic sulfonyl halide bleach activator. BJeaching system 3 did not contain a peroxycarboxylic acid source and bleaching systems 4, 6 0 and 8 did not contain an aromatic sulfonyl halide b~each activator.
EXAMPLE IV
The following granular detergent composition was prepared:
-Sodium C12 linear alkylbenzene sulfonate 10.2 Sodium C14_15 alkyl polyethoxylate2 25su~atç! 4~4 C12_13 alkyl polyethoxylate2 5T* 2.2 Fatty acid from menhaden oil 1.1 Sodium tripolyphosphate 68.9 Protease (Anson units/gram) 0~036 Amylase (Amylase units/gram3 9gO
Sodium silicate (2.0r3 3.3 Water 5 5 Miscellaneous 3~5 ~2(17~5S
.
Surface bleaching performance was determined as in Example 1, but with 3.8 grams of the above granular detergent composition and various bleaching systems. Also, the initial pH of the wash water after addition of the bleach system was about 8.1. The 5results were as follows: ;
% Stain Removal Bleachin~ Sxstem ChiliSpa~hetti Mustard 1. None 53 53 47 2. m-chloroperoxybenzoic acid t2) 53 60 43 3. m-chlorobenzoic acid (2) ~ 1,3-benzenedisulfonyl chloride t2) 83 87 43 % Stain Removal ! I_ Taa G rassMean 1. None 50 53 57 53 2. m-chloroperoxybenzoic acid t2) 60 90 63 63 3. m-chlorobenzoic acid (2) ~ 1,3-benzenedisulfonyl chloride t2) 67 89 63 71~
~ leaching system 3, which is within the compositions of the invention, provided significantly more surface bleaching than bleaching composition 2, which is without the compositions of the 25 invention because it did not contain an aromatic sulfonyl halide bleach activator. Also, it should be noted that since the PKa of m-chloroperoxybenzoic acid is 7.57, the pH of the wash water was optimum for bleaching performance of the m-chloroperoxybenzoic acid alone.
EXAMPLE V
7.00 milliliters of a one molar solution of methylene blue dye in methanol was added to a beaker containing 1.00 liter of dis-tilled water. 5.1 grams of sodium carbonate and 1.3 grams of boric acid was added to the beaker which resulted in the pH of 35 the solution being about 10.00. The temperature of the solution was maintained at 37C.
~2~'75~55 A quantity of m-chloroperoxybenzoic acid was added to the solution to give a 1.25 x 10 11 molar concentration. After 20 minutes, the percent transmittance (T) was measured with a Brinkman Colorimeter Model PC700 equipped with a 440 nm fillter.
5 This measurement indicates the amount of methylene blue dye that is destroyed in the solution; a higher change in percent T indi-cates a larger amount of dye that is des~royed. Immediately after this measurement a quantity of 1,3-benzenedisulfonyl chloride was added to the solution to give a 6 . 25 x 10 5 molar concentratTon, 10 which is an equivalent amount to the m-chloroperoxybenzoic acid.
The percent T was measured after 3û seconds. This entire procedure was repeated but benzoyl peroxide was substituted for the m-chtoroperoxybenzoic acid. The results were as follows:
Bleachin~3 System (Minutes~ Chan~e in ~6 T
15 1. i. m-chloroperoxybenzoic acid (2û) ii. m-chloroperoxybenzoic acid + 1,3-benzenedisulfonyl chloride (20.5) 59 2. i. Benzoyl peroxide (20) il. Benzoyl peroxide + 1 ,3-benzena-~0 disul~onyl chloride (21 ) t7 The addition of 1 ,3-benzenedisulfonyl chloride to either m-chloroperoxybenzoic acid or benzoyl peroxide, which are compositions within the invention, rapidly increases the destruction of the methylene blue dye as compared to the 25 m-chloroperoxybenzoic acid alone, which is without the eompositions of the invention. It is believed that increased methylene blue dye destruction corresponds to increased soiution bleaching efficacy on soils.
EXAMPLE Vl 1.5 Grams of the granular detergent composition olF Example I
and a quantity of m-chloroperoxybenzoic acid equivalent to t5 parts per million of available oxygen were dissolved iin a tergotometer containing one liter of 37C.I water containing 7 grains/gallon water hardness. Then six 5"x5" swatches, three of 35 which were dyed with methylene blue dye and tl ree of which .. .
79~S
were undyed, were placed in the tergotometer. The tergotometer was agitated for 10 minutes and then the swatches were removed and dried.
~E for the three dyed and three undyed swatches was 5 measured. ~E is a measurement of the change in color of the swatch resulting from the treatment in the tergotometer. The -~
greater the ~E value, the greater the change in color. It is believed that a larger ~E value for the dyed swatches represents better surface bleaching performance and a smaller ~E value for 10 the undyed swatches represents better solution bleaching.
The above procedure was repeated with numerous bleaching systems. The results were as foliows:
~E
Bleaching System Dyed Undyed 151. rn-chloroperoxybenzoic acid tl5)3,7 5.9 2. m-chloroperoxybenzoic acid ~15) ~
p-toluenesulfonyl chloride (15)12.8 1.9 3. peroxylauric acid (5) + p-toluene-sulfonyl chloride (5) 8.ll t.6 204. Diperoxydodecanedoic acid (15) + p-toluenesulfonyl chloride 15~ 8.5 1.7 5. p-nitroperoxybenzoic acid (5) + p-toluenesulfonyl chloride (5 ) 8 .1 1 .9 6. m-chloroperoxybenzoic acid (5) 5.3 7.2 257. rn-chloroperoxybenzoic acid t5) ~ p toluenesulfonyl chloride (5) 6.9 2.4 8. m-chloroperoxybenzoic acid (5) + methyl-sulfonyl chloride (5) 1~.6 1~.5
tetracetylglycoluril (TA(iU) ~4.5) 60 70 60 64 10 9. Sodium perborate (13.5) ~ TAGU
t4.5) + 1,3-benzenedisul-fonyl chloride (13.5) 60 77 70 67 Bleaching systems 5, 7 and 9, which are within the composi-tions of the invention, generaily provided signific~ntly more 15 surface bleaching than bleaching systems 2-4, 6 and 8d which are without the compositions of the invention. Bleaching system 2 contained neither a peroxycarboxylic acid source nor an aromatic sulfonyl halide bleach activator. BJeaching system 3 did not contain a peroxycarboxylic acid source and bleaching systems 4, 6 0 and 8 did not contain an aromatic sulfonyl halide b~each activator.
EXAMPLE IV
The following granular detergent composition was prepared:
-Sodium C12 linear alkylbenzene sulfonate 10.2 Sodium C14_15 alkyl polyethoxylate2 25su~atç! 4~4 C12_13 alkyl polyethoxylate2 5T* 2.2 Fatty acid from menhaden oil 1.1 Sodium tripolyphosphate 68.9 Protease (Anson units/gram) 0~036 Amylase (Amylase units/gram3 9gO
Sodium silicate (2.0r3 3.3 Water 5 5 Miscellaneous 3~5 ~2(17~5S
.
Surface bleaching performance was determined as in Example 1, but with 3.8 grams of the above granular detergent composition and various bleaching systems. Also, the initial pH of the wash water after addition of the bleach system was about 8.1. The 5results were as follows: ;
% Stain Removal Bleachin~ Sxstem ChiliSpa~hetti Mustard 1. None 53 53 47 2. m-chloroperoxybenzoic acid t2) 53 60 43 3. m-chlorobenzoic acid (2) ~ 1,3-benzenedisulfonyl chloride t2) 83 87 43 % Stain Removal ! I_ Taa G rassMean 1. None 50 53 57 53 2. m-chloroperoxybenzoic acid t2) 60 90 63 63 3. m-chlorobenzoic acid (2) ~ 1,3-benzenedisulfonyl chloride t2) 67 89 63 71~
~ leaching system 3, which is within the compositions of the invention, provided significantly more surface bleaching than bleaching composition 2, which is without the compositions of the 25 invention because it did not contain an aromatic sulfonyl halide bleach activator. Also, it should be noted that since the PKa of m-chloroperoxybenzoic acid is 7.57, the pH of the wash water was optimum for bleaching performance of the m-chloroperoxybenzoic acid alone.
EXAMPLE V
7.00 milliliters of a one molar solution of methylene blue dye in methanol was added to a beaker containing 1.00 liter of dis-tilled water. 5.1 grams of sodium carbonate and 1.3 grams of boric acid was added to the beaker which resulted in the pH of 35 the solution being about 10.00. The temperature of the solution was maintained at 37C.
~2~'75~55 A quantity of m-chloroperoxybenzoic acid was added to the solution to give a 1.25 x 10 11 molar concentration. After 20 minutes, the percent transmittance (T) was measured with a Brinkman Colorimeter Model PC700 equipped with a 440 nm fillter.
5 This measurement indicates the amount of methylene blue dye that is destroyed in the solution; a higher change in percent T indi-cates a larger amount of dye that is des~royed. Immediately after this measurement a quantity of 1,3-benzenedisulfonyl chloride was added to the solution to give a 6 . 25 x 10 5 molar concentratTon, 10 which is an equivalent amount to the m-chloroperoxybenzoic acid.
The percent T was measured after 3û seconds. This entire procedure was repeated but benzoyl peroxide was substituted for the m-chtoroperoxybenzoic acid. The results were as follows:
Bleachin~3 System (Minutes~ Chan~e in ~6 T
15 1. i. m-chloroperoxybenzoic acid (2û) ii. m-chloroperoxybenzoic acid + 1,3-benzenedisulfonyl chloride (20.5) 59 2. i. Benzoyl peroxide (20) il. Benzoyl peroxide + 1 ,3-benzena-~0 disul~onyl chloride (21 ) t7 The addition of 1 ,3-benzenedisulfonyl chloride to either m-chloroperoxybenzoic acid or benzoyl peroxide, which are compositions within the invention, rapidly increases the destruction of the methylene blue dye as compared to the 25 m-chloroperoxybenzoic acid alone, which is without the eompositions of the invention. It is believed that increased methylene blue dye destruction corresponds to increased soiution bleaching efficacy on soils.
EXAMPLE Vl 1.5 Grams of the granular detergent composition olF Example I
and a quantity of m-chloroperoxybenzoic acid equivalent to t5 parts per million of available oxygen were dissolved iin a tergotometer containing one liter of 37C.I water containing 7 grains/gallon water hardness. Then six 5"x5" swatches, three of 35 which were dyed with methylene blue dye and tl ree of which .. .
79~S
were undyed, were placed in the tergotometer. The tergotometer was agitated for 10 minutes and then the swatches were removed and dried.
~E for the three dyed and three undyed swatches was 5 measured. ~E is a measurement of the change in color of the swatch resulting from the treatment in the tergotometer. The -~
greater the ~E value, the greater the change in color. It is believed that a larger ~E value for the dyed swatches represents better surface bleaching performance and a smaller ~E value for 10 the undyed swatches represents better solution bleaching.
The above procedure was repeated with numerous bleaching systems. The results were as foliows:
~E
Bleaching System Dyed Undyed 151. rn-chloroperoxybenzoic acid tl5)3,7 5.9 2. m-chloroperoxybenzoic acid ~15) ~
p-toluenesulfonyl chloride (15)12.8 1.9 3. peroxylauric acid (5) + p-toluene-sulfonyl chloride (5) 8.ll t.6 204. Diperoxydodecanedoic acid (15) + p-toluenesulfonyl chloride 15~ 8.5 1.7 5. p-nitroperoxybenzoic acid (5) + p-toluenesulfonyl chloride (5 ) 8 .1 1 .9 6. m-chloroperoxybenzoic acid (5) 5.3 7.2 257. rn-chloroperoxybenzoic acid t5) ~ p toluenesulfonyl chloride (5) 6.9 2.4 8. m-chloroperoxybenzoic acid (5) + methyl-sulfonyl chloride (5) 1~.6 1~.5
9. m-chloroperoxybenzoic acid (5) +
dodecanesulfonyl chloride (5) ~.0 5.8
dodecanesulfonyl chloride (5) ~.0 5.8
10. o-carboxyperoxybenzoic acid t2) 9.8 ~.4
11. o-carboxyperoxybenzoic acid (2) ~ p-toluenesulfonyl chloride (8) 12.Q 2.4 Bleaching systems 2-5, 7 and 11, which are, within the com-35 positions of the invention, provided significantly more surface _ _ _ bleaching and solution bleaching than was obtained with bleaching systerns 1, 6, and 8-10, which are without the compositions of the invention because they did not contain an aromatic sulfonyl halide bleach activator.
Claims (14)
1. A bleaching composition comprising:
(a) a peroxycarboxylic acid or salt thereof; and (b) an aromatic sulfonyl halide bleach activator;
wherein the molar ratio of each potential and actual peroxycarboxyl group of (a) to each sulfonyl group that can potentially generate acyl persulfonate is from about 10 to about 0.05.
(a) a peroxycarboxylic acid or salt thereof; and (b) an aromatic sulfonyl halide bleach activator;
wherein the molar ratio of each potential and actual peroxycarboxyl group of (a) to each sulfonyl group that can potentially generate acyl persulfonate is from about 10 to about 0.05.
2. The composition of claim 1 wherein the peroxycarboxylic acid or salt thereof has the general formula:
wherein R is selected from the group consisting of H, a linear or branched alkyl or alkylene group containing from 1 to about 18 carbon atoms, a cyclic alkyl or alkylene group containing from about 3 to about 18 carbon atoms, an aryl group, an aromatic heterocyclic group, a polyarylene group consisting of 2 or more annelated benzenoid rings and groups in which 2 or more aryl arylene substituents are covalently attached, M is H or a cation which provides water solubility dispersibility to the peroxycarboxylic acid and r is from 1 to the total number of hydrogen atoms on R; and the aromatic sulfonyl halide bleach activator has the general formula:
wherein each Y is selected from the group consisting of:
fluorine, chlorine, bromine and any group which provides an anionic moiety in aqueous solution wherein each n is from 0 to about 12 and each n2 is from 0 to about 18, E is selected from the group consisting of an aryl or arylene group, an aromatic heterocyclic group, a polyarylene group consisting of two or more annelated benzenoid rings and groups in which two or more aryl arylene substituents are covalently attached, Q is chlorine, fluorine, or bromine, and each n3 is from 1 to about 3.
wherein R is selected from the group consisting of H, a linear or branched alkyl or alkylene group containing from 1 to about 18 carbon atoms, a cyclic alkyl or alkylene group containing from about 3 to about 18 carbon atoms, an aryl group, an aromatic heterocyclic group, a polyarylene group consisting of 2 or more annelated benzenoid rings and groups in which 2 or more aryl arylene substituents are covalently attached, M is H or a cation which provides water solubility dispersibility to the peroxycarboxylic acid and r is from 1 to the total number of hydrogen atoms on R; and the aromatic sulfonyl halide bleach activator has the general formula:
wherein each Y is selected from the group consisting of:
fluorine, chlorine, bromine and any group which provides an anionic moiety in aqueous solution wherein each n is from 0 to about 12 and each n2 is from 0 to about 18, E is selected from the group consisting of an aryl or arylene group, an aromatic heterocyclic group, a polyarylene group consisting of two or more annelated benzenoid rings and groups in which two or more aryl arylene substituents are covalently attached, Q is chlorine, fluorine, or bromine, and each n3 is from 1 to about 3.
3. The composition of claim 2 wherein the molar ratio of each potential and actual peroxycarboxylate group of (a) to each sulfonyl group that can potentially generate acyl persulfonate is from about 1 to about 0.3.
4. The composition of claim 3 wherein the aromatic sulfonyl halide bleach activator is selected from the group consisting of:
5. The composition of claim 4 wherein the peroxycarboxylic acid or salt thereof has the general formula:
wherein A is fluorine, chlorine, bromine, or -N02, M is selected from the group consisting of H, magnesium, sodium and potassium, T is an alkyl group containing from about 5 to about 18 carbon atoms, r is 1 or 2 and the molar ratio of each potential and actual peroxycarboxyl group of (a) to each sulfonyl group that can potentially generate acyl persulfonate is from about 1 to about 0.7.
wherein A is fluorine, chlorine, bromine, or -N02, M is selected from the group consisting of H, magnesium, sodium and potassium, T is an alkyl group containing from about 5 to about 18 carbon atoms, r is 1 or 2 and the molar ratio of each potential and actual peroxycarboxyl group of (a) to each sulfonyl group that can potentially generate acyl persulfonate is from about 1 to about 0.7.
6. The composition of claim 5 wherein:
(a) the peroxycarboxylic acid or salt thereof has the general formula:
wherein A is fluorine, chlorine, or bromine and M is H
or magnesium; and (b) the aromatic sulfonyl halide bleach activator has the formula:
(a) the peroxycarboxylic acid or salt thereof has the general formula:
wherein A is fluorine, chlorine, or bromine and M is H
or magnesium; and (b) the aromatic sulfonyl halide bleach activator has the formula:
7. The composition of claim 6 wherein the peroxycarboxylic acid or salt thereof has the general formula:
wherein M is H or magnesium.
wherein M is H or magnesium.
8. A bleaching composition comprising:
(a) a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution;
(b) a bleach activator having the general formula:
wherein R is selected from the group consisting of H, a linear or branched alkyl or alkylene group containing from 1 to about 18 carbon atoms, a cyclic alkyl or alkylene group containing from about 3 to about 18 carbon atoms, an aryl group, an aromatic heterocyclic group, a polyarylene group consisting of 2 or more annelated benzenoid rings and groups in which 2 or more aryl arylene substituents are covalently attached, and L is a leaving group, wherein the conjugate acid of the anion formed on L has a pKa in the range of from about 4 to about 13;
wherein the molar ratio of hydrogen peroxide yielded by (a) to (b) is from about 20 to about 0.1;
(c) an aromatic sulfonyl halide bleach activator having the general formula:
wherein each Y is selected from the group consisting of:
-CnF2n+1, fluorine, chlorine, or bromine and any group which provides an anionic moiety in aqueous solution wherein each n is from 0 to about 12 and each n2 is from 0 to about 18, E is selected from the group consisting of an aryl or arylene group, an aromatic heterocyclic group, a polyarylene group consisting of two or more annelated benzenoid rings and groups in which two or more aryl or arylene substituents are covalently attached, Q is fluorine, chlorine, or bromine, and each n3 is from 1 to about 3:
wherein the molar ratio of each potential peroxycarboxyl group formed by (a) + (b) to each sulfonyl group that can potentially generate an acyl persulfonate is from about 10 to about 0.05.
(a) a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution;
(b) a bleach activator having the general formula:
wherein R is selected from the group consisting of H, a linear or branched alkyl or alkylene group containing from 1 to about 18 carbon atoms, a cyclic alkyl or alkylene group containing from about 3 to about 18 carbon atoms, an aryl group, an aromatic heterocyclic group, a polyarylene group consisting of 2 or more annelated benzenoid rings and groups in which 2 or more aryl arylene substituents are covalently attached, and L is a leaving group, wherein the conjugate acid of the anion formed on L has a pKa in the range of from about 4 to about 13;
wherein the molar ratio of hydrogen peroxide yielded by (a) to (b) is from about 20 to about 0.1;
(c) an aromatic sulfonyl halide bleach activator having the general formula:
wherein each Y is selected from the group consisting of:
-CnF2n+1, fluorine, chlorine, or bromine and any group which provides an anionic moiety in aqueous solution wherein each n is from 0 to about 12 and each n2 is from 0 to about 18, E is selected from the group consisting of an aryl or arylene group, an aromatic heterocyclic group, a polyarylene group consisting of two or more annelated benzenoid rings and groups in which two or more aryl or arylene substituents are covalently attached, Q is fluorine, chlorine, or bromine, and each n3 is from 1 to about 3:
wherein the molar ratio of each potential peroxycarboxyl group formed by (a) + (b) to each sulfonyl group that can potentially generate an acyl persulfonate is from about 10 to about 0.05.
9. The composition of claim 8 wherein (a) is selected from the group consisting of sodium perborate monohydrate, sodium per-borate tetrahydrate, sodium carbon peroxyhydrate, sodium pyro-phosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide and mixtures thereof; L is a leaving group, wherein the conjugate acid of the anion formed on L has a pKa in the range of from about 8 to about 11; (c) is selected from the group consisting of:
the molar ratio of hydrogen peroxide yielded by (a) to (b) is from about 3 to about 1 and the molar ratio of each potential peroxycarboxyl group formed by [(a) + (b)] to each sulfonyl group that can potentially generate acyl persulfonate is from about 1 to about 0.3.
the molar ratio of hydrogen peroxide yielded by (a) to (b) is from about 3 to about 1 and the molar ratio of each potential peroxycarboxyl group formed by [(a) + (b)] to each sulfonyl group that can potentially generate acyl persulfonate is from about 1 to about 0.3.
10. The composition of claim 9 wherein (a) is selected from the group consisting of sodium perborate monohydrate, sodium per-borate tetrahydrate and mixtures thereof; L is selected from the group consisting of:
wherein R is as defined above, R2 is an alkyl chain containing from about 1 to about 8 carbon atoms, R3 is H or R2, and Z is H
or a solubilizing group; and (c) has the formula:
and the molar ratio of each potential peroxycarboxyl group formed by [(a) + (b)] to each sulfonyl group that can potentially generate an acyl persulfonate is from about 1 to about 0.7.
wherein R is as defined above, R2 is an alkyl chain containing from about 1 to about 8 carbon atoms, R3 is H or R2, and Z is H
or a solubilizing group; and (c) has the formula:
and the molar ratio of each potential peroxycarboxyl group formed by [(a) + (b)] to each sulfonyl group that can potentially generate an acyl persulfonate is from about 1 to about 0.7.
11. A bleaching composition comprising:
(a) an organic peroxide compound having the general formula:
wherein each R is selected from the group consisting of H, a linear or branched alkyl or alkylene group containing from 1 to about 18 carbon atoms, a cyclic alkyl or alkylene group containing from about 3 to about 18 carbon atoms, an aryl group, an aromatic heterocyclic group, a polyarylene group consisting of 2 or more annelated benzenoid rings and groups in which 2 or more aryl or arylene substituents are covalently attached: and (b) an aromatic sulfonyl halide bleach activator having the general formula:
wherein each Y is selected from the group consisting of:
-CnF2n+1, fluorine, chlorine, or bromine and any group which provides an anionic moiety in aqueous solution wherein each n is from 0 to about 12 and each n2 is from 0 to about 18, E is selected from the group consisting of an aryl arylene group, an aromatic heterocyclic group, a polyarylene group consisting of two or more annelated benzenoid rings and groups in which two or more aryl or arylene substituents are covalently attached, Q is a halogen and each n3 is from 1 to about 3;
wherein the molar ratio of each potential carboxyl group formed by (a) to each sulfonyl group that can potentially generate acyl persulfonate is from about 10 to about 0.05.
(a) an organic peroxide compound having the general formula:
wherein each R is selected from the group consisting of H, a linear or branched alkyl or alkylene group containing from 1 to about 18 carbon atoms, a cyclic alkyl or alkylene group containing from about 3 to about 18 carbon atoms, an aryl group, an aromatic heterocyclic group, a polyarylene group consisting of 2 or more annelated benzenoid rings and groups in which 2 or more aryl or arylene substituents are covalently attached: and (b) an aromatic sulfonyl halide bleach activator having the general formula:
wherein each Y is selected from the group consisting of:
-CnF2n+1, fluorine, chlorine, or bromine and any group which provides an anionic moiety in aqueous solution wherein each n is from 0 to about 12 and each n2 is from 0 to about 18, E is selected from the group consisting of an aryl arylene group, an aromatic heterocyclic group, a polyarylene group consisting of two or more annelated benzenoid rings and groups in which two or more aryl or arylene substituents are covalently attached, Q is a halogen and each n3 is from 1 to about 3;
wherein the molar ratio of each potential carboxyl group formed by (a) to each sulfonyl group that can potentially generate acyl persulfonate is from about 10 to about 0.05.
12. The composition of claim 11 wherein the aromatic sulfonyl halide bleach activator is selected from the group consisting of:
and the molar ratio of each potential peroxycarboxyl group formed by (a) to each sulfonyl group that can potentially generate acyl persulfonate is from about 1 to about 0.3.
and the molar ratio of each potential peroxycarboxyl group formed by (a) to each sulfonyl group that can potentially generate acyl persulfonate is from about 1 to about 0.3.
13. The composition of claim 12 wherein the aromatic sulfonyl halide bleach activator has the formula:
wherein the molar ratio of each potential peroxycarboxyl group formed by (a) to each sulfonyl group that can potentially gener-ate acyl persulfonate is from about 1 to about 0.7.
wherein the molar ratio of each potential peroxycarboxyl group formed by (a) to each sulfonyl group that can potentially gener-ate acyl persulfonate is from about 1 to about 0.7.
14. The composition of claim 13 further comprising a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution wherein the molar ratio of (a) to the peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution is from about 0.1 to about 10.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43056282A | 1982-09-30 | 1982-09-30 | |
| US53245683A | 1983-09-16 | 1983-09-16 | |
| US532,456 | 1983-09-16 | ||
| US430,562 | 1995-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1207955A true CA1207955A (en) | 1986-07-22 |
Family
ID=27028654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000437910A Expired CA1207955A (en) | 1982-09-30 | 1983-09-29 | Bleaching compositions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0105690B1 (en) |
| CA (1) | CA1207955A (en) |
| DE (1) | DE3377361D1 (en) |
| GR (1) | GR81268B (en) |
| IE (1) | IE55976B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9783766B2 (en) | 2015-04-03 | 2017-10-10 | Ecolab Usa Inc. | Enhanced peroxygen stability using anionic surfactant in TAED-containing peroxygen solid |
| US10280386B2 (en) | 2015-04-03 | 2019-05-07 | Ecolab Usa Inc. | Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid |
| US10870818B2 (en) | 2018-06-15 | 2020-12-22 | Ecolab Usa Inc. | Enhanced peroxygen stability using fatty acid in bleach activating agent containing peroxygen solid |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3472571D1 (en) * | 1983-08-27 | 1988-08-11 | Procter & Gamble | Detergent compositions |
| EP0195663A3 (en) * | 1985-03-20 | 1987-05-13 | The Procter & Gamble Company | Bleaching compositions |
| ATE95812T1 (en) * | 1986-11-03 | 1993-10-15 | Monsanto Co | SULPHONE-PEROXYCARBONIC ACIDS. |
| US4824591A (en) * | 1987-09-17 | 1989-04-25 | Monsanto Company | Sulfone peroxycarboxylic acids |
| US4758369A (en) * | 1986-11-03 | 1988-07-19 | Monsanto Company | Sulfone peroxycarboxylic acids |
| US5004558A (en) * | 1986-11-03 | 1991-04-02 | Monsanto Company | Sulfone peroxycarboxylic acids |
| US4927559A (en) * | 1988-04-14 | 1990-05-22 | Lever Brothers Company | Low perborate to precursor ratio bleach systems |
| GB8910725D0 (en) * | 1989-05-10 | 1989-06-28 | Unilever Plc | Bleach activation and bleaching compositions |
| IT201600070454A1 (en) | 2016-07-06 | 2016-10-06 | 3V Sigma Spa | PEROSSIGENATED COMPOUND ACTIVATORS |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4107065A (en) * | 1975-11-05 | 1978-08-15 | Colgate-Palmolive Company | Activated peroxy compound bleaching compositions and bleaching detergent compositions |
| US4292191A (en) * | 1975-11-05 | 1981-09-29 | Colgate-Palmolive Company | Activated peroxy compound bleaching compositions and bleaching detergent compositions |
| US4100095A (en) * | 1976-08-27 | 1978-07-11 | The Procter & Gamble Company | Peroxyacid bleach composition having improved exotherm control |
-
1983
- 1983-09-26 EP EP19830305726 patent/EP0105690B1/en not_active Expired
- 1983-09-26 DE DE8383305726T patent/DE3377361D1/en not_active Expired
- 1983-09-28 GR GR72559A patent/GR81268B/el unknown
- 1983-09-29 IE IE229883A patent/IE55976B1/en unknown
- 1983-09-29 CA CA000437910A patent/CA1207955A/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9783766B2 (en) | 2015-04-03 | 2017-10-10 | Ecolab Usa Inc. | Enhanced peroxygen stability using anionic surfactant in TAED-containing peroxygen solid |
| US10280386B2 (en) | 2015-04-03 | 2019-05-07 | Ecolab Usa Inc. | Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid |
| US10557106B2 (en) | 2015-04-03 | 2020-02-11 | Ecolab Usa Inc. | Enhanced peroxygen stability using anionic surfactant in TAED-containing peroxygen solid |
| US11053459B2 (en) | 2015-04-03 | 2021-07-06 | Ecolab Usa Inc. | Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid |
| US11731889B2 (en) | 2015-04-03 | 2023-08-22 | Ecolab Usa Inc. | Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid |
| US10870818B2 (en) | 2018-06-15 | 2020-12-22 | Ecolab Usa Inc. | Enhanced peroxygen stability using fatty acid in bleach activating agent containing peroxygen solid |
| US11193093B2 (en) | 2018-06-15 | 2021-12-07 | Ecolab Usa Inc. | Enhanced peroxygen stability using fatty acid in bleach activating agent containing peroxygen solid |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3377361D1 (en) | 1988-08-18 |
| IE55976B1 (en) | 1991-03-13 |
| GR81268B (en) | 1984-12-11 |
| EP0105690A1 (en) | 1984-04-18 |
| IE832298L (en) | 1984-03-30 |
| EP0105690B1 (en) | 1988-07-13 |
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| MKEX | Expiry |