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US4536314A Expired / Lapsed US ⏱️ 0.0 years remaining

Bleach compositions comprising non-linear aliphatic peroxycarboxylic acid precursors

Assignee: Procter and Gamble Co
•
Filing: 1984-02-22
•
Granted: 1985-08-20
•
Expires: 2004-02-22
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Abstract

Abstract Detergent compositions, detergent additive products and bleaching compositions containing aliphatic peroxyacid bleach precursors of formula <IMAGE> are provided, where L is a leaving group of defined formula whose conjugate acid has a pKa of from 6 to 13 and <IMAGE> is a non linear acyl group, the carboxylic acid derivative of which has a logPOCT in the range from 1.9 to 4.0 (where POCT is the partition coefficient between octanol and water). New precursor compounds are provided in which <IMAGE> is a C7-C17 branched aliphatic acyl group containing a linear chain of at least 5 carbon atoms extending from and including the carbonyl carbon wherein the branching is on at least the 2- and/or 3- carbon atom.

Inventors

  • 👤 Frederick E. Hardy
  • 👤 David J. Kitko
  • 👤 Cushman M. Cambre

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-25 18:20
CPC Classifications
C; C07; C07C; C07C309/00; C11; C11D; C11D3/00; C11D3/39; C11D3/3902; C11D3/3905; C11D3/3907; C11D3/3945; C11D3/3947

Claims Analysis

Total Claims: 50
Claim 1
Independent Claim 211 words
A non-linear aliphatic peroxycarboxylic acid precursor adapted to form a non linear aliphatic peroxy acid in aqueous alkaline hydrogen peroxide solution wherein the precursor has the general formula: ##STR23## wherein the group: ##STR24## is an organic moiety of non linear structural configuration R II and R III being independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl groups, the group: ##STR25## being the acyl moiety of a carboxylic acid having a log P oct of from about 1.9 to about 4.1, wherein P oct is the partition coefficient of the carboxylic acid between n-octanol and water at 21° C., and L is a leaving group selected from the group consisting of ##STR26## wherein Z is selected from the group consisting of H, R 2 and halide, R 2 is an alkyl group containing from 1 to 4 carbon atoms, x is 0 or an integer from 1 to 4 and Y is selected from the group consisting of --SO 3 M --OSO 3 M --CO 2 M --N + (R 2 ) 3 Q - --N(R 2 ) 2 →O wherein M is selected from the group consisting of H, alkali metal, alkali earth meal, ammonium and substituted ammonium and Q is a halide or methosulphate.
Claim 2
Dependent Claim 211 words
A non-linear aliphatic peroxycarboxylic acid precursor adapted to form a non linear aliphatic peroxy acid in aqueous alkaline hydrogen peroxide solution wherein the precursor has the general formula: ##STR23## wherein the group: ##STR24## is an organic moiety of non linear structural configuration R II and R III being independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl groups, the group: ##STR25## being the acyl moiety of a carboxylic acid having a log P oct of from about 1.9 to about 4.1, wherein P oct is the partition coefficient of the carboxylic acid between n-octanol and water at 21° C., and L is a leaving group selected from the group consisting of ##STR26## wherein Z is selected from the group consisting of H, R 2 and halide, R 2 is an alkyl group containing from 1 to 4 carbon atoms, x is 0 or an integer from 1 to 4 and Y is selected from the group consisting of --SO 3 M --OSO 3 M --CO 2 M --N + (R 2 ) 3 Q - --N(R 2 ) 2 →O wherein M is selected from the group consisting of H, alkali metal, alkali earth meal, ammonium and substituted ammonium and Q is a halide or methosulphate.
Claim 3
Dependent Claim 17 words
A non-linear aliphatic peroxycarboxylic acid precursor according to claim 1 wherein R I is a hydrocarbyl moiety.
Claim 4
Dependent Claim 30 words
A non-linear aliphatic peroxycarboxylic acid precursor according to claim 1 wherein the conjugate acid of leaving group L has a pKa in the range from about 7 to about 11.
Claim 5
Dependent Claim 96 words
A non-linear aliphatic peroxycarboxylic acid precursor according to claim 2 wherein R I is a group of formula ##STR27## wherein R IV and R V are each independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl groups, and the group: ##STR28## is a C 6 -C 16 alkyl group in which at least one of R II , R III , R IV and R V is C 1 -C 4 alkyl, there being a linear alkyl chain of at least five carbon atoms extending from and including the carbonyl carbon.
Claim 6
Dependent Claim 29 words
A non linear aliphatic peroxycarboxylic acid precursor according to claim 1 wherein: ##STR29## is a C 6 -C 12 group wherein R II and R III are hydrogen atoms.
Claim 7
Dependent Claim 19 words
A non-linear aliphatic peroxycarboxylic acid precursor according to claim 5 wherein: ##STR30## is a C 7 -C 9 group.
Claim 8
Dependent Claim 17 words
A non-linear aliphatic peroxycarboxylic acid precursor according to claim 6 wherein R I has the formula ##STR31##
Claim 9
Dependent Claim 49 words
A compound according to claim 6 wherein L has the formula (a) in which Z is H, x is 0 and Y is selected from --SO 3 M and --CO 2 M, the conjugate acid of L having a pKa in the range from about 8 to about 10.
Claim 10
Dependent Claim 15 words
An alkali metal ammonium or tri C 2 -C 3 alkanolammonium 2-ethyl hexanoyl oxybenzene sulphonate.
Claim 11
Dependent Claim 15 words
An alkali metal ammonium or tri C 2 -C 3 alkanolammonium 2-ethyl hexanoyl oxybenzene sulphonate.
Claim 12
Dependent Claim 15 words
An alkali metal ammonium or tri C 2 -C 3 alkanolammonium 3,5,5,trimethyl hexanoyl oxybenzene sulphonate.
Claim 13
Dependent Claim 15 words
An alkali metal ammonium or tri C 2 -C 3 alkanolammonium 3,5,5,trimethyl hexanoyl oxybenzene sulphonate.
Claim 14
Dependent Claim 20 words
2-ethyl hexanoyl oxybenzoic acid and alkali metal, alkaline earth metal, ammonium and tri C 2 -C 3 alkanolammonium salts thereof.
Claim 15
Dependent Claim 20 words
2-ethyl hexanoyl oxybenzoic acid and alkali metal, alkaline earth metal, ammonium and tri C 2 -C 3 alkanolammonium salts thereof.
Claim 16
Dependent Claim 21 words
3,5,5,trimethyl hexanoyl oxybenzoic acid and alkali metal, alkaline earth metal, ammonium and tri C 2 -C 3 alkanol ammonium salts thereof.
Claim 17
Dependent Claim 21 words
3,5,5,trimethyl hexanoyl oxybenzoic acid and alkali metal, alkaline earth metal, ammonium and tri C 2 -C 3 alkanol ammonium salts thereof.
Claim 18
Dependent Claim 211 words
A solid detergent composition comprising an organic surfactant, a source of alkaline hydrogen peroxide and a non-linear aliphatic peroxycarboxylic acid precursor wherein the precursor has the general formula ##STR32## wherein the group: ##STR33## is an organic moiety of non linear structural configuration, R II and R III being independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl groups, the group: ##STR34## being the acyl moiety of a carboxylic acid having a log P oct of from about 1.9 to about 4.1, wherein P oct is the partition coefficient of the carboxylic acid between n-octanol and water at 21° C., and L is a leaving group selected from the group consisting of ##STR35## wherein Z is selected from the group consisting of H, R 2 and halide, R 2 is an alkyl group consisting from 1 to 4 carbon atoms, x is 0 or an integer from 1 to 4 and Y is selected from the group consisting of --SO 3 M --OSO 3 M --CO 2 M --N + (R 2 ) 3 Q - --N(R 2 ) 2 →O wherein M is selected from the group consisting of H, alkali metal, alkali earth metal, ammonium or substituted ammonium and Q is a halide or methosulphate.
Claim 19
Dependent Claim 211 words
A solid detergent composition comprising an organic surfactant, a source of alkaline hydrogen peroxide and a non-linear aliphatic peroxycarboxylic acid precursor wherein the precursor has the general formula ##STR32## wherein the group: ##STR33## is an organic moiety of non linear structural configuration, R II and R III being independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl groups, the group: ##STR34## being the acyl moiety of a carboxylic acid having a log P oct of from about 1.9 to about 4.1, wherein P oct is the partition coefficient of the carboxylic acid between n-octanol and water at 21° C., and L is a leaving group selected from the group consisting of ##STR35## wherein Z is selected from the group consisting of H, R 2 and halide, R 2 is an alkyl group consisting from 1 to 4 carbon atoms, x is 0 or an integer from 1 to 4 and Y is selected from the group consisting of --SO 3 M --OSO 3 M --CO 2 M --N + (R 2 ) 3 Q - --N(R 2 ) 2 →O wherein M is selected from the group consisting of H, alkali metal, alkali earth metal, ammonium or substituted ammonium and Q is a halide or methosulphate.
Claim 20
Dependent Claim 20 words
A solid detergent composition according to claim 13 wherein the group R I of said precursor is a hydrocarbyl moiety.
Claim 21
Dependent Claim 61 words
A solid detergent composition according to claim 14 wherein the organic surfactant is selected from the group consisting of anionic, nonionic and cationic surfactants and mixtures thereof and the source of hydrogen peroxide comprises an alkali metal perborate or precarbonate or a hydrogen peroxide clathrate, the molar ratio of said alkaline hydrogen peroxide to the precursor being at least about 1.5:1.
Claim 22
Dependent Claim 19 words
A solid detergent composition according to claim 15 wherein the group ##STR36## is a C 7 -C 9 group.
Claim 23
Dependent Claim 34 words
A solid detergent composition according to claim 16 wherein L has the formula (a) in which Z is H, x is 0 and Y is selected from --SO 3 M and --CO 2 M.
Claim 24
Dependent Claim 76 words
A solid detergent composition according to claim 16 incorporating a peroxy acetic acid precursor selected from the group consisting of tetracetyl ethylene diamine, tetracetyl methylene diamine, sodium p-acetoxybenzene sulphonate, tetracetyl glycouril, penta acetyl glucose and octa acetyl lactose and mixtures thereof, the amounts of said non-linear aliphatic peroxy acid precursor and peroxyacetic acid precursor being such as to provide a non-linear aliphatic peroxy acid:peracetic acid molar ratio in the range from about 3:1 to about 1:5.
Claim 25
Dependent Claim 39 words
A solid detergent composition according to claim 18 wherein the amounts of non-linear peroxyacid precursor and peracetic acid precursor are such as to give a non-linear aliphatic peroxy acid:peracetic acid molar ratio of from about 2:1 to about 1:3.
Claim 26
Dependent Claim 237 words
A laundry additive product adapted for addition to an aqueous laundry liquor containing a source of alkaline hydrogen peroxide, said product incorporating a non-linear aliphatic peroxy carboxylic acid precursor having the general formula ##STR37## wherein the group: ##STR38## is an organic moiety of non linear structural configuration, R II and R III being independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl groups, the group: ##STR39## being the acyl moiety of a carboxylic acid having a log P oct of from about 1.9 to about 4.1, wherein P oct is the partition coefficient of the carboxylic acid between n-octanol and water at 21° C., and L is a leaving group selected from the group consisting of ##STR40## wherein Z is selected from the group consisting of H, R 2 and halide, R 2 is an alkyl group consisting from 1 to 4 carbon atoms, x is 0 or an integer from 1 to 4 and Y is selected from the group consisting of --SO 3 M --OSO 3 M --CO 2 M --N + (R 2 ) 3 Q - --N(R 2 ) 2 →O wherein M is selected from the group consisting of H, alkali metal, alkali earth metal, ammonium or substituted ammonium and Q is a halide or methosulphate; said product being enclosed within a container which allows access of water to the interior thereof on immersion in the liquor.
Claim 27
Dependent Claim 237 words
A laundry additive product adapted for addition to an aqueous laundry liquor containing a source of alkaline hydrogen peroxide, said product incorporating a non-linear aliphatic peroxy carboxylic acid precursor having the general formula ##STR37## wherein the group: ##STR38## is an organic moiety of non linear structural configuration, R II and R III being independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl groups, the group: ##STR39## being the acyl moiety of a carboxylic acid having a log P oct of from about 1.9 to about 4.1, wherein P oct is the partition coefficient of the carboxylic acid between n-octanol and water at 21° C., and L is a leaving group selected from the group consisting of ##STR40## wherein Z is selected from the group consisting of H, R 2 and halide, R 2 is an alkyl group consisting from 1 to 4 carbon atoms, x is 0 or an integer from 1 to 4 and Y is selected from the group consisting of --SO 3 M --OSO 3 M --CO 2 M --N + (R 2 ) 3 Q - --N(R 2 ) 2 →O wherein M is selected from the group consisting of H, alkali metal, alkali earth metal, ammonium or substituted ammonium and Q is a halide or methosulphate; said product being enclosed within a container which allows access of water to the interior thereof on immersion in the liquor.
Claim 28
Dependent Claim 22 words
A laundry additive product according to claim 20 wherein the container is water impermeable and is provided with a water frangible closure.
Claim 29
Dependent Claim 23 words
A laundry additive product according to claim 21 wherein the container comprises a flexible pouch or bag made of synthetic polymeric film material.
Claim 30
Dependent Claim 18 words
A laundry additive product according to claim 21 wherein the water frangible closure comprises a water soluble adhesive.
Claim 31
Dependent Claim 248 words
A laundry additive product adapted for addition to an aqueous laundry liquor containing a source of alkaline hydrogen peroxide, said product incorporating a non-linear aliphatic peroxycarboxylic acid precursor having the general formula ##STR41## wherein the group: ##STR42## is an organic moiety of non linear structural configuration, R II and R III being independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl groups, the group: ##STR43## being the acyl moiety of a carboxylic acid having a log P oct of from about 1.9 to about 4.1, wherein P oct is the partition coefficient of the carboxylic acid between n-octanol and water at 21° C., and L is a leaving group selected from the group consisting of ##STR44## wherein Z is selected from the group consisting of H, R 2 and halide, R 2 is an alkyl group containing from 1 to 4 carbon atoms, x is 0 or an integer from 1 to 4 and Y is selected from the group consisting of --SO 3 M --OSO 3 M --CO 2 M --N + (R 2 ) 3 Q - --N(R 2 ) 2 →O wherein M is selected from the group consisting of H, alkali metal, alkali earth metal, ammonium or substituted ammonium and Q is a halide or methosulphate; said precursor being in water releasable combination with a non particulate flexible substrate, the weight ratio of said precursor to said substrate being in the range of from about 1:10 to about 30:1.
Claim 32
Dependent Claim 248 words
A laundry additive product adapted for addition to an aqueous laundry liquor containing a source of alkaline hydrogen peroxide, said product incorporating a non-linear aliphatic peroxycarboxylic acid precursor having the general formula ##STR41## wherein the group: ##STR42## is an organic moiety of non linear structural configuration, R II and R III being independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl groups, the group: ##STR43## being the acyl moiety of a carboxylic acid having a log P oct of from about 1.9 to about 4.1, wherein P oct is the partition coefficient of the carboxylic acid between n-octanol and water at 21° C., and L is a leaving group selected from the group consisting of ##STR44## wherein Z is selected from the group consisting of H, R 2 and halide, R 2 is an alkyl group containing from 1 to 4 carbon atoms, x is 0 or an integer from 1 to 4 and Y is selected from the group consisting of --SO 3 M --OSO 3 M --CO 2 M --N + (R 2 ) 3 Q - --N(R 2 ) 2 →O wherein M is selected from the group consisting of H, alkali metal, alkali earth metal, ammonium or substituted ammonium and Q is a halide or methosulphate; said precursor being in water releasable combination with a non particulate flexible substrate, the weight ratio of said precursor to said substrate being in the range of from about 1:10 to about 30:1.
Claim 33
Dependent Claim 20 words
A laundry addtive product according to claim 24 wherein the group R I of said precursor is a hydrocarbyl moiety.
Claim 34
Dependent Claim 19 words
A laundry additive product according to claim 25 wherein the group ##STR45## is a C 7 -C 9 group.
Claim 35
Dependent Claim 34 words
A laundry additive product according to claim 26 wherein L has the formula (a) in which Z is H, x is 0 and Y is selected from --SO 3 M and --CO 2 M.
Claim 36
Dependent Claim 20 words
A laundry additive product according to claim 27 wherein the precursor is an alkali metal 3,5,5 trimethyl hexanoyl oxybenzene sulphonate.
Claim 37
Dependent Claim 232 words
A laundry additive product adapted for addition to an aqueous laundry liquor containing a source of alkaline hydrogen peroxide said product consisting essentially of; (a) a composition incorporating an organic peroxyacid bleach precursor of formula ##STR46## wherein R II , R III , R IV , and R V are each independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl groups, the group ##STR47## is a C 6 -C 16 alkyl group in which at least one of R II , R III , R IV and R V is C 1 -C 4 alkyl, there being a linear chain of at least five carbon atoms extending from and including the carbonyl carbon, L is a leaving group of formula ##STR48## where Y is selected from --SO 3 M and --CO 2 M where M is selected from H, alkali metal or alkali earth metal, said composition also incorporating one or more detergent components selected from the group consisting of organic surfactants, detergent builder salts, chelating agents and mixtures thereof, (b) a non particulate flexible substrate; said composition being in water releasable combination with said substrate, the weight ratio of said precursor to said substrate being in the range from about 1:10 to about 3:1 and the weight of ratio of said detergent components other than said precursor to said substrate being not greater than about 10:1.
Claim 38
Dependent Claim 232 words
A laundry additive product adapted for addition to an aqueous laundry liquor containing a source of alkaline hydrogen peroxide said product consisting essentially of; (a) a composition incorporating an organic peroxyacid bleach precursor of formula ##STR46## wherein R II , R III , R IV , and R V are each independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl groups, the group ##STR47## is a C 6 -C 16 alkyl group in which at least one of R II , R III , R IV and R V is C 1 -C 4 alkyl, there being a linear chain of at least five carbon atoms extending from and including the carbonyl carbon, L is a leaving group of formula ##STR48## where Y is selected from --SO 3 M and --CO 2 M where M is selected from H, alkali metal or alkali earth metal, said composition also incorporating one or more detergent components selected from the group consisting of organic surfactants, detergent builder salts, chelating agents and mixtures thereof, (b) a non particulate flexible substrate; said composition being in water releasable combination with said substrate, the weight ratio of said precursor to said substrate being in the range from about 1:10 to about 3:1 and the weight of ratio of said detergent components other than said precursor to said substrate being not greater than about 10:1.
Claim 39
Dependent Claim 79 words
A laundry additive product according to claim 29 wherein the composition further includes a peracetic acid precursor selected from the group consisting of tetracetyl ethylene diamine tetracetyl methylene diamine, sodium p-acetoxybenzene sulphonate, tetracetyl glycouril, penta acetyl glucose and octa acetyl lactose and mixtures thereof, the amounts of said non-linear aliphatic acid precursor to the peroxyacetic acid precursor being such as to provide a non-linear aliphatic peroxy acid:peracetic acid molar ratio in the range from about 3:1 to about 1:5.
Claim 40
Dependent Claim 15 words
A laundry additive product according to claim 29 wherein the substrate is a laminated sheet.
Claim 41
Dependent Claim 37 words
A laundry additive product according to claim 29 wherein said substrate is a non woven fibrous sheet and the weight ratio of said compound to said substrate is in the range from about 1:2 to about 10:1.
Claim 42
Dependent Claim 50 words
A laundry additive product according to claim 29 incorporating a source of hydrogen peroxide selected from the group consisting of sodium perborate tetrahydrate, sodium perborate monohydrate, sodium persilicate, sodium perpyrophosphate and urea-hydrogen peroxide addition products, said source of hydrogen peroxide being spatially separated from said precursor compound on said substrate.
Claim 43
Dependent Claim 222 words
A bleaching composition consisting essentially of a source of hydrogen peroxide selected from the group consisting of an alkali metal inorganic peroxy salts and hydrogen peroxide clathrates in combination with a non-linear aliphatic peroxy compound precursor of general formula ##STR49## wherein the group: ##STR50## is an organic moiety of non linear structural configuration, R II and R III being independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl groups, the group: ##STR51## being the acyl moiety of a carboxylic acid having a log P oct of from about 1.9 to about 4.1, wherein P oct is the partition coefficient of the carboxylic acid between n-octanol and water at 21° C., and L is a leaving group selected from the group consisting of ##STR52## wherein Z is selected from the group consisting of H, R 2 and halide, R 2 is an alkyl group containing from 1 to 4 carbon atoms, x is 0 or an integer from 1 to 4 and Y is selected from the group consisting of --SO 3 M --OSO 3 M --CO 2 M --N + (R 2 ) 3 Q - --N(R 2 ) 2 →O wherein M is selected from the group consisting of H, alkali metal, alkali earth metal, ammonium or substituted ammonium and Q is a halide or methosulphate.
Claim 44
Dependent Claim 222 words
A bleaching composition consisting essentially of a source of hydrogen peroxide selected from the group consisting of an alkali metal inorganic peroxy salts and hydrogen peroxide clathrates in combination with a non-linear aliphatic peroxy compound precursor of general formula ##STR49## wherein the group: ##STR50## is an organic moiety of non linear structural configuration, R II and R III being independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl groups, the group: ##STR51## being the acyl moiety of a carboxylic acid having a log P oct of from about 1.9 to about 4.1, wherein P oct is the partition coefficient of the carboxylic acid between n-octanol and water at 21° C., and L is a leaving group selected from the group consisting of ##STR52## wherein Z is selected from the group consisting of H, R 2 and halide, R 2 is an alkyl group containing from 1 to 4 carbon atoms, x is 0 or an integer from 1 to 4 and Y is selected from the group consisting of --SO 3 M --OSO 3 M --CO 2 M --N + (R 2 ) 3 Q - --N(R 2 ) 2 →O wherein M is selected from the group consisting of H, alkali metal, alkali earth metal, ammonium or substituted ammonium and Q is a halide or methosulphate.
Claim 45
Dependent Claim 69 words
A bleaching composition comprising an aliphatic percarboxylic acid of formula R--COOOH wherein R is a C 6 -C 16 aliphatic group branched in at least the 2- and/or 3-position with respect to the carbonyl carbon atom, there being a linear alkyl chain of at least 5 carbon atoms extending from and including the carbonyl carbon, in combination with an effective amount of stabilising agent for said aliphatic percarboxylic acid.
Claim 46
Dependent Claim 69 words
A bleaching composition comprising an aliphatic percarboxylic acid of formula R--COOOH wherein R is a C 6 -C 16 aliphatic group branched in at least the 2- and/or 3-position with respect to the carbonyl carbon atom, there being a linear alkyl chain of at least 5 carbon atoms extending from and including the carbonyl carbon, in combination with an effective amount of stabilising agent for said aliphatic percarboxylic acid.
Claim 47
Dependent Claim 52 words
A method of forming a laundry bleaching liquor having a bland odour comprising the step of adding a non-linear aliphatic peroxy acid precursor in accordance with claim 1 to an aqueous liquor containing a source of alkaline hydrogen peroxide in an amount of from about 50 to about 350 parts per million.
Claim 48
Dependent Claim 48 words
A method of forming a laundry bleaching liquor having a bland odour comprising the step of adding a product in accordance with claim 20 to an aqueous liquor containing a source of alkaline hydrogen peroxide in an amount of from about 50 to about 350 parts per million.
Claim 49
Dependent Claim 48 words
A method of forming a laundry bleaching liquor having a bland odour comprising the step of adding a product in accordance with claim 24 to an aqueous liquor containing a source of alkaline hydrogen peroxide in an amount of from about 50 to about 350 parts per million.
Claim 50
Dependent Claim 35 words
An aqueous alkaline laundry bleaching liquor having a bland odour containing from about 2 to about 15 ppm available oxygen produced by perhydrolysis of a non-linear aliphatic peroxy acid precursor in accordance with claim 1.

References Cited (Backward Citations)

US4248928A Cited
US4348293A Cited
US4374747A Cited
US4391723A Cited
US4412934A Cited

USPTO Annuity & Maintenance Windows

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3.5 Years (Year 4) 1988-08-19 1989-02-18 1989-08-20 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1992-08-19 1993-02-18 1993-08-20 $3760.00 Window Closed / Lapsed
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