Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds
  • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
• • 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
  • C11D3/3917—Nitrogen-containing compounds

Definitions

• the present invention relates to laundry detergents with activated bleaching systems.
• peroxygen bleaches are effective for stain and or soil removal from fabrics, but that such bleaches are temperature dependent. At a wash liquor temperature of 60 C, peroxygen bleaches are only partially effective As the wash liquor temperature is lowered below 60 C, peroxygen bleaches become relatively ineffective As a consequence, there has been a substantial amount of industrial research to develop bleaching systems which contain an activator that renders peroxygen bleaches effective at wash liquor temperatures below 60 C.
• TAED tetraacetyl ethylene diamine
• NOBS nonanoyl- oxybenzenesulfonate
• many of the hydrophobic activators developed thus far can promote damage to natural rubber parts used in certain washing machines Because of these negative effects on washing machine parts, the selection of such detergent-added bleaching systems has long been limited.
• DAP diacylperoxide
• the class of hydrophobic bleach activators derived from amido acids forms hydrophobic amido peracids upon perhydrolysis without the production of harmful, oily DAP's
• the DAP's produced by the perhydrolysis reaction of the amido acid-derived bleach activators are insoluble crystalline solids. Such solid DAP's do not form a coating film. Accordingly, the natural rubber machine parts are not exposed to the DAP's for extended periods of time and remain substantially undamaged by the bleaching system of the present invention.
• the present invention thus solves the long-standing need for an effective hydrophobic bleaching system which does not promote free radical and peroxide damage to natural rubber parts in washing machines
• the invention provides a method of cleaning fabrics with a bleaching system in washing machines which have parts made of natural rubber such that the natural rubber is substantially undamaged by the bleaching system.
• the method comprises agitating fabrics in said washing machine in an aqueous liquor comprising a bleaching system comprising a bleach activator which reacts with a source of peroxide in said aqueous liquor to yield a peroxyacid without the formation of oily diacylperoxide (DAP) such that said natural rubber parts are substantially undamaged by the by-products of said reaction.
• a bleaching system comprising a bleach activator which reacts with a source of peroxide in said aqueous liquor to yield a peroxyacid without the formation of oily diacylperoxide (DAP) such that said natural rubber parts are substantially undamaged by the by-products of said reaction.
• DAP oily diacylperoxide
• R is an al yl, aryl, or alkaryl group containing from about I to about
• R is an alkylene, arylene or alkaryiene group containing from about 1 to about 1 carbon atoms, and R is H or an alkyl, aryl, or alkaryl group containing from about 1 to about 10 carbon atoms.
• the bleaching system of said method comprises: a) at least about 0.1%, preferably from about 1% to about 75%, by weight, of a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous liquor; and b) at least about 0.1%. preferably from about 0.1% to about 50%, by weight, of a bleach activator selected from the group consisting of:
• R5 R5 or mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group
• R is an alkylene, arylene or alkaryiene group containing from about 1 to about 14 carbon atoms
• R is H or an alkyl, aryl, or alkaryl group containing from about 1 to about 10 carbon atoms
• L is a leaving group
• R. is H, alkyl, alkaryl, aryl, aralkyl, and wherein R ⁇ R-, R 4 , and R- may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino, COORg (wherein R 6 is H or an alkyl group) and carbonyl functions; and iii) mixtures of i) and ii).
• the molar ratio of hydrogen peroxide yielded by a) to bleach a ⁇ ivator b) is greater than about 1.0. Most preferably, the molar ratio of hydrogen peroxide yielded by a) to bleach activator b) is at least about 1.5.
• the invention also encompasses laundry compositions in granular, paste, liquid, or bar form which comprise the aforesaid bleaching system together with detersive ingredients which are present in the composition at the levels indicated hereinafter.
• Preferred bleach activators of type b)i) are those wherein R is an alkyl
• bleach a ⁇ ivators of type b)i) are those of the above general formulas wherein,
• R 1 is an alkyl group containing from about 7 to about 10 carbon atoms and R 2 contains from about 4 to 5 carbon atoms.
• Preferred bleach a ⁇ ivators of type b)ii) are those wherein R-, R-,, R 4 . and R are H and R . is a phenyl group.
• the peroxygen bleaching compound can be any peroxide source and is preferably a member selected from the group consisting of sodium perborate monohydrate, sodium perborate tetrahydrate, sodium percarbonate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide and mixtures thereof.
• Highly preferred peroxygen bleaching compounds are selected from the group consisting of sodium perborate monohydrate, sodium perborate tetrahydrate, sodium percarbonate and mixtures thereof.
• the most highly preferred peroxygen bleaching compound is sodium percarbonate
• the bleach a ⁇ ivators herein can also be used in combination with rubber-safe, hydrophiiic a ⁇ ivators such as TAED, typically at weight ratios of amido-derived a ⁇ ivators:TAED in the range of 1 :5 to 5: 1, preferably about 1 : 1.
• rubber-safe, hydrophiiic activators comprise the N-acyl caprola ⁇ am a ⁇ ivators wherein the acyl moiety has the formula
• Highly preferred hydrophiiic caprola ⁇ am a ⁇ ivators include formyl caproiactam, acetyl capro ⁇ la ⁇ am, and benzoyl caproiactam .
• the method of cleaning fabrics comprises agitating fabrics in said washing machine in an aqueous liquor comprising a detergent composition which comprises at least about 300 ppm of conventional detergent ingredients, at least about 25 ppm of the bleaching compound and at least about 25 ppm of a bleach a ⁇ ivator.
• the liquor comprises from about 900 ppm to about 20,000 ppm of conventional detergent ingredients, from about 100 ppm to about 25,000 ppm of the bleaching compound and from about 100 ppm to about 2.500 ppm of a bleach a ⁇ ivator.
• the method can be successfully carried out at temperatures below about 60 C but, of course, is quite effective and is still safe to rubber parts at laundry temperatures up to the boil.
• the conventional detergent ingredients employed in fully formulated detergent compositions provided herein can comprise from about 1% to about
• detergent compositions can comprise from about 5% to about 80% of a detersive builder
• Other optional detergent ingredients are also encompassed by the fully-formulated detergent/bleach compositions provided by this invention
• the invention relates to a method for cleaning fabrics in automatic washing machines having parts made of natural rubber which is susceptible to oxidative degradation.
• the bleaching system used in this invention is safe to natural rubber machine pans and to other natural rubber articles which are exposed to the bleaching system, including fabrics containing natural rubber and natural rubber elastic materials.
• the bleaching system employed in the present invention provides effe ⁇ ive and efficient surface bleaching of fabrics which thereby removes stains and or soils, including "dingy" soils, from the fabrics.
• Dingy soils are soils that build up on fabrics after numerous cycles of usage and washing and, thus, eventually cause white fabrics to have a gray or yellow tint. These soils tend to be a blend of paniculate and greasy materials. The removal of this type of soil is sometimes referred to as "dingy fabric clean up”.
• the bleaching systems and a ⁇ ivators herein afford additional advantages in that, unexpe ⁇ edly, they are safer to fabrics and cause less color damage than other a ⁇ ivators when used in the manner provided by this invention.
• the bleaching mechanism and, in particular, the surface bleaching mechanism are not completely understood. However, it is generally believed that the bleach a ⁇ ivator undergoes nucleophilic attack by a perhydroxide anion, which is generated from the hydrogen peroxide evolved by the peroxygen bleach, to form a peroxycarboxylic acid. This reaction is commonly referred to as perhydrolysis
• the bleach activators within the invention can render peroxygen bleaches more efficient even at wash liquor temperatures wherein bleach a ⁇ ivators are not necessary to a ⁇ ivate the bleach, i.e., above about 60°C. Therefore, with bleach systems of the invention, less peroxygen bleach is required to get the same level of surface bleaching performance as is obtained with the peroxygen bleach alone.
• hydrophobic bleach activators employed with this invention are amide substituted compounds of the general formulas: O 0 O 0
• R5 R5 or mixtures thereof, wherein R I . R 2. and R 5 are as defined hereinabove and L can be-essentially any suitable leaving group.
• a leaving group is any group that is displaced from the bleaching activator as a consequence of the nucleophilic attack on the bleach a ⁇ ivator by the perhydroxide anion. This, the perhydrolysis reaction, results in the formation of the peroxycarboxylic acid.
• a group to be a suitable leaving group it must exert an electron attracting effe ⁇ . It should also form a stable entity so that the rate of the back rea ⁇ ion is negligible. This facilitates the nucleophilic attack by the perhy ⁇ droxide anion.
• the L group must be sufficiently rea ⁇ ive for the reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too rea ⁇ ive, this activator will be difficult to stabilize for use in a bleaching composition.
• These chara ⁇ eristics are generally paralleled by the pKa of the conjugate acid of the leaving group, although exceptions to this convention are known. Ordinarily, 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 6 to about 1 1 and most preferably from about 8 to about
• Preferred bleach a ⁇ ivators are those of the above general formula l 1 22 55 wherein n RR ,, RR aanndd R R a arree as defined for the peroxyacid and L is sele ⁇ ed from the group consisting of:
• R is an alkyl, aryl, or alkaryl group containing
• R is an alkyl chain containing from 1
• R is H or R
• Y is H or a solubilizing group.
• the prefe ⁇ ed solubilizing groups are -SO M , -CO 2 M ,-SO , " M , -N + (R 3 ) 4 X " and CK-N(R 3 ) 3 and most preferably -SO 3 " M and -CO 2 " M + wherein R is an alkyl chain containing from about 1 to about 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach a ⁇ ivator.
• M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide methylsulfate or acetate anion.
• bleach activators with a leaving group that does not contain a solubilizing groups should be well dispersed in the bleaching solution in order to assist in their dissolution.
• Preferred bleach a ⁇ ivators are those of the above general formula wherein L is sele ⁇ ed from the group consisting of:
• R is as defined above and Y is -SO, ⁇ M or -CO- ' M wherein M is as defined above
• Another important class of bleach a ⁇ ivators which provide organic peracids as described herein ring-opens as a consequence of the nucleophilic attack on the carbonyl carbon of the cyclic ring by the perhydroxide anion.
• This ring-opening rea ⁇ ion involves attack at the ring carbonyl by hydrogen peroxide or its anion
• Examples of ring-opening bleach a ⁇ ivators can be found in U.S. Patent 4,966.723. Hodge et al, issued Oct. 30, 1990.
• Such a ⁇ ivator compounds disclosed by Hodge include the a ⁇ ivators of the benzoxazin-type, having the formula:
• R. is H, alkyl, alkaryl, aryl, aralkyl, and wherein I , K ⁇ , K., and K, may be the same or different substituents sele ⁇ ed from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl-amino, COOR, (wherein R fi is H or an alkyl group) and carbonyl functions.
• a preferred a ⁇ ivator of the benzoxazin-type is:
• the bleach activators employed herein will comprise at least about 0.1%, preferably from about 0.1% to about 50%, more preferably from about 1% to about 30%, most preferably from about 3% to about 25%, by weight of the bleaching system or detergent composition.
• the bleaching systems wherein the bleach activator is used, also have as an essential component a peroxygen bleach capable of releasing hydrogen peroxide in aqueous solution.
• the peroxygen bleaching systems useful herein are those capable of yielding hydrogen peroxide in an aqueous liquor. These compounds are well known in the an and include hydrogen peroxide and the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates, and the like. Mixtures of two or more such bleaching compounds can also be used, if desired.
• Preferred peroxygen bleaching compounds include sodium perborate, commercially available in the form of mono-, tri-, and tetra-hydrate, sodium percarbonate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Particularly prefened are sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate. Sodium percarbonate is especially preferred because it is very stable during storage and yet still dissolves very quickly in the bleaching liquor. It is believed that such rapid dissolution results in the formation of higher levels of percarboxylic acid and, thus, enhanced surface bleaching performance.
• Highly preferred percarbonate can be in uncoated or coated form.
• the average panicle size of uncoated percarbonate ranges from about 400 to about 1200 microns, most preferably from about 400 to about 600 microns.
• the preferred coating materials include mixtures of carbonate and sulphate, silicate, borosilicate, or fatty carboxylic acids
• the peroxygen bleaching compound will comprise at least about 0.1%, preferably from about 1% to about 75%, more preferably from about 3% to about 40%, most preferably from about 3% to about 25%, by weight of the bleaching system or detergent composition.
• the weight ratio of bleach a ⁇ ivator to peroxygen bleaching compound in the bleaching system ranges form about 2:1 to about 1 :5. In preferred embodiments, the ratio ranges from about 1 : 1 to about 1 :3.
• bleach a ⁇ ivator bleaching compound systems herein are useful per se as bleaches
• bleaching systems are especially useful in compositions which can comprise various detersive adjuncts such as sur- fa ⁇ ants, builders, enzymes, and the like as disclosed hereinafter.
• detersive Surfa ⁇ ant such as sur- fa ⁇ ants, builders, enzymes, and the like as disclosed hereinafter.
• the amount of detersive surfa ⁇ ant included in the fully-formulated detergent compositions afforded by the present invention can vary from about
• the detersive surfactants comprise from about 5% to about 80% by weight of the composition.
• the detersive surfa ⁇ ant can be nonionic, anionic, ampholytic, zwitterionic. or cationic. Mixtures of these surfactants can also be used.
• Prefened detergent compositions comprise anionic detersive surfactants or mixtures of anionic surfa ⁇ ants with other surfa ⁇ ants, especially nonionic surfa ⁇ ants.
• Nonlimiting examples of surfa ⁇ ants useful herein include the conventional C . , -C . « alkyl benzene sulfonates and primary, secondary, and random alkyl sulfates, the C jQ -C.g alkyl alkoxy sulfates, the C, Q -C,g alkyl polyglycosides and their conesponding sulfated polyglycosides, ,2-C, g alpha-sulfonated fatty acid esters, C, 2 -C,g alkyl and alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), j ⁇ -C. g betaines and sulfobetaines ("sultaines”), C. Q -C. g amine oxides, and the like.
• Other conven ⁇ tional useful surfa ⁇ ants are listed in standard texts.
• One particular class of adjun ⁇ nonionic surfactants especially useful herein comprises the polyhydroxy fatty acid amides of the formula:
• R is H. Cj-Cg hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C.-C, alkyl, more preferably C. or C- alkyl, most preferably C. alkyl (i.e.. methyl), and R is a C ⁇ -C ⁇ hydrocarbyl moiety, preferably straight chain C--.-C.
• Q alkyl or alkenyl more preferably straight chain Cg-C. ⁇ , alkyl or alkenyl, most preferably straight chain C, ,-C.g alkyl or alkenyl, or mixture thereof
• Z is a potyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
• Z preferably will be derived from a reducing sugar in a reductive amination reaction, more preferably Z is a glycityl moiety.
• Suitable reducing sugars include glucose, fru ⁇ ose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
• high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
• Z preferably will be selected from the group consisting of -CH 2 -(CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n .- -CH 2 OH, -CH 2 -(CHOH) 2 (CHOR , )(CHOH)-CH 2 OH, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most prefened are glycityls wherein n is 4, particularly -CH ⁇ CHOH ⁇ -O ⁇ OH.
• R can be, for example, N-methyl, N-ethyl, N-propyl,
• R is preferably methyl or hydroxyalkyl.
• R is preferably C 2 -Cg alkyl, especially n-propyl, iso-propyl, n-butyl, iso-butyl, pentyl, hexyl and 2-ethyI hexyl.
• R -CO-N * *- can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
• Optional detergent ingredients employed in the present invention contain inorganic and/or organic detersive builders to assist in mineral hardness control. If used, these builders comprise from about 5% to about 80% by weight of the detergent compositions.
• Inorganic detersive builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta- phosphates), phosphonates. phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
• non-phosphate builders are required in some locales.
• silicate builders are the alkali metal silicates, particularly those having a SiO ⁇ Na-O ratio in the range 1.6.1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12. 1987 to H. P. Rieck, available from Hoechst under the trademark "S S", SKS-6 is an especially prefened layered silicate builder.
• Carbonate builders especially a finely ground calcium carbonate with
• carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
• Aluminosilicate builders are especially useful in the present invention.
• Prefened aluminosilicates are zeolite builders which have the formula:
• aluminosilicate ion exchange materials are commercially available These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived.
• M ⁇ hods for producing aluminosilicate ion exchange materials are disclosed in U.S Patent 3,985,669, Krummel, et al, issued O ⁇ ober 12, 1976, and U.S. Patent 4,605,509, Corkill, et al, issued Aug. 12, 1986.
• Prefened synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), (including those disclosed in
• the aluminosilicate has a particle size of about 0.1-10 microns in diameter
• Organic d ⁇ ersive builders suitable for the purposes of the present invention include, but are not restri ⁇ ed to, a wide variety of polycarboxylate compounds, such as ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3.635,830, issued Januaiy 18, 1972. See also "TMS TDS" builders of U.S. Patent 4.663.071. issued to Bush et al, on May 5, 1987.
• detersive builders include the ether hydroxypolycar- boxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether,
• Citrate builders e g . citric acid and soluble salts thereof (particularly sodium salt), are prefened polycarboxylate builders that can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders.
• detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
• the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
• Phosphonate builders such as ethane- l-hydroxy-l,l-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
• the conventional detergent ingredients employed herein can be sele ⁇ ed from typical detergent composition components such as detersive surfa ⁇ ants and detersive builders.
• the detergent ingredients can include one or more other detersive adjun ⁇ s or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition.
• Usual detersive adjun ⁇ s of detergent compositions include the- ingredients set forth in U.S. Pat. No. 3,936,537, Baskerville et al. Adjun ⁇ s which can also be included in detergent compositions employed in the present invention, in their conventional art-established levels for use (generally from
• the detergent ingredients include enzymes, especially proteases, lipases, and celluiases, color speckles, suds boosters, suds suppressors, antitarnish and/or anticonosion agents, soil-suspending agents, soil release agents, dyes, fillers, optical brighteners. germicides, alkalinity sources, hydrotropes, antioxidants, enzyme stabilizing agents, perfumes, solvents, solubilizing agents, clay soil removal/anti-redeposition agents, polymeric dispersing agents, processing aids, fabric softening components, static control agents, etc.
• enzymes especially proteases, lipases, and celluiases, color speckles, suds boosters, suds suppressors, antitarnish and/or anticonosion agents, soil-suspending agents, soil release agents, dyes, fillers, optical brighteners.
• germicides alkalinity sources, hydrotropes, antioxidants, enzyme stabilizing agents, perfumes, solvents, solubilizing agents, clay soil removal/anti-
• Bleach systems optionally, but preferably, will also comprise a chelant which not only enhances bleach stability by scavenging heavy metal ions which tend to decompose bleaches, but also assists in the removal of polyphenolic stains such as tea stains, and the like.
• a chelant including the amino- phosphonates, available as DEQUEST from Monsanto, the nitrilotriacetates, the hydroxyethyl-ethylenediamine triacetates, and the like, are known for such use.
• Preferred biodegradable, non-phosphorus chelants include ethylene- diamine disuccinate ("EDDS"; see U.S.
• the detergent compositions employed herein can comprise, in addition to the bleaching system of the present invention, one or more other conventional bleaching agents, a ⁇ ivators, or stabilizers which do not rea ⁇ with or otherwise harm natural rubber. In general, the formulator will ensure that the bleach compounds used are compatible with the detergent formulation.
• optional bleach a ⁇ ivators for incorporation in this invention include tetraacetyl ethylene diamine (TAED) and N-acyl caprola ⁇ ams.
• TAED tetraacetyl ethylene diamine
• N-acyl caprola ⁇ ams Highly prefened N-acyl caprolactams include benzoyl caprola ⁇ am and those wherein the acyl moieties have the formula R -CO- wherein R is H or an alkyl, aryl, arkaryl, or alkoxyaryl group containing from 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms.
• Such bleaching compounds and agents can be optionally included in detergent compositions in their conventional art-established levels of use, generally from 0% to about 15%, by weight of detergent composition.
• Bleaching a ⁇ ivators of the invention are especially useful in conventional laundry detergent compositions such as those typically found in granular detergents or laundry bars.
• U.S. Patent 3,178,370, Okenfuss, issued April 13, 1965. describes laundry detergent bars and processes for making them.
• Philippine Patent 13,778. Anderson, issued Sept. 23, 1980, describes synthetic detergent laundry bars Methods for making laundry detergent bars by various extrusion methods are well known in the art.
• 6-Nonanamidocaproic Acid fNACA 6-Nonanamidocaproic Acid fNACA
• the reaction is carried out in a 12L 3 -necked flask equipped with a thermometer, addition funnel and mechanical stiner
• a solution made from 212g (5.3 moles) of sodium hydroxide and 6L of water (cooled to room temperature) is added 694.3g (5.3 moles) of 6-aminocaproic acid.
• This mixture is cooled to 10°C and a solution of 694.3g (5.3 moles) of nonanoyl chloride in IL of ether is added in a slow stream (about 2.5 hours) keeping the temperature at 10-15°C.
• a solution of 694.3g (5.3 moles) of nonanoyl chloride in IL of ether is added in a slow stream (about 2.5 hours) keeping the temperature at 10-15°C.
• the reaction is maintained at pH
• NACA-C1 Acid Chloride
• NACA-OBS (6-NonanamidocaprovDoxybcnzenesulfonate (NACA-OBS) -
• the rea ⁇ or is a 12L, 3-necked flask equipped with a condenser, mechanical stiner and static argon supply.
• To the reactor are added 647g of the above NACA-Cl toluene solution (1 43 moles), 6L of toluene and 310.8g (1.43 moles) of disodium p-phenolsulfonate (disodium p-phenolsulfonate is previously prepared and dried in a vacuum oven before use (1 10°C, 0.1mm hg, 18 hours). This mixture is refluxed for 18 hours.
• EXAMPLE II A granular detergent compositions is prepared comprising the following ingredients.
• Component Weight % C. 2 linear alkyl benzene sulfonate 22
• Aqueous crutcher mixes of heat and alkali stable components of the detergent compositions are prepared and spray-dried.
• the other ingredients are admixed so that the composition contains the ingredients tabulated at the levels shown.
• the detergent granules with bleach activator are added together with 5 lb. (2.3 kg) of previously laundered fabrics, including natural rubber articles such as elastic fabrics, to an automatic washing machine equipped with a natural rubber sump hose. A ⁇ ual weights of detergent and bleach activator are taken to provide a 950 ppm concentration of the former and 50 ppm concentration of the latter in the 17 gallon (65 I) water-fill machine.
• the water used has 7 grains gallon hardness and a pH of 7 to 7.5 prior to (about 9 to about 10.5 after) addition of the detergent and bleaching system.
• the fabrics are laundered at 35°C (95°F) for a full cycle (12 min.) and rinsed at 2I°C (70°F)
• the laundering method is repeated for 2,000 wash cycles without rupture of, or significant damage to, the natural rubber parts, or damage to the natural rubber articles.
• EXAMPLE III A granular detergent composition is prepared comprising the following ingredients.
• Aqueous crutcher mixes of heat and alkali stable components of the detergent composition are prepared and spray-dried.
• the other ingredients are admixed so that the composition contains the ingredients tabulated at the levels shown.
• the detergent granules with bleach activator are added via the dispensing drawer together with 5 lb. (2.3 kg) of previously laundered fabrics to an automatic washing machine equipped with a natural rubber sump hose. Actual weights of detergent and bleach a ⁇ ivator are taken to provide a 8,000 ppm concentration of the former and 400 ppm concentration of the latter in the 17 I water-fill machine
• the water used has 7 grains gallon hardness and a pH of 7 to 7.5 prior to (about 9 to about 10.5 after) addition of the detergent and bleaching system
• a detergent composition is prepared by a procedure identical to that of Example III, with the single exception that an equivalent amount of nonanoyloxybenzenesulfonate (NOBS) is substituted for the (6-Nonanamido- caproyl)oxybenzenesulfonate bleach a ⁇ ivator in Example III.
• NOBS nonanoyloxybenzenesulfonate
• the laundering method of Example III is repeated for 1200 cycles at about which time the natural rubber sump hose ruptures.
• EXAMPLE V A detergent composition is prepared by a procedure identical to that of Example III, with the single exception that an equivalent amount of benzoyloxybenzenesulfonate (BOBS) is substituted for the (6-Nonanamido- caproyl)oxybenzenesuIfonate bleach a ⁇ ivator in Example III
• BOBS benzoyloxybenzenesulfonate
• 6-Nonanamido- caproyloxybenzenesuIfonate bleach a ⁇ ivator The laundering method of Example III is repeated for 1200 cycles at about which time the natural rubber sump hose ruptures.
• a d ⁇ ergent composition is prepared by a procedure identical to that of Example III, with the exceptions that 15% of a 1 : 1 mixture of tetraacetyl ethylene diamine and (6-NonanamidocaproyI)oxybenzenesulfonate bleach a ⁇ ivator is substituted for the bleach a ⁇ ivator in Example III and the amount of sodium percarbonate is 30%.
• the laundering method of Example III is repeated for 2,000 cycles without rupture of, or significant damage to, the natural rubber parts
• EXAMPLE VII A detergent composition is prepared by a procedure identical to that of Example III, with the single exception that 15% of a 1: 1 mixture of benzoyl caproiactam and (6-Nonanamidocaproyl)oxybenzenesulfonate is substituted for the bleach a ⁇ ivator in Example III and the amount of sodium percarbonate is
• Example III 30% The laundering method of Example III is repeated for 2,000 cycles without rupture of, or significant damage to, the natural rubber parts.
• EXAMPLE VIH A detergent composition is prepared by a procedure identical to that of Example III. with an equivalent amount of a benzoxazin-type bleaching activator, as disclosed in U S Patent 4,966,723, Hodge et al, is substituted for the bleach activator in Example III The laundering method of Example III is repeated for 2,000 cycles without rupture of, or significant damage to, the natural rubber parts EXAMPLE IX
• a detergent composition is prepared by a procedure identical to that of
• Example III with the single exception that 6% of a 1: 1 mixture of (6-Nonan- amidocaproyl)oxybenzenesulfonate and a benzoxazin-type bleaching activator, as disclosed in U S Patent 4,966,723, Hodge et al, is substituted for the bleach a ⁇ ivator in Example III
• the laundering method of Example III is repeated for 2,000 cycles without rupture of, or significant damage to, the natural rubber parts.
• EXAMPLE X A detergent composition is prepared by a procedure identical to that of Example III, with the single exception that 6% of a 1 : 1 mixture of tetraacetyl ethylene diamine and a benzoxazin-type bleaching a ⁇ ivator, as disclosed in U.S. Patent 4,966,723, Hodge et al, is substituted for the bleach activator in Example III.
• the laundering method of Example III is repeated for 2,000 cycles without rupture of, or significant damage to, the natural rubber parts.
• the bleach a ⁇ ivators may be processed with a range of organic and inorganic substances to achieve a rapid dispersion in the bleaching liquor and to insure good stability in the detergent composition.
• the bleach a ⁇ ivators are preferably employed in paniculate form.
• An example of prefened caprola ⁇ am bleach a ⁇ ivator particles is an agglomerate of about 65%, by weight, b ⁇ nzoyl caprola ⁇ am; about 7% of a builder, such as aluminium silicate; about 15% sodium carbonate; about 9% dispersant, such as a polyacrylate polymer; and about 4% of a solubilizing agent, such as a linear alkyl sulfonate.
• Another example of a prefened caprola ⁇ am bleach a ⁇ ivator particle is an agglomerate of about 80% to about
• benzoyl caprola ⁇ am 85%, by weight, benzoyl caprola ⁇ am and about 15% to about 20% of a binder, such as tallow alcohol ethoxylates, preferably TAE25.
• a binder such as tallow alcohol ethoxylates, preferably TAE25.
• An example of a preferred amido-derived bleach a ⁇ ivator particle comprises a 1 :1 : 1 mixture of (6-o ⁇ anamidocaproyI)oxybenzenesulfonate, (6- decanamidocaproyl)oxybenzenesulfonate, and citric acid powder.
• the mixture is intimately mixed in a food mixer for 5-10 minutes.
• To the resultant mixture is added tallow alcohol ethoxylate (TAE25) nonionic surfactant at 50° C until granules are formed Typically successful granulations are achieved with a ratio of bleach a ⁇ ivator/citric acid solid mixtures.nonionic binding agent of 3.5: 1.
• TAE25 tallow alcohol ethoxylate
• a typical particle composition is about 40% to about 60%, preferably about 55%, by weight, of the bleach activator or mixture of bleach activators; about 20% to about 40%, preferably about 25%, by weight, of citric acid; and about 15% to about 30%, preferably about 20%, by weight of TAE25 binding agent.
• a 2:1 mixture of (6-decanamidocaproyl)oxyben- zenesulfonate and citric acid powder may be used.
• the composition on the granule is 55% bleach a ⁇ ivator, 25% citric acid, and 20% TAE25 binding agent.
• Other prefened organic binding agents include anionic surfa ⁇ ants (Cj2 linear alkyl benzene sulfonates), polyethylene glycols, and TAE50.
• the particle size of the resulting granules may be varied according to the desired performance/stability. Fine particles ( ⁇ 250 um) show improved solubility, though coarse particles (>1 180 um) are more stable at high temperatures moist environment. A typically prefened particle size range is 250-1 180 um; particles conforming to this specification show excellent stability and solubility.
• a laundry bar suitable for hand-washing soiled fabrics is prepared by standard extrusion processes and comprises the following:

Landscapes

• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)

Applications Claiming Priority (5)

Publications (2)

Family

ID=26744644

Family Applications (1)

Country Status (11)

Families Citing this family (16)

Family Cites Families (4)

• 1994
  • 1994-05-12 EP EP94917980A patent/EP0699233B1/de not_active Expired - Lifetime
  • 1994-05-12 CA CA002161211A patent/CA2161211C/en not_active Expired - Fee Related
  • 1994-05-12 HU HU9503298A patent/HU216639B/hu not_active IP Right Cessation
  • 1994-05-12 CZ CZ953058A patent/CZ305895A3/cs unknown
  • 1994-05-12 DE DE69417413T patent/DE69417413T2/de not_active Expired - Fee Related
  • 1994-05-12 JP JP7500719A patent/JPH08510778A/ja active Pending
  • 1994-05-12 BR BR9406307A patent/BR9406307A/pt not_active Application Discontinuation
  • 1994-05-12 AT AT94917980T patent/ATE178091T1/de active
  • 1994-05-12 AU AU69492/94A patent/AU6949294A/en not_active Abandoned
  • 1994-05-12 CN CN94192173A patent/CN1057792C/zh not_active Expired - Fee Related
  • 1994-05-12 WO PCT/US1994/005370 patent/WO1994028104A1/en not_active Ceased

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events