Title of Invention

"A DETERGENT COMPOSITIONS"

Abstract A content management system allows users to post information into pre-authorized areas of public and private internet and intranet web sites. An automated computer-implemented on-line calendar system posts event information associated with a plurality of entities. Each entity has its own calendar. A calendar event database accepts event entry calendar input information from a plurality of content providers and stores the event entries. Each event entry is associated with one or more entities specified by the content provider. A calendar assembler generates calendars of events for each of the entities using the information stored in the calendar event database. The event entries include private entries which appear only on the calendar of an...
Full Text TECHNICAL FIELD
The present invention relates to compositions, in either liquid or granular form, for use in laundry applications, wherein the compositions comprise certain cyclic amine based polymer, oligomer or copolymer materials in combination with hydrophobically modified carboxy methyl cellulose. This combination imparts appearance and integrity benefits to fabrics and textiles laundered in washing solutions formed from such compositions.
BACKGROUND OF THE INVENTION
It is, of course, well known that alternating cycles of using and laundering fabrics and textiles, such as articles of worn clothing and apparel, will inevitably adversely affect the appearance and integrity of the fabric and textile items so used and laundered. Fabrics and textiles simply wear out over time and with use. Laundering of fabrics and textiles is necessary to remove soils and stains which accumulate therein and thereon during ordinary use. However, the laundering operation itself, over many cycles, can accentuate and contribute to the deterioration of the integrity and the appearance of such fabrics and textiles.
Deterioration of fabric integrity and appearance can manifest itself in several ways. Short fibers are dislodged from woven and knit fabric/textile structures by the mechanical action of laundering. These dislodged fibers may form lint, fuzz or "pills" which are visible on the surface of fabrics and diminish the appearance of newness of the fabric. Further, repeated laundering of fabrics and textiles, especially with bleach-containing laundry products, can remove dye from fabrics and textiles and impart a faded, worn out appearance as a result of diminished color intensity, and in many cases, as a result of changes in hues or shades of color.
Given the foregoing, there is clearly an ongoing need to identify materials which could be added to laundry detergent products that would associate themselves with the fibers of the fabrics and textiles laundered using such detergent products and thereby reduce or minimize the tendency of the laundered fabric/textiles to deteriorate in appearance. Any such detergent product additive material should, of course, be able to benefit fabric appearance and integrity without unduly interfering with the ability of the laundry detergent to perform its fabric cleaning
function. The present invention is directed to the use of a mixture of certain cyclic amine based polymer, oligomer or copolymer materials and hydrophobically modified carboxy methyl cellulose (CMC) in laundry applications that perform in this desired manner.
SUMMARY OF THE INVENTION
The present invention is directed to a detergent composition comprising:
a) from about 1% to about 80% by weight of surfactants selected from the group
consisting of nonionic, anionic, cationic, amphotenc zwittenonic surfactants and
mixtures thereof; and
b) at least about 0.01%, preferably at least about 0.1%, most preferably at least
about 0.5% and less than about 50%, preferably less than about 25.0%, most
preferably less than about 5.0%, by weight, of a mixture of cyclic amine based
polymers, oltgomers or copolymers and hydrophobically modified cellulosic based
polymers or oligomers.
The cyclic amine based polymer, oligomer or copolymer materials which are suitable for use in laundry operations and provide the desired fabric appearance and integrity benefits can be characterized by the following general formula:
(Formula Removed)
wherein;
independently selected from the group consisting of H,C1-C12 alkyl, substituted alkyl, (Formula Removed)
W compnses at least one cyclic constituent selected from the group consisting of:
(Formula Removed)
in addition to the at least one cyclic constituent, W may also comprise an aliphatic or substituted aliphatic moiety of the general structure;
(Formula Removed)
-each B is independently C1-C12 alkylene, C1-C12 substituted alkylene, C3-C12 alkenylene, Cg C12 dialkylarylene, C8-C12 dialkylarylenediyl, and -(R5O)nR5-;
-each D is independently C2-C6 alkylene;
-each Q is independently selected from the group consisting of hydroxy, C1-C18 alkoxy, C hydroxyalkoxy, ammo, C1-C18 alkylamino, dialkylamino, trialkylamino groups, heterocyclic monoamino groups and diamino groups;
-each RI is independently selected from the group consisting of H, C1-C8 alkyl and C1-C8 hydroxyalkyl;
-each R2 is independently selected from the group consisting of C1-C12 alkylene, C1-C12 alkenylene, -CH2-CH(OR])-CH2, C8-C12 alkarylene, C4-Ci2 dihydroxyalkylene, poly(C2-C4 alkyleneoxy)alkylene, H2CH(OH)CH2OR2OCH2CH(OH)CH2-, and C3-C12 hydrocarbyl moieties;
provided that when R: is a C3-C12 hydrocarbyl moiety the hydrocarbyl moiety can comprise from about 2 to about 4 branching moieties of the general structure:
(Formula Removed)
each R3 is independently selected from the group consisting of H, O, R2, C1-C20 hydroxyalkyl, C1-C20 alkyl, substituted alkyl, C6-C11 aryl, substituted aryl, C7-C11 alkylaryl, C1-C20 ammoalkyl, -(CH2)hCOOM, -(CH2)hS03M, CH2CH(OH)SO3M, -(CH2)hOSO3M,
(Formula Removed)
-each R4 is independently selected from the group consisting of H,C1-C22alkyl, C
hydroxyalkyl, aryl and C7-C22 alkylaryl;
-each R5 is independently selected from the group consisting of C2-C8 alkylene, C2-C8 alkyl substituted alkylene; and
A is a compatible monovalent or di or polyvalent anion; M is a compatible cation; b = number necessary to balance the charge; each x is independently from 3 to about 1000; each c is independently 0 or 1 ; each h is independently from about 1 to about 8; each q is independently from 0 to about 6; each n is independently from 1 to about 20; each r is independently from 0 to about 20; and each t is independently from 0 to 1 .
Cellulosic based polymer or oligomer materials which are suitable for use in laundry operations and provide the desired fabric appearance and integrity benefits can be characterized by the following general formula:
(Formula Removed)
wherein each R is selected from the group consisting of R2, RC, and
wherein:
each R2 is independently selected from the group consisting of H and Cj-C4 alkyl;
each RC is
wherein each Z is independently selected from the group consisting of M, R2, RC, and RH;
each RH is independently selected from the group consisting of €5 -€20 alkyl, C5-C7
cycloalkyl, C7-C20 alkylaryl,C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, C1-C20 alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2-hydroxyalkyl, (R4)2N-alkyl, (R4)2N-2-hydroxyalkyl, (R4)3 N-alkyl, (R4)3 N-2-hydroxyalkyl, C6-C12 aryloxy-2-hydroxyalkyl,

(Formula Removed)
each R4 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl,C7-C20 arylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl;
each R5 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (R4)2N-alkyl, and (R4)3 N-alkyl;
wherein:
M is a suitable cation selected from the group consisting of Na, K, l/2Ca, and l/2Mg; each x is from 0 to about 5; each y is from about 1 to about 5; and provided that:
the Degree of Substitution for group RH is between about 0.0005 and-0.1, more preferably
between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05; the Degree of Substitution for group RC wherein Z is H or M is between about 0.2 and 2.0, more preferably between about 0.3 and 1.0, and most preferably between about 0.4 and 0.7;
if any RH bears a positive charge, it is balanced by a suitable anion; and two R4's on the same nitrogen can together form a ring structure selected from the group
consisting of piperidine and morpholine.
The cyclic amine based polymer, oligomer or copolymer materials defined above can be used, along with the hydrophobically modified cellulosic based polymers or oligomers, as a washing solution additive in either granular or liquid form. Alternatively, they can be admixed to granular detergents, dissolved in liquid detergent compositions or added to a fabric softening composition.
The ratio of the hydrophobically modified cellulosic to cyclic amine based polymer, oligomer or copolymer materials is within the range of 1000:1 to 1:1000 and is preferably between 100:1 to 50:1, more preferably between 50:1 to 1:1, even more preferably between 10:1 to 1:1.
The laundry detergent compositions herein comprise from about 1% to 80% by weight of a detersive surfactant, from about 0.01% to 80% by weight of an organic or inorganic detergency builder and from about 0.01% to 5% by weight of the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers based fabric treatment materials of the present invention. The detersive surfactant and detergency builder materials can be any of those useful in conventional laundry detergent products.
Aqueous solutions of the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers of the subject invention comprise from about 0.01% to 80% by weight of the mixture of cyclic amine based polymers, oligomers or copoSymers and hydrophobically modified cellulosic based polymers or oligomers
fabnc treatment matenals dissolved in water and other ingredients such as stabilizers and pH
adjusters.
In its method aspect, the present invention relates to the laundering or treating of fabrics
and textiles in aqueous washing or treating solutions formed from effective amounts of the detergent comnositions described herein, or formed from the individual components of such compositions. Laundering of fabrics and textiles in such washing solutions, followed by nnsing and drying, imparts fabric appearance benefits to the fabric and textile articles so treated. Such benefits can include improved overall appearance, pill/fuzz reduction, antifadmg, improved abrasion resistance, and/or enhanced softness. It has been surprisingly determined that the a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers according to this invention imparts fabric appearance and integrity benefits that are greater than the benefits achieved by a corresponding amount of either component by itself.
DETAILED DESCRIPTION OF THE INVENTION
As noted, when fabric or textiles are laundered in wash solutions which comprise the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers of the present invention fabric appearance and integrity are enhanced. The mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers can be added to wash solutions by incorporating them into a detergent composition, a fabric softener or by adding them separately to the washing solution. The mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers are described herein primarily as liquid or granular detergent additives but the present invention is not meant to be so limited. The mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers, detergent composition components, optional ingredients for such compositions and methods of using such compositions, are described in detail below. All percentages are by weight unless other specified.
A) Cyclic amine Based Polymer. Oligomer or Copolymer Materials
An essential component of the compositions of the present invention comprises one or
more cyclic amine based polymer, oligomer or copolymer. Such materials have been found to
impart a number of appearance benefits to fabrics and textiles laundered in aqueous washing
solutions formed from detergent compositions which contain a mixture of cyclic amine based
polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers fabnc treatment matenals. Such fabric appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc. The cyclic amine based fabnc treatment matenais used in the compositions and methods herein can provide such fabnc appearance benefits with acceptably little or no loss in cleaning performance provided by the laundry detergent compositions into which such materials are incorporated.
The cyclic amine based polymer, oligomer or copolymer component of the compositions herein may comprise combinations of these cyclic amine based materials. For example, a mixture of piperadine and epihalohydin condensates can be combined with a mixture of morpholme and epihalohydnn condensates to achieve the desired fabnc treatment results. Moreover, the molecular weight of cyclic amine based fabric treatment matenals can vary within the mixture as is illustrated in the Examples below.
As will be apparent to those skilled in the art, an oligomer is a molecule consisting of only a few monomer units while polymers comprise considerably more monomer units. For the present invention, oligomers are defined as molecules having an average molecular weight below about 1,000 and polymers are molecules having an average molecular weight of greater than about 1,000. Copolymers are polymers or oligomers wherein two or more dissimilar monomers have been simultaneously or sequentially polymenzed. Copolymers of the present invention can include, for example, polymers or oligomers polymerized from a mixture of a primary cyclic amine based monomer, e.g., piperadine, and a secondary cyclic amine monomer, e.g., morpholine.
The mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers of the detergent compositions herein will generally comprise from about 0.01% to about 5% by the weight of the detergent composition. More preferably, the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers will comprise from about 0.1% to about 4% by weight of the detergent compositions, most preferably from about 0.75% to about 3%. However, as discussed above, when used as a washing solution additive, i.e. when mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers is not incorporated into a detergent composition, the concentration of mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers can comprise from about 0.1% to about 80% by weight of the additive material.
Cyclic amine based polymer, oligomer or copolymer materials which are suitable for use in laundry operations and provide the desired fabnc appearance and integrity benefits can be characterized by the general formula given in the Summary of the Invention.
Preferred compounds that fall within this general structure include compounds:
- wherein each P,j is H; and
-at least one W is selected from the group consisting of:
(Formula Removed)
those:Even more preferred compounds for the fabric appearance and integrity benefits are
-wherein each R1 is H; and
-at least one W is selected from the group consisting of:
(Formula Removed)
And most preferred compounds for the fabnc appearance and integrity benefits are those:
wherein each R1 is H; and
-at least one W is selected from the group consisting of: and
Preferred compounds to be used as the linking group R2 include, but are not limited to; polyepoxides, ethylenecarbonate, propylenecarbonate, urea, a, P-unsaturated carboxylic acids, esters of a, P-unsaturated carboxylic acids, amides of a, P-unsaturated carboxylic acids, anhydrides of a, P-unsaturated carboxylic acids, di- or polycarboxylic acids, esters of di- or polycarboxylic acids, amides of di- or polycarboxylic acids, anhydrides of di- or polycarboxylic acids, glycidylhalogens, chloroformic esters, chloroacetic esters, derivatives of chloroformic esters, derivatives of chloroacetic esters, epihalohydrins, glycerol dichlorohydrins, bis-(halohydnns). polyetherdihalo-compounds, phosgene, polyhalogens, functionalized glycidyl ethers and mixtures thereof. Moreover, R2 can also comprise a reaction product formed by reacting one or more of polyetherdiammes, alkylenediamines, polyalkyienepolyamlnes, alcohols, alkyleneglycols and polyalkyleneglycols with a,ß-unsaturated carboxylic acids, esters of a, P-unsaturated carboxylic acids, amides of a, p-unsaturated carboxylic acids and anhydrides of a, p-unsaturated carboxylic acids provided that the reaction products contain at least two double
bonds, two carboxylic groups, two amide groups or two ester groups.
Additionally preferred cyclic amine based polymer, oligomer or copolymer materials for
use herein include adducts of two or more compositions selected from the group consisting of
piperazine, piperadine, epichlorohydrin, epichlorohydnn benzyl quat, epichlorohydrin methyl
quat, morpholine and mixtures thereof.
These cyclic amine based polymers can be linear or branched. One specific type of
branching can be intorduced using a polyfunctional crosslinking agent. An example of such such
(Formula Removed)
B) Hvdrophobically Modified Cellulosic Based Polymers or Oligomers The essential component of the compositions of the present invention comprises one or more cellulosic based polymer or oligomer. Such materials have been found to impart a number of appearance benefits to fabrics and textiles laundered in aqueous washing solutions formed from detergent compositions which contain such cellulosic based fabric treatment materials. Such fabric appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc. The cellulosic based fabric treatment materials used in the compositions and methods herein can provide such fabric appearance benefits with acceptably little or no loss in cleaning performance provided by the laundry detergent compositions into which such materials are incorporated.
As will be apparent to those skilled in the art, an oligomer is a molecule consisting of only a few monomer units while polymers comprise considerably more monomer units. For the present invention, oligomers are defined as molecules having an average molecular weight below about 1,000 and polymers are molecules having an average molecular weight of greater than about 1,000. One suitable type of cellulosic based polymer or oligomer fabric treatment material for use herein has an average molecular weight of from about 5,000 to about 2,000,000, preferably from about 50,000 to about 1,000,000.
The cellulosic based fabric treatment component of the detergent compositions herein will generally comprise from about 0.1% to about 5% by the weight of the detergent composition. More preferably, such cellulosic based fabric treatment materials will comprise from about 0.5% to about 4% by weight of the detergent compositions, most preferably from about 0.75% to about 3%. However, as discussed above, when used as a washing solution additive, i.e. when the cellulosic based fabric treatment component is not incorporated into a detergent composition, the
concentration of the cellulosic based component can comprise from about 0.1% to about 80% by weight of the additive material.
One suitable group of cellulosic based polymer or oligomer materials for use herein is characterized by the following formula:
(Formula Removed)
wherein each R is selected from the group consisting of R2, RC, and
(Formula Removed)
wherein:
each R2 is independently selected from the group consisting of H and C1-C4 alkyl;
wherein each Z is independently selected from the group consisting of M, R2, RC. and RH;
(Formula Removed)
each RH is independently selected from the group consisting of €5 -€20 alkyl, €5-07 cycloalkyl, 07-020 alkylaryl, 07-020 arylalkyl, substituted alkyl, hydroxyalkyl, alkoxy-2-hydroxyalkyl, 07-020 alkylaryloxy-2-hydroxyalkyl, (R4)2N-alkyl, hydroxyalkyl, (R4)3 N-alkyl, (R4)3 N-2-hydroxyalkyl, C6-C12 aryloxy-2-hydroxyalkyl,
(Formula Removed)
each R4 is independently selected from the group consisting of H, C1-C20alkyl, C cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, aminoalkyl, alkylaminoalkyl,
dialkylammoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl;
each R5 is independently selected from the group consisting of H, C1-C20 alkul C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (R4)2N-alkuy, and (R4)3 N-alkyl; wherein:
M is a suitable cation selected from the group consisting of Na, K, l/2Ca, and l/2Mg; each x is from 0 to about 5; each y is from about 1 to about 5; and provided that:
the Degree of Substitution for group RH is between about 0.0005 and 0.1, more preferably
between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05; the Degree of Substitution for group RC wherein Z is H or M is between about 0.2 and 2.0, more preferably between about 0.3 and 1.0, and most preferably between about 0.4 and 0.7;
if any RH bears a positive charge, it is balanced by a suitable anion; and two R4*s on the same nitrogen can together form a ring structure selected from the group consisting of piperidine and morpholine.
The "Degree of Substitution" for group RH, which is sometimes abbreviated herein "DSRH", means the number of moles of group RH components that are substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six membered ring as shown in the repeating unit of the general structure above.
The "Degree of Substitution" for group RC, which is sometimes abbreviated herein "DSRc", means the number of moles of group RC components, wherein Z is H or M, that are substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six membered ring as shown in the repeating unit of the general structure above. The requirement that Z be H or M is necessary to insure that there are a sufficient number of carboxy methyl groups such that the resulting polymer is soluble. It is understood that in addition to the required number of RC components wherein Z is H or M, there can be, and most preferably are, additional RC components wherein Z is a group other than H or M.
The production of materials according to the present invention is further defined in the Examples below.
C) Detersive Surfactant
The detergent compositions herein comprise from about 1% to 80% by weight of a detersive surfactant. Preferably such compositions comprise from about 5% to 50% by weight of surfactant. Detersive surfactants utilized can be of the aniomc, nonionic, zwitterionic, ampholytic or cationic type or can comprise compatible mixtures of these types. Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Noms, "rssued May 23, 1972, U.S. Patent 3,919,678, Laughlm et al., issued December 30, 1975, U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980. All of these patents are incorporated herein by reference. Of all the surfactants, anionics and nomonics are preferred.
Useful anionic surfactants can themselves be of several different types. For example, 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, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms.
Additional non-soap anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 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.) Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11-13 LAS.
Preferred nonionic surfactants are those of the formula R.(OC2H4)nOH, wherein R. is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to about 80. Particularly preferred are condensation products of C12-C15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
Additional suitable surfactants, including polyhydroxy fatty acid amides and amine based surfactants, are disclosed in co-pending PCT Application WO98/14300, Published March 25, 1999, entitled Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith, which was filed on September 15, 1997, in the name of Panandiker et al. The entire disclosure of the Panandiker et al. reference is incorporated herein by reference.
D) Detergent Builder
The detergent compositions herein may also comprise from about 0.1% to 80% by weight of a detergent builder. Preferably such compositions in liquid form will comprise from about 1% to 10% by weight of the builder component. Preferably such compositions in granular form will comprise from about 1% to 50% by weight of the builder component. Detergent builders are well known in the art and can comprise, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders.
Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates. Suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al., and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al., both of which are incorporated herein by reference. Particularly preferred polycarboxylate builders are the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuccmate and tartrate disuccinate described in U.S. Patent 4,663,071, Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.
Examples of suitable nonphosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates. Particularly preferred are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of SiC>2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Also preferred are aluminosilicates including zeolites. Such materials and their use as detergent builders are more fully discussed in Corkill et al., U. S. Patent No. 4,605,509, the disclosure of which is incorporated herein by reference. Also discussed in U. S. Patent No. 4,605,509 are crystalline layered silicates which are suitable for use in the detergent compositions of this invention.
E) Optional Detergent Ingredients
In addition to the surfactants, builders and mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers hereinbefore described, the detergent compositions of the present invention can also include any number of additional optional ingredients. These include conventional detergent composition components such as enzymes and enzyme stabilizing agents, suds boosters or suds suppressers, anti-tamish and antieorrosion agents, bleaching agents, soil suspending agents, soil release
agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical bnghteners, dyes and perfumes.
A preferred optional ingredients for incorporation into the detergent compositions herein comprises a bleaching agent, e.g., a peroxygen bleach. Such peroxygen bleaching agents may be organic or inorganic in nature. Inorganic peroxygen bleaching agents are frequently utilized in combination with a bleach activator.
Useful organic peroxygen bleaching agents include percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, Issued November 20, 1984; European Patent Application EP-A-133,354, Banks et al., Published February 20, 1985; and U.S. Patent 4,412,934. Chung et al., Issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in U.S. Patent 4,634,551, Issued January 6, 1987 to Burns et al.
Inorganic peroxygen bleaching agents may also be used, generally in paniculate form, in the detergent compositions herein. Inorganic bleaching agents are in fact preferred. Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials. For example, sodium perborate (e.g. mono- or tetra-hydrate) can be used. Suitable inorganic bleaching agents can also include sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used. Frequently inorganic peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble surfactants. For example, coated percarbonate particles are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.
Inorganic peroxygen bleaching agents, e.g., the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during use of the compositions herein for fabric laundering/bleaching) of the peroxy acid corresponding to the bleach activator. Various non-limiting examples of activators are disclosed in U.S. Patent 4,915,854, Issued April 10, 1990 to Mao et al.; and U.S. Patent 4,412,934 Issued November 1, 1983 to Chung et al. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical and preferred. Mixtures thereof can also be used. See also the hereinbefore referenced U.S. 4,634,551 for other typical bleaches and activators useful herein.
Other useful amido-denved bleach activators are those of the formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2c(O)L
wherein R1 is an alky! group containing from about 6 to about 12 carbon atoms, R^ is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about ! to about 10 carbor: atoms, wd L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the riucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenol sulfonate.
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzene-sul-fonate, (6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as described in the hereinbefore referenced U.S. Patent 4,634,551.
Another class of useful bleach activators comprises the benzoxazm-type activators disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October 30, 1990, incorporated herein by reference. See also U.S. Patent 4,545,784, Issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
If utilized, peroxygen bleaching agent will generally comprise from about 2% to 30% by weight of the detergent compositions herein. More preferably, peroxygen bleaching agent will comprise from about 2% to 20% by weight of the compositions. Most preferably, peroxygen bleaching agent will be present to the extent of from about 3% to 15% by weight of the compositions herein. If utilized, bleach activators can comprise from about 2% to 10% by weight of the detergent compositions herein. Frequently, activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1.
Additional suitable bleaching agents and bleach activators are disclosed in co-pending PCT Application WO98/14300, Published March 25, 1999, entitled Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith, which was filed on September 15, 1997, in the name of Panandiker et al. The entire disclosure of the Panandiker et al. reference was incorporated by reference above.
Another highly preferred optional ingredient in the detergent compositions herein is a detersive enzyme component. Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric
laundering, and for fabric restoration. Suitable enzymes include proteases, amylases, Hpases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability, optimal thermostabiliry, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry detergent composition. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases. Enzymes are normally incorporated into detergent compositions at levels sufficient to provide a "cleaning-effective amount". The term "cleaning-effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active levels may be desirable in highly concentrated detergent formulations.
Cellulases usable herein include those disclosed in U.S. Patent No. 4,435,307, Barbesgoard et al., March 6, 1984, and GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo.
The enzyme-containing compositions herein may optionally also comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
The compositions of the present invention may also include dye transfer inhibiting agents such as polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinyipyrroIidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. These agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%. and more preferably from about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-AX-P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
The N-O group can be represented by the following general structures:
(Formula Removed)
wherein Rj, R2, R3 are aliphatic, aromatic, beterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups. The atnine oxide unit of the polyamine N-oxides has a pKa Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyasmine oxides can be obtained in almost any degree of polymerization.
Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000.
The most preferred poryamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4. This preferred class of materials can be referred to as "PVNO".
Further suitable dye transfer inhibitors can be found in U. S. Pat. No. 5,466,802, issued Nov. 14,1995 to Panandiker et al., which is hereby incorporated by reference. F) Detergent Composition Preparation
The detergent compositions according to the present invention can be in liquid, paste or granular form. Such compositions can be prepared by combining the essential and optional components in the requisite concentrations in any suitable order and by any conventional means. The forgoing description of uses for the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers defined herein are intended to be exemplary and other uses will be apparent to those skilled in the art and are intended to be within the scope of the present invention.
Granular compositions, for example, are generally made by combining base granule ingredients, e.g., surfactants, builders, water, etc., as a slurry, and spray drying the resulting slurry to a low level of residual moisture (5-12%). The remaining dry ingredients, e.g., granules of the essential mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers, can be admixed in granular powder form with the spray dried granules in a rotary mixing drum. The liquid ingredients, e.g., solutions of the essential mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers, enzymes, binders and perfumes, can be sprayed onto the resulting granules to form the finished detergent composition. Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/1. In such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt.
Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations. Liquid compositions according to the present invention can also be in
"compact form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. Addition of the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers to liquid detergent or other aqueous compositions of this invention may be accomplished by simply mixing into the liquid solutions the desired mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers.
The methods and compositions heretofore disclosed may also be applied towards the production of particles that may be used as one of the component detergent granules in a granular detergent composition.
G) Fabnc Laundenng Method
The present invention also provides a method for laundering fabrics in a manner which imparts fabnc appearance benefits provided by the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers used herein. Such a method employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore described or formed from the individual components of such compositions. Contacting of fabrics with washing solution will generally occur under conditions of agitation although the compositions of the present invention may also be used to form aqueous unagitated soaking solutions for fabnc cleaning and treatment.
Agitation is preferably provided in a washing machine for good cleaning. Washing is preferably followed by drying the wet fabnc in a conventional clothes dryer. An effective amount of a high density liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.
H) Fabric Conditioning and Softening
The mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers hereinbefore described as components of the laundry detergent compositions herein may also be used to treat and condition fabrics and textiles in the absence of the surfactant and builder components of the detergent composition embodiments of this invention. Thus, for example, a fabric conditioning composition compnsing only the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers themselves, or comprising an aqueous solution of the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers, may be added during the rinse cycle of a conventional home laundering operation in order to impart the desired fabric appearance and ;ntegrity benefits hereinbefore described.
Additional suitable fabric softening agents are disclosed in co-pending PCT Application WO98/14300, Published March 25, 1999, entitled Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith, which was filed on September 15, 1997, in the name of Panandiker et ai. The entire disclosure of the Panandiker et al. reference was incorporated by reference above
The compositions of the present invention comprise at least about 1%, preferably from about 10%, more preferably from about 20% to about 80%, more preferably to about 60% by weight, of the composition of one or more fabric softener actives.
EXAMPLES
The following examples illustrate the compositions and methods of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention.
EXAMPLE 1
Synthesis of the adduct of imidazole and epichlorohydin (Ratio of imidazole:epichlorohydrin 1:1):
The polycationic condensate is prepared by reacting imidazole and epichlorohydnn. To a round bottomed flask equipped with a magnatic stirrer, condenser and a thermometer are added imidazole (0.68 moles) and 95 mL water. The solution is heated to 50°C followed by dropwise addition of epichlorohydnn (0.68 moles). After all the epichlorohydnn is added, the temperature is raised to 80°C until all the alkylating agent is consumed. The condensate produced had molecular weight of about 12,500.
EXAMPLE 2
Synthesis of the adduct of imidazoie and epichlorohydin (Ratio of imidazole:epichlorohydrin 1.4:1)
To a round bottomed flask equipped wtth a magnatic stirrer, condenser and a thermometer are added imidazole (0.68 moles) and 95 mL water. The solution is heated to 50°C followed by dropwise addition of epichlorohydrin (0.50 moles). After all the epichlorohydnn is added, the temperature is raised to 80°C until all the alkylating agent is consumed. The condensate produced had molecular weight of about 2000.
EXAMPLE 3 Synthesis of the adduct of piperazine, morpholine and epichlorohydin (Ratio 1.8/0.8/2.0)
Into a round bottom flask equipped with stirrer, thermometer, dropping funnel and reflux condenser 154.8 g (1.8 mole) of piperazine and 69.6 g (0.8 mole) of morpholine and 220 ml of water are added. After a clear solution at 40°C is obtained, the solution is heated to 55-65°C and with vigorous stirring 185 g (2 mole) of epichlorohydrin is added at such a rate, that the temperature does not exceed 80°C. After all the epichlorohydrin is added the reaction mixture is
heated to 85°C until all of the alkylating agents is consumed (negative Preussmann test after 4 hours). 108.8 g (0.68 mole) of 25% NaOH and 40 g of water are added and the reaction mixture is stirred for another hour at 85°C. Then an additional 47 g of water is added and the mixture is allowed to cool to room temperature.
EXAMPLE 4 Synthesis of the adduct of piperazine/morpholine/epi, in a ratio of 1.8/0.8/2.0
Into a round bottom flask equipped with stirrer, thermometer, dropping funnel and reflux condenser 154.8 g (1.8 mole) of piperazine and 69.6 g (0.8 mole) of morpholine and 220 ml of water are added. After a clear solution at 40°C is obtained, the solution is heated to 55-65°C and with vigorous stirring 185 g (2 mole) of epichlorohydnn is added at such a rate, that the temperature does not exceed 80°C. After all the epichlorohydrin is added the reaction mixture is heated to 85°C until all of the alkylating agents has been consumed (negative Preussmann test after 4 hours). 108.8 g (0.68 mole) of 25% NaOH and 40 g of water is added and the reaction mixture is stirred for another hour at 85°C. Then an additional 47 g of water are added and the mixture is allowed to cool to room temperature.
EXAMPLE 5 Adduct of piperazine/morpholine/epi from Example 4,100% oxidized
233.6 g (equivalent to 1,292 mole oxidizable nitrogen atoms) of the material from Example 4 above is mixed with 22.1 g (0.276) of 50% NaOH and then heated to 55-65°C. At that temperature 102.4 g (1,421 mole) of H2O2 (47.2%) is added dropwise over a period of 3.5 hours. After the addition is complete, the reaction mixture is held at the same temperature for 3 more hours and is then stirred at room temperature overnight. Pt/C was added, unreacted H2O2 destroyed and the solution then filtered.
The reaction product is characterized as follows:
water content 58%
pH 5.6
chloride content 1.593 mmole/g
EXAMPLE 6
Synthesis of the adduct of imidazoSe/piperazisne/epi, is a ratio 1.0/3.0/4.0
68.8g (1.0 mole) of limidazole and 260.6 g (3.0 mole) of piperazine are dissolved in 700.2 g of water and at a temperature of 50-60°C, 370 g (4.0 mole) of epichlorhydnn is added dropwise. After the addition is complete, the reaction mixture is stirred for additional 5 hours at 80°C.
EXAMPLE 7 Adduct of imidazole/piperazine/epi from Example 6, 100% oxidized
To 237 g of the product from Example 6 above (equivalent to 1,022 mole of oxidizable nitrogen atoms) 80.7 g (1.12 mole) of a 47.2% solution of H2O2 in water is added over a period of 5 hours at 40°C. After that, the mixture is heated to 50-60°C until the theoretical amount of H2O2 has been consumed. Unreacted H2O2 is destroyed by using Pt/C and the solution is then filtered.
The reaction product is characterized as follows:
(Formula Removed)
EXAMPLE 8 Synthesis of hydrophobically modified CMC Materials
The carboxylation of cellulose to produce CMC is a procedure that is well known to those skilled in the art. One method of producing the modified CMC materials of this invention, is to add during the CMC making process the material, or materials, to be substituted. An example of such as procedure is given below. This same procedure can be utilized with the other substituent materials described herein by replacing the hexylchloride with the substituent material, or materials, of interest, for example, cetylchloride. The amount of material that should be added to the CMC making process to achieve the desired degree of substitution will be easily calculated by those skilled in the art in light of the following Examples.
EXAMPLE 9
This example illustrates the preparation of a hydrophobically modified carboxymethyl cellulose and is representative of preparation of all of the cellulose ether derivatives of this invention.
Cellulose (20 g), sodium hydroxide (10 g), water (30 g), and ethanol (150 g) are charged into a 500 ml glass reactor. The resulting alkali cellulose is stirred 45 minutes at 25°C Then monochloroacetlc acid (15 g) and hexylchonde (1 g) are added and the temperature raised over time to 95°C and held at 95°C for 150 minutes. The reaction is cooled to 70°C, and then cooled to 25°C. Neutralization is accomplished by the addition of a sufficient amount of nitric acid/acetic acid to achieve a slurry pH of between 8 and 9. The slurry is filtered to obtain a hexyletherof CMC.
EXAMPLE 10 Cellulosic Polymers Used in Test Detergent Compositions
Representative modified cellulosic polymers for use in the liquid and granular detergent compositions described below are characterized in Tables 10 A and 10 B. The General Polymer Parameters are common to all of the polymers, while the specific chemical structure of the materials tested are listed under the Specific Polymer Parameters.

(Table Removed)
Table 10 B Table Specific Polymer Parameters
(Table Removed)
CMC = Carboxymethylcellulose
* Manufactured by Metsa Specialty Chemicals
** Manufactured by Akzo
***DSRn for these materials was in the range of from about 0.001 to about 0.1
EXAMPLE 11 The following are idealized chemical structures for certain cyclic amine based polymers,
oligomers or copolymers of this invention. Side reactions expected to occur during the condensation are not shown.
Table 11
(Table Removed)
EXAMPLE 12 Granular Detergent Test Composition Preparation
Several heavy duty granular detergent compositions are prepared containing a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers These granular detergent compositions all have the following basic formula:
Table 12
(Table Removed)
EXAMPLE 13 Liquid Detergent Test Composition Preparation
Several heavy duty liquid detergent compositions are prepared a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers. These liquid detergent compositions all have the following basic
formula:
Table 13
(Table Removed)

EXAMPLE 14 Granular Detergent Test Composition Preparation
Several granular detergent compositions are prepared containing a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophoblcally modified cellulosic based polymers or oligomers. Such granular detergent compositions all have the following basic formula:
Table 14

(Table Removed)
EXAMPLE 15
A detergent agglomerate which may be used as a paniculate component in a detergent composition is prepared according to the following formulas and ranges. The granule may be manufactured by agglomeration methods known to those skilled in the art; some of which are described in the present application.

(Table Removed)
1: Dispersant is Na Polyacrylate 4500, Polyethylene Glycol or a mixture of both.




1. A detergent composition chaiacterized by:
a) from 1% to 80% by weight of surfactants selected from the group consisting of
nonionic, amonic, cationic, amphotenc zwitteriomc surfactants and mixtures thereof; and c) ai ieast 0.0%, preferably at least 0.1%, most preferably at lesst 0.5% and no more than 50%, preferably no more than 25.0%, most preferably no more than 5.0%, by weight, of a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers.
2. The detergent composition of claim 1, wherein the hydrophobically modified cellulosic based polymers or oligomers are of the general formula:
(Formula Removed)
wherein each R is selected from the group consisting of R2, RO and
(Formula Removed)
wherein:
each RT is independently selected from the group consisting of H and Cj-C4 alkyl;
eachRcis
wherein each Z is independently selected from the group consisting of M, R2, RC.a nd RH; each RH is independently selected from the group consisting of C5-C20 alkyl,C5-C7
cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, C1-C20
alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2-hydroxyalkyl, (R4)2N-alkyl, hydroxyalkyl, (R4)3 N-alkyl, (R4)3 N-2-hydroxyalkyl, C6-C12 aryloxy-2-hydroxyalkyl,
(Formula Removed)
each R4 is independently selected from the group consisting of H, C7-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, ammoalkyl, alkylammoalkyl, dialkyiaminoalkyl, piperidmoalkyl, morpholinoalkyl, cycloalkylammoalkyl and hydroxyalkyl;
cycloalkyl, C7-C20 alkylaryl,C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (R4)2N-alkyl, and (R4 each R5 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7
)3 N-alkyl;
wherein:
M is a suitable cation selected from the group consisting of Na, K, l/2Ca, and l/2Mg;
each x is from 0 to 5;
each y is from 1 to 5; and provided that:
the Degree of Substitution for group RH is between 0.0005 and 0. 1, more preferably between
0.005 and 0.05, and most preferably between 0.01 and 0.05; the Degree of Substitution for group RC wherein Z is H or M is between 0.2 and 2.0, more
preferably between 0.3 and 1.0, and most preferably between 0.4 and 0.7; if any RH bears a positive charge, it is balanced by a suitable anion; and
two R4's on the same nitrogen can together form a ring structure selected from the group
consisting of piperidine and morpholine.
3. The detergent composition of any of claims 1-2, wherein the cyclic amine based
polymers', oligomers or copolymers are of the general formula:
(Formula Removed)
wherem;
each T is independently selected from the group consisting of H, C1-C12 alkyl, substituted alkyl,
C7-C12 alkylaryl,
-(CH2)hCOOM, -(CH2)hSO3M, CH2CH(OH)SO3M, -(CH2)hOSO3M,
(Formula Removed)
-wherein W is characterized by at least one cyclic constituent selected from the group consisting (Formula Removed)
in addition to the at least one cyclic constituent, W may also comprise an aliphatic or substituted aliphatic moiety of the general structure;
(Formula Removed)
-each B is independently C1-C12 alkylene,C1-C12 substituted alkylene, C3-C12 alkenylene, Cg-
C12 dialkylarylene, C8-C12 dialkylarylenediyl, and -each D is independently C2-C6 alkylene;
-each Q is independently selected from the group consisting of hydroxy, C1-C18 alkoxy, C2-C18 hydroxyalkoxy, ammo, C1-C18 alkylamino, dialkylamino, trialkylammo groups,
heterocyclic monoamino groups and diamino groups; -each RI is independently selected from the group consisting of H, C1-C8 allcyl and C1-C8
hydroxyalkyl;
-each R2 is independently selected from the group consisting of C1-C12 alkylene, C1-C12 alkenylene, -CH2-CH(OR1)-CH2, C8-C2 alkarylene, C4-C12dihydroxyalkylene, poly(C2-C4 alkyleneoxy)alkylene, H2CH(OH)CH2OR2OCH2CH(OH)CH2-. and C3-C12 hydrocarbyl moieties;
provided that when R2 is a C3-C12 hydrocarbyl moiety the hydrocarbyl moiety can comprise from about 2 to about 4 branching moieties of the general structure:
(Formula Removed)
-each R3 is independently selected from the group consisting of H, O, R2, C1-C20 hydroxyalkyl, C1-C20 alkyl. substituted alkyl, C8-C11 aryl, substituted aryl, C7-C11 alkylaryl,
ammoaikyl,
-(CH2)hCOOM, -(CH2)hSO3M, CH2CH(OH)SO3M, -(CH2)hOSO3M,
(Formula Removed)
-each R4 is independently selected from the group consisting of H, C7-C22 alkyl, C
(Formula Removed)
hydroxyalkyl, aryl and C7-C22alkylaryl; -each R5 is independently selected from the group consisting of C2-C8 alkylene, C2-C8 alkyl
substituted alkylene; and
A is a compatible monovalent or di or polyvalent anion;
M is a compatible cation;
b = number necessary to balance the charge;
each x is independently from 3 to 1000;
each c is independently 0 or 1;
each h is independently from I to 8;
each q is independently from 0 to 6; each n is independently from 1 to 20; each r is independently from 0 to 20; and each t is independently from 0 to 1.
4. The detergent composition of any of claims 1-3, wherein each Rj is H and at least one W
is selected from the group consisting of:
5. The detergent composition of any of claims 1-4, wherein each Rj is H and at least one W
is selected from the group consisting of:
(Formula Removed)
6. The detergent composition of any of claims 1-5, wherein each Rj is H and at least one W
is selected from the group consisting of:
7. The detergent composition of any of claims 1-6, wherein each RH is independently
selected from the group consisting of C5-C20 alkyl. C5-Cy cycloalkyl, C7-C20 alkylaryl, C7 C20 arylalkyl, substituted alkyl, hydroxyalkyl, C\-C2Q alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2-hydroxyalkyl, (R4)2N-alkyl. (R4)2N-2-hydroxyalkyl, (R4)3N-alkyl, (R4)3 N-2-hydroxyalkyl, and C6-C12 aryloxy-2-hydroxyaIkyl.
8. A laundry additive composition characterized by:
a) from 1% to 80% by weight of water; and
b) from 0.01% to 5.0%, preferably from 0.1% to 4.0%. by weight of a mixture of
cyclic amine based polymers, oligomers or copolymers and hydrophobically modified
cellulosic based polymers or oligomers.

9. The detergent composition of any of claims 1-8. wherein the composition further is
characterized by an inorganic peroxygen bleaching compound, which is preferably selected from
the group consisting of alkali metal salts of perborate, percarbonate and mixtures thereof, and a
bleach activator, which is preferably nonanoyloxybenzene sulfonate.
10. The detergent composition of any of claims 1-9, wherein the composition further is
characterized by a cellulase enzyme.
11. A detergent composition, substantially as hereinbefore
described with reference to the foregoing exampj.es.
12. A laundry additive composition, substantially as
re described wita reference t, the foregoing examples.

Documents:

IN-PCT-2001-00254-DEL-Correspondence Others-(21-06-2011).pdf

IN-PCT-2001-00254-DEL-Form-27-(21-06-2011).pdf

IN-PCT-2001-00254-DEL-Petition-137-(21-06-2011).pdf

inpct-2001-del-254-abstract.pdf

inpct-2001-del-254-assinment.pdf

inpct-2001-del-254-claims.pdf

inpct-2001-del-254-correspondence-others.pdf

inpct-2001-del-254-correspondence-po.pdf

inpct-2001-del-254-description (complete).pdf

inpct-2001-del-254-form-1.pdf

inpct-2001-del-254-form-19.pdf

inpct-2001-del-254-form-2.pdf

inpct-2001-del-254-form-26.pdf

inpct-2001-del-254-form-3.pdf

inpct-2001-del-254-form-5.pdf

inpct-2001-del-254-gpa.pdf

inpct-2001-del-254-pct-210.pdf

inpct-2001-del-254-pct-409.pdf

inpct-2001-del-254-pct-416.pdf

inpct-2001-del-254-petition-137.pdf

inpct-2001-del-254-petition-138.pdf


Patent Number 214686
Indian Patent Application Number IN/PCT/2001/00254/DEL
PG Journal Number 09/2008
Publication Date 29-Feb-2008
Grant Date 14-Feb-2008
Date of Filing 29-Mar-2001
Name of Patentee THE PROCTOR & GAMBLE COMPANY
Applicant Address ONE PROCTOR & GAMBLE PLAZA, CINCINNATI, STATE OF OHIO, USA
Inventors:
# Inventor's Name Inventor's Address
1 PANANDIKER, RAJAN KESHAV 6484 OREGON PASS, WEST CHESTER, OHIO, 45069,U.S.A.
2 LEUPIN, JENNIFER ANN 7974 FAWNCREEEK DRIVE, CINCINNATI, OHIO, 45249, U.S.A.
3 WERTZ, WILLIAM CONRAD 1273 MORGAN ROAD WEST HARRISON, IN 47060, USA
PCT International Classification Number G06F 17/30
PCT International Application Number PCT/US99/23116
PCT International Filing date 1999-10-06
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/103978 1998-10-13 U.S.A.
2 60/148053 1999-08-10 U.S.A.