WO2000022078A1 - Compositions detergentes pour lessives comportant une combinaison d'oligomeres a base d'amines cycliques et de carboxy methyl cellulose a hydrophobie modifiee - Google Patents

Compositions detergentes pour lessives comportant une combinaison d'oligomeres a base d'amines cycliques et de carboxy methyl cellulose a hydrophobie modifiee Download PDF

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Publication number
WO2000022078A1
WO2000022078A1 PCT/US1999/023146 US9923146W WO0022078A1 WO 2000022078 A1 WO2000022078 A1 WO 2000022078A1 US 9923146 W US9923146 W US 9923146W WO 0022078 A1 WO0022078 A1 WO 0022078A1
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Prior art keywords
group
alkyl
hydroxyalkyl
oligomers
based polymers
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PCT/US1999/023146
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English (en)
Inventor
Rajan Keshav Panandiker
Jennifer Ann Leupin
William Conrad Wertz
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to US09/806,882 priority Critical patent/US6835707B1/en
Priority to CA002346293A priority patent/CA2346293C/fr
Priority to AU11017/00A priority patent/AU1101700A/en
Priority to DE69923855T priority patent/DE69923855T2/de
Priority to AT99954739T priority patent/ATE289627T1/de
Priority to EP99954739A priority patent/EP1121408B1/fr
Priority to JP2000575972A priority patent/JP2002527576A/ja
Priority to BRPI9914520-0A priority patent/BR9914520B1/pt
Publication of WO2000022078A1 publication Critical patent/WO2000022078A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • 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
    • C11D3/3915—Sulfur-containing compounds
    • 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
    • C11D3/40—Dyes ; Pigments

Definitions

  • the present invention relates to compositions, m either liquid or granular form, for use in laundry applications, wherein the compositions comp ⁇ se certain cyclic amine based polymer, ohgomer or copolymer materials m combination with hydrophobically modified carboxy methyl cellulose This combination imparts appearance and integrity benefits to fab ⁇ cs and textiles laundered in washing solutions formed from such compositions.
  • fab ⁇ c integrity and appearance can manifest itself in several ways. Short fibers are dislodged from woven and knit fab ⁇ c/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 fab ⁇ c. Further, repeated launde ⁇ ng of fab ⁇ cs 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 m many cases, as a result of changes in hues or shades of color.
  • the present invention is directed to a detergent composition
  • a detergent composition comprising: a) from about 1% to about 80% by weight of surfactants selected from the group consisting of noniomc, amonic, catiomc, amphote ⁇ c 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, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers.
  • the cyclic am e based polymer, oligomer or copolymer mate ⁇ als which are suitable for use in laundry operations and provide the desired fab ⁇ c appearance and mteg ⁇ ty benefits can be characterized by the following general formula:
  • each T is independently selected from the group consisting of H, C ⁇ -Cj2 alkyl, substituted alkyl, C7-C12 alkylaryl, -(CH 2 )hCOOM, -(CH 2 )hS0 3 M, CH 2 CH(OH)SO 3 M, -(CH 2 )hOSO 3 M,
  • W may also comprise an aliphatic or substituted aliphatic moiety of the general structure
  • each B is independently C ⁇ -C ⁇ 2 alkylene, C ⁇ -C j2 substituted alkylene, C3-C1 2 alkenylene, Cg- C j 2 dialkylarylene, Cg-C ⁇ 2 dialkylarylenediyl, and -(R5O) n R5- ;
  • each D is independently C -Cg alkylene
  • each Q is independently selected from the group consisting of hydroxy, g alkoxy, C 2 -C ⁇ g hydroxyalkoxy, ammo, Cj-Ci g alkylamino, dialkylamino, t ⁇ alkylamino groups, heterocyc c monoamino groups and diammo groups;
  • each R j is independently selected from the group consisting of H, Cj-Cg alkyl and Ci -Cg hydroxyalkyl;
  • each R 2 is independently selected from the group consisting of C1 -Ci 2 alkylene, Cj-C j 2 alkenylene, -CH -CH(OR ⁇ )-CH 2 , Cg-C ⁇ alkarylene, C4-Cj 2 dihydroxyalkylene, poly(C 2 -C alkyleneoxy)alkylene, H 2 CH(OH)CH 2 OR 2 OCH 2 CH(OH)CH 2 -, and C 3 - C 12 hydrocarbyl moieties; provided that when R 2 is a C 3 -C ⁇ 2 hydrocarbyl moiety the hydrocarbyl moiety can comprise from about 2 to about 4 branching moieties of the general structure:
  • R 3 is independently selected from the group consisting of H, O, R2, C 1-C20 hydroxyalkyl, C1-C20 alkyl, substituted alkyl, Cg-Cj ⁇ aryl, substituted aryl, C7-C1 ⁇ alkylaryl, C1-C20 ammoalkyl, -(CH 2 )hCOOM, -(CH 2 )hS0 3 M, CH 2 CH(OH)SO 3 M, -(CH 2 ) OSO 3 M,
  • each R4 is independently selected from the group consisting of H, C 1-C22 alkyl, Ci -C22 hydroxyalkyl, aryl and C -C22 alkylaryl;
  • -each R5 is independently selected from the group consisting of C2-C alkylene, C2-Cg alkyl substituted alkylene;
  • 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
  • each t is independently from 0 to 1.
  • Cellulosic based polymer or oligomer materials which are suitable for use laundry operations and provide the desired fabric appearance and mteg ⁇ ty benefits can be characte ⁇ zed by the following general formula:
  • each R is selected from the group consisting of R2, Re, and
  • each R 2 is independently selected from the group consisting of H and C 1-C4 alkyl
  • each Rcs -( CH 2) -C-OZ wherein each Z is independently selected from the group consisting of M, R , Re, and R H ; each R H is independently selected from the group consisting of C5 -C 2 o alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, C1 -C20 alkoxy-2 -hydroxyalkyl, C7-C 2 Q alkylaryloxy-2-hydroxyalkyl, (R4)2N-alkyl, (R4)2N-2- hydroxyalkyl, (R4) 3 N-alkyl, ( 4) 3 N-2 -hydroxyalkyl, aryloxy-2 -hydroxyalkyl,
  • each R4 is independently selected from the group consisting of H, C 1-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C 2 Q arylalkyl, aminoalkyl, alkylammoalkyl, dialkylaminoalkyl, pipe ⁇ dinoalkyl, morphohnoalkyl, cycloalkylaminoalkyl and hydroxyalkyl;
  • each R5 is independently selected from the group consisting of H, C ⁇ -C Q alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (R4) 2 N-alkyl, and (R ⁇ 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 R H 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 Re 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 R H bears a positive charge, it is balanced by a suitable amon; and two R4's on the same nitrogen can together form a ring structure selected from the group consisting of pipe ⁇ dme and morphohne.
  • the cyclic amme based polymer, oligomer or copolymer matenals defined above can be used, along with the hydrophobically modified cellulosic based polymers or oligomers, as a washing solution additive m either granular or liquid form. Alternatively, they can be admixed to granular detergents, dissolved in liquid detergent compositions or added to a fab ⁇ c softening composition.
  • the ratio of the hydrophobically modified cellulosic to cyclic amme based polymer, oligomer or copolymer mate ⁇ als 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 amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers based fab ⁇ c treatment mate ⁇ als of the present invention.
  • the detersive surfactant and detergency builder mate ⁇ als 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 comp ⁇ se from about 0.01% to 80% by weight of the mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers fabric treatment mate ⁇ als dissolved in water and other ingredients such as stabilizers and pH adjusters.
  • the present invention relates to the launde ⁇ ng or treating of fab ⁇ cs and textiles in aqueous washing or treating solutions formed from effective amounts of the detergent compositions described herein, or formed from the individual components of such compositions Launde ⁇ ng of fab ⁇ cs and textiles m such washing solutions, followed by raising and drying, imparts fabric appearance benefits to the fab ⁇ c and textile articles so treated Such benefits can include improved overall appearance, pill/fuzz reduction, antifading, improved abrasion resistance, and/or enhanced softness It has been surprisingly determined that the a mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers according to this invention imparts fab ⁇ c appearance and integrity benefits that are greater than the benefits achieved by a corresponding amount of either component by itself
  • compositions of the present invention comp ⁇ ses one or more cyclic amine based polymer, oligomer or copolymer
  • mate ⁇ als 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 fab ⁇ c treatment mate ⁇ als.
  • Such fab ⁇ c appearance benefits can include, for example, improved overall appearance of the laundered fab ⁇ cs, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc.
  • the cyclic amme based fab ⁇ c treatment mate ⁇ als used in the compositions and methods herein can provide such fab ⁇ c appearance benefits with acceptably little or no loss m cleaning performance provided by the laundry detergent compositions into which such mate ⁇ als are incorporated.
  • the cyclic amine based polymer, oligomer or copolymer component of the compositions herein may comprise combinations of these cyclic amme based matenals.
  • a mixture of piperadine and epihalohyd ⁇ n condensates can be combined with a mixture of morphohne and epihalohyd ⁇ n condensates to achieve the desired fabric treatment results.
  • the molecular weight of cyclic amine based fabric treatment matenals can vary within the mixture as is illustrated m the Examples below.
  • an oligomer is a molecule consisting of only a few monomer units while polymers compnse considerably more monomer units.
  • 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 polyme ⁇ zed Copolymers of the present invention can include, for example, polymers or oligomers polyme ⁇ zed from a mixture of a p ⁇ mary cyclic amine based monomer, e.g., piperadine, and a secondary cyclic amine monomer, e.g., morphohne.
  • 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 comp ⁇ se 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 comp ⁇ se from about 0.1% to about 4% by weight of the detergent compositions, most preferably from about 0.75% to about 3%
  • a washing solution additive i.e.
  • the concentration of mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers can compnse from about 0.1% to about 80% by weight of the additive matenal Cyclic amme based polymer, oligomer or copolymer mate ⁇ als which are suitable for use in laundry operations and provide the desired fabnc appearance and integrity benefits can be charactenzed by the general formula given in the Summary of the Invention.
  • Preferred compounds that fall within this general structure include compounds:
  • each R j is H
  • -at least one W is selected from the group consisting of:
  • -at least one W is selected from the group consisting of:
  • -at least one W is selected from the group consisting of:
  • Preferred compounds to be used as the linking group R 2 include, but are not limited to: polyepoxides, ethylenecarbonate, propylenecarbonate, urea, ⁇ , ⁇ -unsaturated carboxylic acids, esters of ⁇ , ⁇ -unsaturated carboxylic acids, amides of ⁇ , ⁇ -unsaturated carboxylic acids, anhydrides of ⁇ , ⁇ -unsaturated carboxylic acids, di- or polycarboxylic acids, esters of di- or polycarboxy c acids, amides of di- or polycarboxylic acids, anhydndes of di- or polycarboxylic acids, glycidylhalogens, chloroformic esters, chloroacetic esters, denvatives of chloroformic esters, derivatives of chloroacetic esters, epihalohydnns, glycerol dichlorohyd ⁇ ns, bis- (halohyd ⁇ ns), polyetherd
  • cyclic amme based polymer, oligomer or copolymer materials for use herein include adducts of two or more compositions selected from the group consisting of piperazme, piperadine, epichlorohyd ⁇ n, epichlorohydnn benzyl quat, epichlorohyd ⁇ n methyl quat, morphohne and mixtures thereof.
  • cyclic amine based polymers can be linear or branched.
  • One specific type of branching can be intorduced using a polyfunctional crosslinkmg agent.
  • An example of such such polymer is exemplified below
  • the essential component of the compositions of the present invention compnses one or more cellulosic based polymer or oligomer.
  • Such matenals 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 fab ⁇ c treatment matenals.
  • Such fab ⁇ c 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 matenals used in the compositions and methods herein can provide such fab ⁇ c appearance benefits with acceptably little or no loss in cleaning performance provided by the laundry detergent compositions into which such mate ⁇ als are incorporated.
  • an oligomer is a molecule consisting of only a few monomer units while polymers comp ⁇ se considerably more monomer units.
  • 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 fabnc treatment mate ⁇ al 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 fabnc treatment component of the detergent compositions herein will generally compnse from about 0.1% to about 5% by the weight of the detergent composition. More preferably, such cellulosic based fabnc treatment mate ⁇ als will compnse from about 0.5% to about 4% by weight of the detergent compositions, most preferably from about 0.75% to about 3%
  • concentration of the cellulosic based component can comp ⁇ se from about 0.1% to about 80% by weight of the additive material.
  • each R is selected from the group consisting of R2, Re, and
  • each R2 is independently selected from the group consisting of H and C1 -C4 alkyl
  • each R H IS independently selected from the group consisting of C5 -C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, C ⁇ -C 2 o alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2 -hydroxyalkyl, (R4)2N-alkyl, (R4>2N-2- hydroxyalkyl, (R4) 3 N-alkyl, (R4) 3 N-2-hydroxyalkyl, Cg-C ⁇ aryloxy-2 -hydroxyalkyl,
  • each R4 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, ammoalkyl, alkylammoalkyl, dialkylammoalkyl, p ⁇ e ⁇ dinoalkyl, mo holmoalkyl, cycloalkylammoalkyl and hydroxyalkyl; each R5 is independently selected from the group consisting of H, C ⁇ -C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (R 4 ) 2 N-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 R H 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 Re 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 R H bears a positive charge, it is balanced by a suitable anion; and two R4's on the same nitrogen can together form a nng structure selected from the group consisting of pipendme and morphohne.
  • the "Degree of Substitution” for group R H which is sometimes abbreviated herein “DS RH ", means the number of moles of group R H components that are substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six membered ⁇ ng as shown in the repeating unit of the general structure above.
  • the "Degree of Substitution" for group Re which is sometimes abbreviated herein “DS R c”, means the number of moles of group Re components, wherein Z is H or M, that are substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six membered nng 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 Re components wherein Z is H or M, there can be, and most preferably are, additional Re components wherein Z is a group other than H or M.
  • the detergent compositions herein compnse from about 1% to 80% by weight of a detersive surfactant. Preferably such compositions compnse from about 5% to 50% by weight of surfactant.
  • Detersive surfactants utilized can be of the anionic, noniomc, zwittenomc, ampholytic or catiomc type or can comp ⁇ se compatible mixtures of these types.
  • Detergent surfactants useful herein are described U.S. Patent 3,664,961, Noms, issued 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, a onics and nomonics are preferred.
  • Useful anionic surfactants can themselves be of several different types.
  • water-soluble salts of the higher fatty acids i.e., "soaps”
  • 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.
  • non-soap anionic surfactants which are suitable for use herein include the water- soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfu ⁇ c reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfunc acid ester group.
  • 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 1 1 to 13 , abbreviated as C ⁇ ⁇ . ⁇ 3 LAS.
  • Preferred noniomc surfactants are those of the formula R. (OC2H4) n OH, wherein R. is a
  • Particularly preferred are condensation products of C 12-C15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., Ci2-C ⁇ alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
  • the detergent compositions herein may also compnse from about 0.1% to 80% by weight of a detergent builder.
  • a detergent builder Preferably such compositions in liquid form will compnse from about 1% to 10% by weight of the builder component.
  • granular form will comp ⁇ se from about 1% to 50% by weight of the builder component.
  • Detergent builders are well known in the art and can compnse, for example, phosphate salts as well as va ⁇ ous organic and inorganic nonphosphorus builders
  • Water-soluble, nonphosphorus organic builders useful herein include the vanous 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.
  • Particularly preferred polycarboxylate builders are the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuccmate and tartrate disuccinate descnbed in U.S. Patent 4,663,071, Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.
  • nonphosphorus, inorganic builders include the silicates, aluminosihcates, borates and carbonates. Particularly preferred are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of S1O2 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 aluminosihcates including zeolites. Such mate ⁇ als 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.
  • the detergent compositions of the present invention can also include any number of additional optional ingredients.
  • additional optional ingredients include conventional detergent composition components such as enzymes and enzyme stabilizing agents, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, bleaching agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelatmg agents, organic and inorganic fillers, solvents, hydrotropes, optical b ⁇ ghteners, dyes and perfumes.
  • a preferred optional ingredients for incorporation into the detergent compositions herein comprises a bleaching agent, e.g., a peroxygen bleach.
  • a bleaching agent e.g., a peroxygen bleach.
  • 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 percarboxy c 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- nonylammo-4-oxoperoxybuty ⁇ c 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.
  • Highly preferred bleaching agents also include 6-nonylam ⁇ no-6-oxoperoxycapro ⁇ c acid (NAPAA) as described m U.S. Patent 4,634,551, Issued January 6, 1987 to Burns et al.
  • NAPAA 6-nonylam ⁇ no-6-oxoperoxycapro ⁇ c acid
  • Inorganic peroxygen bleaching agents may also be used, generally in particulate form, the detergent compositions herein Inorganic bleaching agents are in fact preferred
  • Such inorganic peroxygen compounds include alkali metal perborate and percarbonate mate ⁇ als.
  • sodium perborate e g.
  • 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.
  • coated percarbonate particles are available from vanous commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.
  • Inorganic peroxygen bleaching agents e.g., the perborates, the percarbonates, etc.
  • 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-limit g 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
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamme
  • R 1 N(R 5 )C(O)R 2 C(0)L or R 1 C(0)N(R 5 )R 2 C(O)L wherein R* is an alkyl group containing from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R ⁇ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophihc attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenol sulfonate.
  • bleach activators of the above formulae include (6-octanam ⁇ do- caproyl)oxybenzenesulfonate, (6-nonanam ⁇ docaproyl) oxybenzene-sul-fonate, (6-decanam ⁇ do- caproyl)oxybenzenesulfonate and mixtures thereof as descnbed in the hereinbefore referenced U.S. Patent 4,634,551.
  • Another class of useful bleach activators compnses 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.
  • peroxygen bleaching agent will generally comprise from about 2% to 30% by weight of the detergent compositions herein. More preferably, peroxygen bleaching agent will comp ⁇ se 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.
  • 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
  • Panandiker et al. The entire disclosure of the Panandiker et al. reference was incorporated by reference above.
  • Another highly preferred optional ingredient m the detergent compositions herein is a detersive enzyme component.
  • Enzymes can be included in the present detergent compositions for a vanety of purposes, including removal of protem-based, carbohydrate-based, or t ⁇ glyce ⁇ de-based stains from substrates, for the prevention of refugee dye transfer in fab ⁇ c laundermg, and for fab ⁇ c restoration.
  • Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable o ⁇ gm, such as vegetable, animal, bacte ⁇ al, fungal and yeast ongm.
  • Preferred selections are influenced by factors such as pH- activity and/or stability, optimal thermostabihty, and stability to active detergents, builders and the like.
  • bacterial or fungal enzymes are preferred, such as bacte ⁇ al amylases and proteases, and fungal cellulases.
  • Detersive enzyme means any enzyme having a cleaning, stam 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 "clean g-effective amount" The term “cleaning-effective amount” refers to any amount capable of producing a cleaning, stam removal, soil removal, whitening, deodo ⁇ zmg, or freshness improving effect on substrates such as fabncs.
  • 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 m 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 m 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 comp ⁇ se from about
  • 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, comp ⁇ se calcium ion, bone 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.
  • compositions of the present invention may also include dye transfer inhibiting agents such as polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrroIidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof.
  • dye transfer inhibiting agents such as polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrroIidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof.
  • dye transfer inhibiting agents such as polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrroIidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof.
  • These agents typically comprise from about 0.01% to about
  • 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:
  • R 3 (R 3 )z wherein R j , R 2 , R3 are aliphatic, aromatic, heterocyclic 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 amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • 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.
  • 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 polyamine 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.
  • 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.
  • PVNO poly(4-vinylpyridine-N-oxide)
  • the detergent compositions according to the present invention can be 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 amme 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 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%).
  • base granule ingredients e.g., surfactants, builders, water, etc.
  • the remaining dry ingredients e.g., granules of the essential mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers, can be admixed in granular powder form with the spray dned granules in a rotary mixing drum.
  • 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
  • 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.
  • 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 chlondes, typically sodium sulphate; "compact" detergents typically comp ⁇ se 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 amme 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
  • 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
  • the present invention also provides a method for laundering fabncs m a manner which imparts fabnc appearance benefits provided by the mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers used herein
  • a method employs contacting these fabncs with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore descnbed or formed from the individual components of such compositions
  • Contacting of fabncs 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 fab ⁇ c cleaning and treatment
  • Agitation is preferably provided in a washing machine for good cleaning Washing is preferably followed by drying the wet fabric 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
  • a fabnc conditioning composition comp ⁇ sing only the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers themselves, or compnsmg 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 dunng the nnse cycle of a conventional home laundenng operation in order to impart the desired fabnc appearance and mtegnty benefits hereinbefore des
  • compositions of the present invention comp ⁇ se 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 fab ⁇ c softener actives.
  • the polycatio c condensate is prepared by reacting imidazole and epichlorohyd ⁇ n. 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 epichlorohyd ⁇ n (0.68 moles). After all the epichlorohyd ⁇ n is added, the temperature is raised to 80°C until all the alkylatmg agent is consumed. The condensate produced had molecular weight of about 12,500.
  • reaction mixture After all the epichlorohyd ⁇ n is added the reaction mixture is heated to 85°C until all of the alkylatmg 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 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 H202 (47.2%) is added dropwise over a penod 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 contentl .593 mmole/g
  • EXAMPLE 6 Synthesis of the adduct of imidazole/piperazine/epi, in a ratio 1.0/3.0/4.0 68.8g (1.0 mole) of midazole and 260.6 g (3.0 mole) of piperazme are dissolved m 700.2 g of water and at a temperature of 50-60°C, 370 g (4.0 mole) of epichlorhyd ⁇ n is added dropwise. After the addition is complete, the reaction mixture is stirred for additional 5 hours at 80°C.
  • the reaction product is characterized as follows: water content' 58.6% pH 2.86 chloride content: 3.694 mmole/g
  • 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 mate ⁇ als of this invention is to add dunng the CMC making process the material, or matenals, to be substituted.
  • An example of such as procedure is given below.
  • This same procedure can be utilized with the other substituent mate ⁇ als descnbed herein by replacing the hexylchlo ⁇ de with the substituent material, or mate ⁇ als, of interest, for example, cetylchlonde.
  • the amount of mate ⁇ al 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 11 The following are idealized chemical structures for certain cyclic amme based polymers, oligomers or copolymers of this invention. Side reactions expected to occur dunng the condensation are not shown.
  • 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:
  • granular detergent compositions are prepared containing a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers. Such granular detergent compositions all have the following basic formula:
  • a detergent agglomerate which may be used as a particulate 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.
  • Dispersant is Na Polyacrylate 4500, Polyethylene Glycol or a mixture of both.

Abstract

L'invention porte sur des compositions détergentes et traitantes pour tissus comportant entre environ 0,01 % et environ 5,0 %, en poids de polymères, oligomères ou copolymères à base d'amines cycliques, et des polymères et oligomères à base de cellulose à hydrophobie modifiée.
PCT/US1999/023146 1998-10-13 1999-10-06 Compositions detergentes pour lessives comportant une combinaison d'oligomeres a base d'amines cycliques et de carboxy methyl cellulose a hydrophobie modifiee WO2000022078A1 (fr)

Priority Applications (8)

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US09/806,882 US6835707B1 (en) 1998-10-13 1999-10-06 Laundry detergent compositions with a combination of cyclic amine based polymers and hydrophobically modified carboxy methyl cellulose
CA002346293A CA2346293C (fr) 1998-10-13 1999-10-06 Compositions detergentes pour lessives comportant une combinaison d'oligomeres a base d'amines cycliques et de carboxy methyl cellulose a hydrophobie modifiee
AU11017/00A AU1101700A (en) 1998-10-13 1999-10-06 Laundry detergent compositions with a combination of cyclic amine based polymersand hydrophobically modified carboxy methyl cellulose
DE69923855T DE69923855T2 (de) 1998-10-13 1999-10-06 Waschmittelzusammensetzungen enthaltend eine kombination von auf cyklischem amin basierenden copolymeren und hydrophob modifizierten cellulosen
AT99954739T ATE289627T1 (de) 1998-10-13 1999-10-06 Waschmittelzusammensetzungen enthaltend eine kombination von auf cyklischem amin basierenden copolymeren und hydrophob modifizierten cellulosen
EP99954739A EP1121408B1 (fr) 1998-10-13 1999-10-06 Compositions detergentes pour lessives comportant une combinaison d'oligomeres a base d'amines cycliques et de cellulose a hydrophobie modifiee
JP2000575972A JP2002527576A (ja) 1998-10-13 1999-10-06 環状アミンをベースとするポリマーと疎水変性したカルボキシメチルセルロースとの組み合わせをもつ洗濯洗剤組成物
BRPI9914520-0A BR9914520B1 (pt) 1998-10-13 1999-10-06 composiÇÕes detergentes de lavagem de roupa com uma combinaÇço de polÍmeros baseados em aminas cÍclicas e carboxi metil celulose hidrofobicamente modificada e composiÇço aditiva de lavagem de roupa.

Applications Claiming Priority (4)

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US10397898P 1998-10-13 1998-10-13
US60/103,978 1998-10-13
US14805399P 1999-08-10 1999-08-10
US60/148,053 1999-08-10

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WO2000047705A1 (fr) * 1999-02-10 2000-08-17 The Procter & Gamble Company Compositions de detergent a lessive avec un constituant preservant l'apparence des tissus
US6790822B1 (en) 1999-01-13 2004-09-14 The Proctor & Gamble Company Detergent compositions having an anionically modified cellulose polymer
US6803355B1 (en) 1999-02-10 2004-10-12 The Procter & Gamble Company Laundry detergent compositions with fabric enhancing component
US6833347B1 (en) 1997-12-23 2004-12-21 The Proctor & Gamble Company Laundry detergent compositions with cellulosic polymers to provide appearance and integrity benefits to fabrics laundered therewith
US6835707B1 (en) * 1998-10-13 2004-12-28 The Procter & Gamble Company Laundry detergent compositions with a combination of cyclic amine based polymers and hydrophobically modified carboxy methyl cellulose
WO2006130575A2 (fr) * 2005-05-31 2006-12-07 The Procter & Gamble Company Compositions detergentes renfermant un polymere et leur utilisation
WO2006130442A1 (fr) * 2005-05-31 2006-12-07 The Procter & Gamble Company Composition detergente

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CN106478948B (zh) * 2010-02-24 2019-05-07 瑞立普萨公司 用作胆汁酸螯合剂的聚咪唑
EP2689001B1 (fr) * 2011-05-20 2017-09-27 Dow Global Technologies LLC Procédé pour la promotion de la libération des saletés par les tissus
WO2019111937A1 (fr) * 2017-12-06 2019-06-13 花王株式会社 Composition détergente pour produit textile

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WO1999014295A1 (fr) * 1997-09-15 1999-03-25 The Procter & Gamble Company Compositions de detergent a lessive comportant des polymeres cellulosiques qui conferent un aspect et une integrite avantageux aux tissus laves a l'aide de celles-ci

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DE19643281A1 (de) * 1996-10-21 1998-04-23 Basf Ag Verwendung von polykationischen Kondensationsprodukten als farbfixierenden Zusatz zu Waschmitteln und Wäschenachbehandlungsmitteln
WO1999014295A1 (fr) * 1997-09-15 1999-03-25 The Procter & Gamble Company Compositions de detergent a lessive comportant des polymeres cellulosiques qui conferent un aspect et une integrite avantageux aux tissus laves a l'aide de celles-ci
WO1999014301A1 (fr) * 1997-09-15 1999-03-25 The Procter & Gamble Company Compositions de detergent a lessive et de traitement de tissus comportant des polymeres d'amines cycliques oxydes

Cited By (8)

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Publication number Priority date Publication date Assignee Title
US6833347B1 (en) 1997-12-23 2004-12-21 The Proctor & Gamble Company Laundry detergent compositions with cellulosic polymers to provide appearance and integrity benefits to fabrics laundered therewith
US6835707B1 (en) * 1998-10-13 2004-12-28 The Procter & Gamble Company Laundry detergent compositions with a combination of cyclic amine based polymers and hydrophobically modified carboxy methyl cellulose
US6790822B1 (en) 1999-01-13 2004-09-14 The Proctor & Gamble Company Detergent compositions having an anionically modified cellulose polymer
WO2000047705A1 (fr) * 1999-02-10 2000-08-17 The Procter & Gamble Company Compositions de detergent a lessive avec un constituant preservant l'apparence des tissus
US6803355B1 (en) 1999-02-10 2004-10-12 The Procter & Gamble Company Laundry detergent compositions with fabric enhancing component
WO2006130575A2 (fr) * 2005-05-31 2006-12-07 The Procter & Gamble Company Compositions detergentes renfermant un polymere et leur utilisation
WO2006130442A1 (fr) * 2005-05-31 2006-12-07 The Procter & Gamble Company Composition detergente
WO2006130575A3 (fr) * 2005-05-31 2007-06-21 Procter & Gamble Compositions detergentes renfermant un polymere et leur utilisation

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AU1101700A (en) 2000-05-01
DE69923855T2 (de) 2005-12-29
JP2002527576A (ja) 2002-08-27
ATE289627T1 (de) 2005-03-15
BR9914520B1 (pt) 2008-11-18
BR9914520A (pt) 2001-06-26
CA2346293C (fr) 2009-01-06
CN1330704A (zh) 2002-01-09
ES2238854T3 (es) 2005-09-01
DE69923855D1 (de) 2005-03-31
CA2346293A1 (fr) 2000-04-20

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