WO1997022651A1 - Tensioactifs non ioniques et vecteurs obtenus a partir d'ethers glycidiliques gras - Google Patents

Tensioactifs non ioniques et vecteurs obtenus a partir d'ethers glycidiliques gras Download PDF

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Publication number
WO1997022651A1
WO1997022651A1 PCT/US1996/020776 US9620776W WO9722651A1 WO 1997022651 A1 WO1997022651 A1 WO 1997022651A1 US 9620776 W US9620776 W US 9620776W WO 9722651 A1 WO9722651 A1 WO 9722651A1
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alkyl
reaction product
formula
alkenyl
moiety
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PCT/US1996/020776
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English (en)
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Eugene Paul Gosselink
Mark Hsiang-Kuen Mao
Alan Edward Sherry
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The Procter & Gamble Company
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Publication of WO1997022651A1 publication Critical patent/WO1997022651A1/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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers

Definitions

  • the present invention relates to nonionic surfactants and carriers synthesized from monoalkyl ethers of polyethylene glycol and fatty glycidyl ethers, monoalkyl ethers of polyethylene glycol and olefin epoxides or glycidyl ethers derived from monoalkyl ethers of polyethylene glycol with fatty alcohols or ethoxylated fatty alcohols.
  • the present invention further relates to laundry detergent and hard surface cleaning compositions comprising the non-ionic surfactants ofthe present invention.
  • surfactants for cleaning has been known since ancient times and continues to be an area of intense research interest.
  • the word surfactant is a contraction ofthe term surface-active agent that was coined in 1950 and has become universally accepted to describe organic substances with certain characteristic features in structure and properties.
  • Surfactants are divided into several categories based on their molecular structure, namely anionic, cationic, nonionic, zwitterionic and ampholytic. Until the modern era of synthetic organic chemistry, known surfactants were comprised almost entirely ofthe anionic variety.
  • Nonionic surfactants unlike anionic and cationic surfactants, carry no discreet charge when dissolved in aqueous media. They are compatible with ionic and amphoteric surfactants and are generally used in combination with one or more other surfactants. Nonionic surfactants have found wide utility in laundry detergents, household and industrial cleaning products, medical formulations and a wide variety of applications where they are used alone or as an adjunct to ionic surfactants. Their usage is unique in that they can be formulated into non-aqueous or low polarity solutions.
  • linear alkyl alcohols can serve as nonionic surfactants in an extremely limited sense
  • most modern nonionic surfactants are comprised of ethoxylated aliphatic alcohols, the degree of ethoxy lation determining much ofthe surface activity and solubility characteristics ofthe particular target molecule.
  • One problem facing chemists and formulators alike, is the ability to control the number of oxyethylene units, or degree of ethoxylation, in the final product. Normally the degree of ethoxylation is an average value and represents a range of ethoxylation.
  • a routine method for synthesizing nonionic surfactants that comprises ethoxylated linear alcohols involves treating the parent alcohol with ethylene oxide in the presence of a base catalyst.
  • Those skilled in the art have sought for many years to develop a method that produces nonionic surfactants with a narrow range of ethoxylation values.
  • Nonionic surfactants derived from ethoxylated linear alcohols typically contain a terminal hydroxyl group which is a key functionality in te ⁇ ns of their inherent physical properties.
  • nonionic surfactants comprising an internal secondary alcohol functionality are rare and the present methods for their preparation are tedious and severely limited in scope.
  • the present invention comprises a method for synthesizing nonionic surfactants comprising an interior secondary alcohol functionality in the form of a 2- hydroxypropoxy moiety while further comprising an ethoxylated segment, said ethoxylated segment may optionally have a wide or narrow statistical distribution of ethyleneoxy residues.
  • the present invention allows for the usage of polyethylene glycols that are of sufficient volatility that they may be pre-purified prior to use and therefore yield a nonionic surfactant having a degree of ethoxylation narrower than the range achievable by ethylene oxide elongation of fatty alcohols.
  • the hydroxyl group functionality of the propoxy spacer can be further functionalized by the formulator.
  • the nonionic surfactants ofthe present invention may additional!)' comprise a terminal hydroxyl moiety.
  • the high degree of synthetic options afforded by the process ofthe present invention allows for substitution ofthe linear alkyl alcohol moiety with other desirable functional chains such as branched alkyl alcohols (guerbet alcohols), cyclic aliphatic (e.g., cyclohexyl alcohols), and di-alkyl substituted aromatic alcohols.
  • branched alkyl alcohols guerbet alcohols
  • cyclic aliphatic e.g., cyclohexyl alcohols
  • di-alkyl substituted aromatic alcohols di-alkyl substituted aromatic alcohols.
  • the present invention relates to a novel class of nonionic sur actants comprising the 2-hydroxypropoxy moiety, the 2,5-substituted dioxane moiety and a process for preparing said nonionic surfactants.
  • the 2-hydroxypropyleneoxy moiety of the present invention has, as one embodiment, the general structure depicted below, which is used for the sole purpose of depicting the said 2- hydr oxy propyleneoxy moiety.
  • This 1 ,2-propyleneoxy [oxy(methyl-l,2-ethandiyl)j moiety does not comprise the free hydroxyl moiety ofthe 2-hydroxypropyleneoxy functional group.
  • process ofthe present invention can be modified by the formulator to produce nonionic surfactants that are 2,5-disubstituted dioxanes.
  • nonionic surfactants that are suitable for use in medical compositions as a carrier, surfactant, suspending agent, or adjunct ingredient.
  • R is C ] -C22 linear alkyl, C3-C2 2 branched alkyl, C 3 -C 22 linear alkenyl, C 22 branched alkenyl, C5-C2 2 cyclic alkyl, C 5 -C22 cyclic alkenyl, aryl or C ⁇ -C 22 alkyl substituted aromatic;
  • R 4 is C -C alkylene
  • R 5 is hydrogen or R
  • A has the formula:
  • R 6 is A, halogen, or hydroxyl; p is from 0 to 100; v is 0 or 1 ; w is 0 or 1 ; ; is from 0 to 100; y is from 0 to 2; z is from 0 to 3; w + z is at least 1.
  • the present invention also relates to processes for preparing the above described nonionic surfactants ofthe present invention.
  • the present invention further relates to nonionic surfactants of the formula:
  • R is C r C 22 linear alkyl, C 3 -C 22 branched alkyl, C 3 -C 2 2 linear alkenyl, C 3 - C 2 2 branched alkenyl, C 5 -C 2 2 cyclic alkyl, C 5 -C 2 2 cyclic alkenyl, aryl or C r C 2 2 alkyl substituted aromatic;
  • R 3 is hydrogen, C r C 2 2 alkyl or alkenyl;
  • R 4 is C 2 -C 4 alkylene;
  • p is from 0 to 100;
  • x is from 0 to 100.
  • the present invention further relates to novel nonionic solvents useful for carriers, as non-aqueous cleaning solvents, or as surfactant boosters.
  • the present invention further relates to cleaning compositions comprising at least 0.01% ofthe nonionic surfactants described herein.
  • the present invention comprises compounds that are the reaction products of glycidyl ethers and polyethylene glycols of olefin epoxides and polyethylene glycols in the presence of an acid or a base catalyst.
  • the present invention also comprises compounds that result from the reaction of alcohols, polyethylene glycols and epihalohydrins in the presence of either a base or in the presence of an acid and a base catalyst in separate steps.
  • the nonionic surfactants ofthe present invention have me formula:
  • R units are linear alkylene moieties comprising from 1 to about 22 carbon atoms, branched alkylene moieties comprising from 3 to about 22 carbon atoms, linear alkenylene moieties comprising from 3 to about 22 carbon atoms, branched alkenylene moieties comprising from 3 to about 22 carbon atoms, cyclic alkylene moieties comprising from 5 to about 22 carbon atoms with at least 3 carbon atoms comprising the alkylene ring.
  • R units are also comprised of one or more aromatic rings.
  • the aromatic rings can be fused or bonded in series or can be linked by an alkyl chain or the aromatic rings may be alkyl substituted as in the case of 1 ,4- phenylene moieties provide that the total number of carbon atoms in the rings and pendant chains does not exceed 22 carbon atoms in number.
  • An example of a fused aromatic ring is naphthalene. This adduct can be suitably attached to an alkyl chain or can be bonded directly to the oxygen atom of the ROH alcohol. Bonding of the aromatic and substituted aromatic rings can be at any ring position.
  • R can also be one or more aromatic rings connected in series, for example, two benzene rings bonded to one another by a covalent bond, for example, a bi-phenyl moiety ofthe formula:
  • R is also any aromatic ring, whether fused or joined in series by covalent bonding that is substituted by one or more alkyl groups provided the total number of carbon atoms in the R moiety does not exceed 22.
  • R units comprise C r C 2 2 linear alkyl, C 3 -C 2 2 branched alkyl, C 3 -C 22 linear alkenyl, C 3 -C 2 2 branched alkenyl, C 5 -C 2 2 cyclic alkyl, C 5 -C 2 2 cyclic alkenyl, aryl or C1-C22 alkyl substituted aromatic moieties.
  • Preferred R units are linear alkyl, branched alkyl and alkyl substituted aromatic.
  • Preferred linear alkyl moieties comprise Cg-C2o "fatty" alkyl, more preferably the Cg-C j g "fatty" alkyl chains.
  • Preferred branched alkyl groups are the 2-alkyl substituted C 8 -C 22 "Guerbet" alkyl chains. Examples of Guerbet alkyl chains are 2-ethylhexyl, 2-propylheptyl, 2- butyloctyl and 2-pentylnonyl.
  • Preferred alkyl substituted aromatic groups comprise 4-alkylphenyl, and 1,4-dialkyl substituted phenyl compounds (1,4-phenylene). Examples include 4-octylphenyl, 4-nonylphenyl, 4-methylbenzyl, 4-ethylphenyl and 2-(4-methylphenyl)ethyl. More preferred is 4-nonylphenyl.
  • R 2 units are hydrogen, alkyl groups comprising 1-4 carbon atoms (such as methyl, ethyl, propyl, butyl) or moieties ofthe formula
  • R 4 is a C2-C 4 alkylene moiety such that the -(OR 4 )- unit comprises, for example, ethyleneoxy, propyleneoxy, butyleneoxy, 2-methylethyleneoxy units and mixtures thereof.
  • Preferred R 4 is ethylene.
  • an R 4 units comprises 2 moles of a C2-C4 alkylene oxides such as butylene oxide, this results in the R 4 unit having the general formula:
  • C2-C4 alkylene oxide moiety can be accomplished after the nonionic surfactant backbone is assembled as an optional replacement for the R 2 hydrogen atom.
  • the C 2 -C4 alkylene oxide moieties may also be intioduced into ihe molecule as a pre-formed adduct combined with the R moiety in the form of an R(OR 4 ) p OH alcohol reactant.
  • the nonionic surfactants ofthe present invention have the value of p from 0 to about 100, preferably from about 4 to about 24, more preferably from about 4 to about 12.
  • R 2 is hydrogen and when R 2 has the formula
  • R 5 unit is equal to R and the indices p and v are both equal to 0 and w is equal to 0 or 1.
  • p is preferably 2 to 100, more preferably 4 to 50, most preferably 4 to 12.
  • R 7 units have the formula:
  • R 6 is R, halogen, or hydroxyl.
  • R 6 is preferably halogen, most preferably chlorine.
  • a units are polyethylene glycols units having the formula:
  • R 3 is hydrogen, C j-C 4 alkylene or alkenylene, preferably R 3 units are methyl.
  • the R 4 units comprising A are the same as those described herein above.
  • the value of x is from 0 to 100, preferably from 2 to 20, most preferably from 4 to 12.
  • nonionic surfactants ofthe present invention having the general formula R(OR 4 )pO— CH 2
  • R2- OCHCH 2 - z there is a need for at least one of the R, R 2 or A moieties to have a hydrophobic character and in addition for at least one ofthe R, R 2 or A moieties lo have a hydrophilic character in order for the compounds of the present invention to exhibit surfactant behavior.
  • These hydrophilic and hydrophobic portions can be introduced in separate reaction steps, such as the capping of the R 2 hydroxy moiety, or they can be introduced as a pre-formed adducts as in the case of alkoxylated fatty alcohols, i.e. R(OR 4 )pOH alcohols, or the glycidyl ether of alkoxylated fatty alcohols.
  • the value of y is from 0 to 2, preferably 0.
  • the value of z is 0, 1 , 2 or 3, preferably 1 or 2, more preferably 1.
  • the present invention also relates to nonionic surfactants of Ihe following formula:
  • these 2,5-disubstituted dioxane units are formed when two equivalents of an epihalohydrin are condensed with one equivalent of an R(OR 4 ) p OH or R 3 O(R 4 O) x H unit to form an intermediate having the formula
  • the above intermediate can further react with one equivalent of an R(OR 4 ) p OH or R 3 O(R 4 O) x H moiety, in the presence of a base, to form a 2,5-disubstituted dioxane having the structure
  • R(OR 4 ) p OH and R 3 O(R O) x H are used, however the formulator may chose two equivalents ofthe same moiety, for example two moles of R(OR ) p OH.
  • the above example represents R 5 equal to R and the indices m, v, y, and z all having the value 0; w is equal to 1.
  • R, R 3 ,and R 4 units and the indices p and x are further described herein below.
  • the 2,5-disubstituted dioxane embodiment comprises R units are linear alkylene moieties comprising from 1 to about 22 carbon atoms, branched alkylene moieties comprising from 3 to about 22 carbon atoms, linear alkenylene moieties comprising from 3 to about 22 carbon atoms, branched alkenylene moieties comprising from 3 to about 22 carbon atoms, cyclic alkylene moieties comprising from 5 to about 22 carbon atoms with at least 3 carbon atoms comprising the alkylene ring.
  • R units are also comprised of one or more aromatic rings.
  • the aromatic rings can be fused or bonded in series or can be linked by an alkyl chain or the aromatic rings may be alkyl substituted as in the case of 1 ,4-phenylene moieties provide that the total number of carbon atoms in the rings and pendant chains does not exceed 22 carbon atoms in number.
  • An example of a fused aromatic ring is naphthalene, which can be suitably attached to an alkyl chain or can be bonded directly to the oxygen atom. Bonding ofthe aromatic and substituted aromatic rings can be at any ring position.
  • R is also one or more aromatic rings connected in series, for example, two benzene rings bond to one another by a covalent bond, for example, a bi-phenyl moiety ofthe formula:
  • R is also any aromatic ring, whether fused or joined in series by covalent bonding that is substituted by one or more alkyl groups provided the total number of carbon atoms in the R moiety does not exceed 22.
  • Preferred R units are linear alkyl, branched alkyl and alkyl substituted aromatic.
  • Preferred linear alkyl moieties comprise C6-C 2 o "fatty" alkyl, more preferably the "fatty" alkyl chains.
  • Preferred branched alkyl groups are the 2-alkyl substituted Cg-C 2 2 "guerbet" alkyl chains. Examples of guerbet alkyl chains are 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl and 2-pentylnonyl.
  • Preferred alkyl substituted aromatic groups comprise 4-alkylphenyl, and 1 ,4-dialkyl substituted phenyl compounds. Examples include 4-octylphenyl, 4-nonylphenyl, 4- methylbenzyl, 4-ethylphenyl and 2-(4-methylphenyl)ethyl.
  • R 3 is hydrogen or R, preferred R 3 is selected from the group consisting essentially of methyl, ethyl, propyl, butyl, and mixtures thereof.
  • R 4 is a C 2 -C 4 alkylene moiety such that the moiety -(OR 4 )- comprises, for example ethyleneoxy, propyleneoxy, butyleneoxy units and mixtures thereof; preferred R 4 is ethylene.
  • the value of p is from 0 to about 100, preferably from about 6 to about 24, more preferably from about 6 to about 12.
  • the compounds ofthe present invention may also be use as nonionic solvents useful as carriers, as non-aqueous cleaning solvents, or as surfactant boosters.
  • compounds ofthe present invention having p equal to 0 and x from 1 to about 4, wherein R is Ci -Cg linear or branched alkyl; R ⁇ is hydrogen, methyl, ethyl or mixtures thereof; and R ⁇ is methyl or ethyl, can be used in as carriers and co-solvents in a number of non-aqueous or low-aqueous cleaning applications.
  • non-aqueous or low-aqueous cleaning solvents according to the present invention has the formula and the formula
  • non-aqueous cleaning compositions is defined as cleaning compositions that comprise no water or only small amounts of water (generally less than 1-3%) that is used in processing.
  • low-aqueous cleaning compositions is defined as cleaning compositions wherein the amount of water present is less than 50% ofthe liquid carriers or solvents.
  • the cleaning compositions ofthe present invention comprise at least 0.01%, preferably 0.1% to 50%, more preferably 1% to about 10% by weight of detersive surfactant.
  • the cleaning compositions ofthe present invention comprise carriers and other adjunct materials.
  • the a partial list ofthe adjunct materials suitable for use in the practice ofthe present invention are further listed herein below.
  • the cleaning compositions ofthe present invention also optionally comprise carriers.
  • liquid carriers comprise water but other suitable carriers are such solvents as methanol, ethanol, n-propanol, isopropanol and the like which are commonly used in hard surface cleaning compositions.
  • the nonionic surfactants of the present invention can be used in conjunction with low aqueous carrier, that is, carriers that comprise less than 50% water. Additionally, the nonionic surfactants of the present invention can be used with other solvents and in non-aqueous modes of delivery.
  • a preferred non-classical solvent for use herein is butoxypropoxypropanol (BPP), methoxypropoxypropanol (MPP), ethoxypropoxypropanol (EPP), propoxy- propoxypropanol (PPP), butoxypropanol, tributoxypropanol and all isomers and mixtures thereof.
  • Additional solvents include C 4 -Cg polyethylene glycol derivatives, examples of which are hexylene glycol, hexylene diglyme and butylene diglycol.
  • BPP when used in conjunction with the nonionic surfactants ofthe present invention in cleaning compositions comprising 1,2- octanediol, the amount ofthe latter material can be minimized.
  • it allows for the formulation of effective cleaning compositions comprising the nonionic surfactants of the present invention without the use of water or conventional solvents.
  • Carriers are not limited to liquids and may comprise filler salts and perlite abrasives in the case of hard surface cleaners having general scouring application.
  • Inert ingredients such as silicon dioxide and pumice are also compatible with the nonionic surfactants ofthe present invention.
  • the use ofthe nonionic surfactants of the present invention in gels and lanolin based carrier systems is also an acceptable embodiment.
  • Preferred lotion and cream embodiments comprise, for example, white petrolatum, cetyl alcohol, stearyl alcohol, Sorbitan monooleate, Sorbitan monostearate, Macrogol 400, Macrogol 4000 and the like as further described in Surfactant Systems: Their chemistry, pharmacy and biology, Attwood, D.; and Florence, A.T.; Chapman and Hall (1983), inco ⁇ orated herein by reference in its entirety.
  • Fig. I is an example of a preferred embodiment ofthe present invention wherein R is a Cj2 linear alkyl group, R 2 is hydrogen, R 3 is methyl, x is 6, y is 0 and z is 1.
  • Fig. II represents an embodiment ofthe present invention wherein R is a C 10 guerbet alkyl group, R 2 is hydrogen, R 3 is methyl, x is 4, y is 1 and z is 1.
  • Fig. Ill represents an embodiment wherein R is an alkyl substituted phenyl group (i.e., (4-nonyl)phenyl) R 2 is methyl, R 3 is methyl, p is 0, x is 3, y is 0 and z is 1.
  • Fig IV represents an embodiment wherein R is linear alkyl (n-hexyl), R 2 is hydrogen, R 3 is methyl, x is 16, y is 0 and z is 2.
  • Fig. V represents an embodiment ofthe present invention wherein R is hexyl, R 3 is methyl, R 5 is R, p is equal to 0, x is equal to 3, v is equal to 0, w is equal to 1, y is equal to 0, and z is equal to 0.
  • the present invention comprises the methods for preparing the nonionic surfactants ofthe present invention.
  • base means any alkaline reagent suitable for the required de-protonation of a hydroxyl moiety.
  • suitable bases include, but is not limited to, sodium metal, potassium metal, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide and other like inorganic hydroxides.
  • Preferred bases are sodium metal, sodium hydride, more preferred is sodium metal.
  • KOH and NaOH are preferred bases because water can be removed by heat and/or vacuum.
  • the term "acid” means any acidic substance or reagent capable of catalyzing the required epoxide ring opening reactions or other like catalysts.
  • acids suitable for the processes to the present invention are hydrochloric acid, sulfuric acid methanesulfonic acid and Lewis acids.
  • Preferred are the Lewis acids, most preferred Lewis acids are boron trifluoride, gaseous or as a complex such as boron trifluoride etherate, stannic chloride and titanium tetrachloride.
  • the acids used in the neutralization steps of the processes ofthe present invention are not required to be the same acids that are used for the purpose of catalyzing the epoxide ring opening reactions.
  • the acids used for the neutralization step form inorganic salts that are acceptable for remaining in the product or are salts that are easily removed during the optional purification steps.
  • a preferred acid used for neutralization is methanesulfonic acid.
  • epichlorohydrin is used as an example of an epihalohydrin.
  • epibromohydrin or epiiodohydrin are both suitable for the processes ofthe present invention.
  • Preferred halohydrin is epichlorohydrin.
  • the processes disclosed in the present invention further provide the formulator with optional purification steps.
  • the formulator may seek purity of a varying degree.
  • a nonionic surfactant prepared for use as a medical adjunct may require a narrower range of ethoxylation or higher level of purity not necessary or desirable for other applications.
  • embodiments ofthe present invention that are intended for application in low aqueous or non-aqueous systems, and hence have a low tolerance for residual inorganic materials can be optionally neutralized by acids or bases that are suitable for removal by non-aqueous techniques.
  • the nonionic surfactants ofthe present invention can be prepared by several processes described herein.
  • the product ofthe reaction will afford nonionic surfactants of suitable purity such that the surfactants may be used without further purification. It has also been suprisingly found that minor reaction by-products when left in the product matrix, enhance the desired properties of certain nonionic surfactants when used in specific surfactant applications.
  • the formation of branched, bis-polyethylene glycol surfactants such as those depicted in figures II and III, constitutes a desirable product mixture of certain nonionic surfactants that result in increased cleaning performance in certain cleaning applications.
  • the nonionic surfactants of the present invention can be prepared using pre-formed glycidyl ethers. These pre ⁇ formed glycidyl ethers are available from various commercial sources (i.e. Aldrich Chemical Co.) or they can be easily prepared, isolated and purified by methods known to those skilled in the art. Polyethylene glycol monomethyl ethers (i.e., MPEG 350 and MPEG 550) are also available from commercial sources (Aldrich Chemical Co.) in high purity and known degree of ethoxylation. The reaction of glycidyl ethers and polyethylene glycols for the preparation of the nonionic surfactants ofthe present invention, is depicted in Scheme I:
  • x is from 0 to about 100; p is from 0 to 100; z is equal to 1; R 2 is hydrogen or C r C 4 alkyl; R 3 is C r C 4 alkyl or C r C 4 alkenyl; R 4 is C 2 -C 4 alkyl; comprising the steps of: a) reacting a glycidyl ether ofthe formula O
  • R is C1-C22 linear alkyl, C 3 -C 2 2 branched alkyl, C3-C22 linear alkenyl, C 4 -C 2 branched alkenyl, C5-C22 cyclic alkyl, aryl or C
  • a further example ofthe process ofthe present invention provides for the optional replacement of the hydrogen atom ofthe secondary hydroxyl group with an alkyl moiety as depicted in Scheme II.
  • the resulting 2-hydroxypropyloxy nonionic surfactant is further reacted to convert ihe R 2 hydrogen moiety to an alkyl moiety, said process comprises the steps of: a) reacting a glycidyl ether ofthe formula
  • step (b) optionally: i) neutralizing the crude alkaline nonionic surfactant reaction product formed in step (a) to form a crude nonionic surfactant reaction product; or ii) adding sufficient base to convert the R 2 functionality to an alkoxide; and c) optionally further reacting the reaction product of step (b) (ii) wherein R 2 is converted to a C ⁇ -C 4 alkyl moiety by reaction with a
  • alkylating agents suitable for converting the R 2 substituent from a hydrogen atom, as depicted in Fig. VI above, to a C C 4 alkyl moiety are those typically used by one skilled in the art.
  • methyl chloride, dimethyl sulfate, ethyl bromide, propyl iodide and butyl methanesulfonate are suitable for use in converting the R 2 group from a hydrogen atom to a C ] -C 4 alkyl group such as methyl, ethyl, propyl and butyl respectively.
  • R 2 has the formula
  • R 7 has the formula:
  • R 3 is C r C alkyl or C3-C 4 alkenyl; x is from 0 to 100; p is from 0 to 100, v is 0 or 1; w is 0 or 1 ; x is from 2 to about 100; y is 0, 1 or 2; z is from 0 to 3; w + z is greater than 1 ; comprising the steps of: a) reacting an alcohol ofthe formula R(OR 4 ) p OH wherein R is C ⁇ -C 22 linear alkyl, C 4 -C22 branched alkyl, C 5 -C 22 cyclic alkyl, C 5 -C22 cyclic alkenyl, aromatic, or Cj-C 22 alkyl substituted aromatic; with an epihalohydrin first in the presence of an acid catalyst, then in the presence of sufficient base to form a glycidyl ether of ihe formula
  • step (c) optionally further reacting the reaction product of step (c) wherein R 2 is hydrogen with sufficient base to convert the R 2 moiety to an alkoxide intermediate, followed by treatment with either: i) an alkylating agent whereby R 2 is converted to a C1-C 4 alkyl moiety; said alkyl moiety selected from the group consisting of methyl, ethyl, propyl, butyl, and mixtures thereof; or ii) a C2-C alkylene oxide whereby R 2 is converted to an C 2 -C 4 hydroxyalkyl moiety or polyoxyalkylene moiety; f) optionally purifying the reaction product formed in step (c); or g) optionally purifying the reaction product
  • nonionic surfactants that are suitably prepared by the process ofthe present invention are those comprising the 2,5-disubstituted dioxane ring system wherein treatment of the alcohol ROH with an excess of epihalohydrin and a Lewis acid catalyst is followed in a second chemical process step by treatment ofthe reaction solution with polyethylene glycol in the presence of a base catalyst.
  • Scheme IV depicts the formation of these 2,5-disubstituted dioxane polyethylene glycol nonionic surfactants as represented by figure VIII.
  • the process for preparing non linear nonionic surfactants ofthe present invention as depicted in Scheme IV comprises the steps of: comprising the steps of: a) reacting an alcohol ofthe formula ROH wherein R is C ⁇ -C 2 2 linear alkyl, C 4 -C 22 branched alkyl, C5-C22 cyclic alkyl, C5-C22 cyclic alkenyl, aromatic, or C1-C22 alkyl substituted aromatic; with
  • Nonionic surfactants ofthe present invention can be prepared using epihalohydrin, an alcohol ROH, and the monoalky I ether of polyethylene glycol.
  • R 2 has the formula
  • R 7 has the formula:
  • R 3 is C j -C 4 alkyl or C3-C alkenyl; x is from 0 to 100; p is from 0 to 100; v is 0 or 1; w is 0 or 1; x is from 2 to about 100; y is 0, 1 or 2; z is 1, 2 or 3; w + z is at least 1 ; comprising the steps of: a) reacting an alcohol ofthe formula:
  • R 3 (OCH 2 CH 2 ) x OH wherein R 3 and x are as defmed above; and an epihalohydrin in the presence of acid catalyst to form an acidic crude halohydrin reaction product ofthe formula
  • step (a) optionally purifying the crude halohydrin reaction product formed in step (a); c) reacting the halohydrin reaction product of step (a) or step (b) with at least one equivalent of base to form a glycidyl ether ofthe formula
  • R(OR ) p OH wherein R is C ⁇ -C 2 2 linear alkyl, C 3 -C 22 branched alkyl, C3-C2 2 linear alkenyl, C3-C22 branched alkenyl, C5-C22 cyclic alkyl, C5-C2 2 cyclic alkenyl, aryl or C1-C22 alkyl substituted aromatic; in the presence of sufficient base to form an alkaline crude nonionic surfactant reaction product; e) neutralizing the alkaline reaction product formed in step (d) to form a crude nonionic surfactant reaction product; f) optionally further reacting the reaction product of step (e) wherein R 2 is hydrogen with sufficient base to convert the R 2 moiety to an alkoxide then further reacting the crude product from step (e) with either: i) an alkylating agent whereby R 2 is converted to a C ] -C 4 alkyl moiety; said alkyl moiety selected from the group consisting of
  • Example II Example II
  • Polyethylene glycol monomethyl ether comprising 7.2 ethoxylate units per mole (MPEG-350) (55.1 gm, 0.126 mol) and sodium metal (0.29 gm, .013 gm-atm) is weighed into a 250 mL 3-neck round bottom flask equipped with a magnetic stirring bar, modified Claisen head, reflux condenser and thermometer, and is heated to 120° C under argon blanketing, for two hours or until the sodium is completely consumed.
  • Hexyl-glycidyl ether (20.0 gm, 0.126 mol) is added and the solution is stirred at 120° C for six hours. At this point the solution pH is approximately 12. The solution is then neutralized with methanesulfonic acid and centrifuged to remove the salts. Yield is approximately 61 gm.
  • Polyethylene glycol monomethyl ether comprising 7.2 ethoxylate units per mole (MPEG-350) (47.0 gm, 0.134 mol) and sodium metal (0.31 gm, 0.013 gm-atm) is weighed into a 250 mL 3-neck round bottom flask equipped with a magnetic stirring bar, modified Claisen head, reflux condenser and thermometer, and is heated to 120° C under argon blanketing, for two hours or until the sodium is completely consumed.
  • 2-ethyl-hexylglycidyl ether (25.0 gm, 0.134 mol) is added and the solution is stirred at 120° C for six hours. At this point the solution pH is approximately 12. The solution is then neutralized with methanesulfonic acid and centrifuged to remove the salts. Yield is approximately 63 gm.
  • Polyethylene glycol monomethyl ether comprising 4 ethoxylate units per mole (MPEG-208) (25.0 gm, 0.120 mol) and sodium metal (0.4 gm, 0.017 gm-atm) is weighed into a 250 mL 3-neck round bottom flask equipped with a magnetic stirring bar, modified Claisen head, reflux condenser and thermometer, and is heated to 120° C under argon blanketing, for two hours or until the sodium is completely consumed.
  • Hexyl-glycidyl ether (19.0 gm, 0.120 mol) is added and the solution is stirred at 120° C for six hours. At this point the solution pH is approximately 12.
  • the solution is then neutralized with methanesulfonic acid and centrifuged to remove the salts. Yield is approximately 34 gm.
  • Polyethylene glycol monomethyl ether comprising 11.8 ethoxylate units per mole (MPEG-550) (70.0 gm, 0.127 mol) and sodium metal (0.29 gm think 0.0126 gm- atm) is weighed into a 250 mL 3-neck round bottom flask equipped with a magnetic stirring bar, modified Claisen head, reflux condenser and thermometer, and is heated to 120° C under argon blanketing, for two hours or until the sodium is completely consumed.
  • Decyl-glycidyl ether (27.0 gm, 0.126 mol) is added and the solution is stirred at 120° C for six hours. At this point the solution pH is approximately 12. The solution is then neutralized with methanesulfonic acid and centrifuged to remove the salts. Yield is approximately 67 gm.
  • Polyethylene glycol monomethyl ether comprising 11.8 ethoxylate units per mole (MPEG-550) (70.0 gm, 0.127 mol) and sodium metal (0.29 gm, 0.0126 gm-atm) is weighed into a 250 mL 3-neck round bottom flask equipped with a magnetic stirring bar, modified Claisen head, reflux condenser and thermometer, and is heated to 120° C under argon blanketing, for two hours or until the sodium is completely consumed.
  • 2-butyloctyl-glycidyl ether (30.5 gm, 0.126 mol) is added and the solution is stirred at 120° C for six hours. At this point the solution pH is approximately 12. The solution is then neutralized with methanesulfonic acid and centrifuged to remove the salts. Yield is approximately 73 gm.
  • Polyethylene glycol monomethyl ether comprising 11.8 ethoxylate units per mole (MPEG-550) (70.0 gm, 0.127 mol) and sodium metal (0.29 gm, 0.0126 gm- atm) is weighed into a 250 mL 3-neck round bottom flask equipped with a magnetic stirring bar, modified Claisen head, reflux condenser and thermometer, and is heated to 120° C under argon blanketing, for two hours or until the sodium is completely consumed.
  • 2-ethyl-hexylglycidyl ether 47.4 gm, 0.268 mol
  • the solution pH is approximately 1 1.
  • the solution is then neutralized with methanesulfonic acid and centrifuged to remove the salts. Yield is approximately 83 gm.
  • the laundry detergents and hard surface cleaning compositions ofthe present invention may comprise one or more ofthe following ingredients.
  • Nonlimiting examples of surfactants include the conventional Cj i-Cjg alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C ⁇ o ⁇ 20 alkyl sulfates ("AS"), the CI Q-CI g secondary (2,3) alkyl sulfates ofthe formula CH3(CH2) x (CHOSO3 " M + ) CH 3 and CH3 (CH2) y (CHOS ⁇ 3 " M + ) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the Ci ⁇ -Cig a lkyl alkoxy sulfates ("AE x S"; especially EO 1-7 eth
  • the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C ⁇ 2-C 1 g betaines and sulfobetaines ("sultaines"), CjQ-Cig amine oxides, and the like, can also be included in the overall compositions.
  • the C ⁇ Q-CJ g N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the Cj2- ⁇ N- methylglucamides.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Cj ⁇ -Cig N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C j 2-C ⁇ g glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C ⁇ Q-C ⁇ soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • ADJUNCT INGREDIENTS Enzymes - Enzymes can be included in the present detergent compositions for a variety of pu ⁇ oses, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from surfaces such as textiles or dishes, for the prevention of refugee dye transfer, for example in laundering, and for fabric restoration.
  • Suitable enzymes include proteases, amylases, lipases, 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 optima, thermostability, 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 means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition.
  • Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases.
  • Preferred enzymes for laundry pu ⁇ oses include, but are not limited to, proteases, cellulases, lipases and peroxidases.
  • Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility.
  • Enzymes are normally inco ⁇ orated into detergent or detergenl additive compositions at levels sufficient to provide a "cleaning-effective amount".
  • 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, dishware and the like.
  • typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram ofthe detergent composition.
  • 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 also be desirable in highly concentrated detergent formulations.
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis.
  • One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo.
  • proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo.
  • proteases include those of WO 9510591 A to Procter & Gamble .
  • a protease having decreased adso ⁇ tion and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.
  • an especially preferred protease is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent applications of A.
  • Amylases suitable herein, especially for, but not limited to automatic dishwashing pu ⁇ oses include, for example, ⁇ -amylases described in GB 1,296,839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful.
  • Engineering of enzymes for improved stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol. 260, No. 1 1, June 1985, pp 6518-6521.
  • amylases herein share the characteristic of being "stability-enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide / tetraacetylethylenediamine in buffered solution at pH 9- 10; thermal stability, e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g., at a pH from about 8 to about 11, measured versus the above- identified reference-point amylase. Stability can be measured using any ofthe art- disclosed technical tests. See, for example, references disclosed in WO 9402597.
  • Stability-enhanced amylases can be obtained from Novo or from Genencor International.
  • One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Baccillus amylases, especialy the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors.
  • Oxidative stability-enhanced amylases vs. the above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein.
  • Such preferred amylases include (a) an amylase according to the hereinbefore inco ⁇ orated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, ofthe methionine residue located in position 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B.
  • subtilis or B.stearothermophilus
  • Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant.
  • oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enhanced amylase can be used, for example as derived by site- directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5.
  • U.S. 4,435,307, Barbesgoard et al, March 6, 1984 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM 1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
  • Suitable cellulases are also disclosed in GB-A- 2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • CAREZYME® Novo is especially useful. See also WO 9117243 to Novo.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms ofthe Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P.” Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB .
  • Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.
  • Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution.
  • oxygen sources e.g., percarbonate, perborate, hydrogen peroxide, etc.
  • Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo- peroxidase.
  • Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
  • a range of enzyme materials and means for their inco ⁇ oration into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26. 1985. Enzyme materials useful for liquid detergent formulations, and their inco ⁇ oration into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques.
  • Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
  • Enzyme Stabilizing System - Enzyme-containing including but not limited to, liquid compositions, herein may 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 ofthe detergent composition.
  • One stabilizing approach is the use of water-soluble sources of calcium and'or magnesium ions in the finished compositions which provide such ions to the enzymes.
  • Calcium ions are generally more effective than magnesium ions and are preferred herein if only one type of cation is being used.
  • Typical detergent compositions, especially liquids will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes inco ⁇ orated.
  • Preferably water-soluble calcium or magnesium salts axe employed including for example calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts corresponding to the exemplified calcium salts may be used. Further increased levels of Calcium and/or Magnesium may of course be useful, for example for promoting the grease-cutting action of certain types of surfactant.
  • Borate stabilizers when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use.
  • Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible though the use of such substituted boron derivatives.
  • Stabilizing systems of certain cleaning compositions may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions.
  • chlorine bleach scavengers While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme, for example during dish- or fabric-washing, can be relatively large; accordingly, enzyme stability to chlorine in- use is sometimes problematic.
  • Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used.
  • EDTA ethylenediaminetetracetic acid
  • MEA monoethanolamine
  • special enzyme inhibition systems can be inco ⁇ orated such that different enzymes have maximum compatibility.
  • scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired.
  • the chlorine scavenger function can be performed by ingredients separately listed under better recognized functions, (e.g., hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme-containing embodiment ofthe invention; even then, the scavenger is added only for optimum results.
  • the formulator will exercise a chemist's normal skill in avoiding the use of any enzyme scavenger or stabilizer which is majorly incompatible, as formulated, with other reactive ingredients, if used.
  • ammomum salts can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in US 4,652,392, Baginski et al.
  • the detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
  • bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, ofthe detergent composition, especially for fabric laundering.
  • the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% ofthe bleaching composition comprising the bleaching agent-plus-bleach activator.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning pu ⁇ oses that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • bleaching agent that can be used without restriction encompasses 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, U.S. Patent Application 740,446, Bums et al, filed June 3, 1985, European Patent Application 0,133,354, 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 as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium 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.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller them about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • Mixtures of bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) ofthe peroxy acid corresponding to the bleach activator.
  • bleach activators Various nonlimiting 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.
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • amido-derived bleach activators are those ofthe formulae: R 1 N(R 5 )C(O)R 2 C(O)L or R 1 C(O)N(R 5 )R2c(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 ofthe nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenyl sulfonate.
  • bleach activators ofthe above formulae include (6- octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesul- fonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, inco ⁇ orated herein by reference.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, inco ⁇ orated herein by reference.
  • a highly preferred activator ofthe benzoxazin- type is:
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams ofthe formulae: wherein R ⁇ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
  • lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, inco ⁇ orated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos.
  • Preferred examples of these catalysts include Mn ⁇ 2( u "C)3(l,4,7-trimethyl-l,4,7-triazacyclo- nonane)2(PF f j)2, Mn ⁇ 2 u "0) 1 ( u_ 0 Ac )2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2- (ClO4)2, Mn IV 4(u-O)6( 1 ,4,7-triazacyclononane)4(Cl ⁇ 4)4, Mn ⁇ Mn ] v (u-O) j (u- OAc)2_( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2(Cl ⁇ 4)3, Mn ⁇ ( 1 ,4 J-trimethyl- 1 ,4,7-triazacyclononane)- (OCH3)3(PFg
  • metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,61 1.
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
  • compositions and processes herein can be adjusted to provide on the order of at least one: part per ten million ofthe active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, ofthe catalyst species in the laundry liquor.
  • Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
  • the compositions will typically comprise at least about 1% builder.
  • Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder.
  • Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, ofthe detergent builder.
  • Lower or higher levels of builder are not meant to be excluded.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammomum and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta- phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • polyphosphates exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta- phosphates
  • phosphonates phosphonates
  • phytic acid e.g., silicates
  • carbonates including bicarbonates and sesquicarbonates
  • sulphates sulphates
  • aluminosilicates aluminosilicates.
  • non-phosphate builders are required in some locales.
  • compositions herein function su ⁇ risingly well even in the presence ofthe so-called "weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6: 1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na2Si ⁇ 5 mo ⁇ hology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x O2 x +i yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 , as the alpha, beta and gamma forms.
  • delta-Na2Si ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amo ⁇ hous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the pu ⁇ oses ofthe present invention include, but are not restricted to, a wide variety of poly carboxy late compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5- trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., C12-C1 g monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali menal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- 1 -hydroxy- 1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021 ; 3,400,148 and 3,422,137) can also be used.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, poly functionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo- triacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammomum salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions ofthe invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in trie compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene.
  • EDDS ethylenediamine disuccinate
  • [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • these chelating agents will generally comprise from about 0.1% to about 10% by weight ofthe detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
  • Clay Soil Removal/Anti-redeposition Agents The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight ofthe water-soluble ethoxylates amines; liquid detergent compositions typically contain about 0.01% to about 5%.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 1 1 1 ,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
  • CMC carboxy methyl cellulose
  • Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be inco ⁇ orated into the compositions ofthe present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines.
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • the detergent compositions herein may also contain non-surfactant suds suppressors.
  • non-surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovending alcohols, aliphatic Cj -C40 ketones (e.g., stearone), etc.
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 50°C, and a minimum boiling point not less than about 1 10°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of: (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25°C;
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene- polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
  • the primary silicone suds suppressor is branched/crossl inked and preferably not linear.
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorganosi
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.
  • Preferred is a weight ratio of between about 1 : 1 and 1 :10, most preferably between 1 :3 and 1 :6, of polyethylene glycokcopolymer of polyethylene-polypropylene glycol.
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC Ll 01.
  • suds suppressors useful herein comprise the branched alcohols (e.g., 2- alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
  • Secondary cilcohols include the C -Ci fj alkyl alcohols having a Cj-Ci g chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5: 1.
  • suds should not form to the extent that they overflow the washing machine.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • compositions herein will generally comprise from 0% to about 5% of suds suppressor.
  • monocarboxylic fatty acids, and salts therein will be present typically in amounts up to about 5%, by weight, of the detergent composition.
  • Silicone suds suppressors are typicaJly utilized in amounts up to about 2.0%, by weight, ofthe detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, ofthe composition.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.
  • the alcohol suds suppressors are typically used at 0.2%-3% by weight ofthe finished compositions.
  • Fabric Softeners Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning.
  • Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981.
  • Polymeric Soil Release Agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a suffi ⁇ cient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit ofthe soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxy
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3S(CH2) n OCH2CH2O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Cj-Cg vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., Cj-Cg vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300- 5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al. the anionic end- capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy- 1,2- propylene units.
  • the repeat units form the backbone ofthe oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)- ethanesulfonate.
  • Said soil release agent also comprises from about 0.5% to about 20%, by weight ofthe oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, ofthe detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight ofthe composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
  • 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 ⁇ , R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1 ; and the nitrogen ofthe N-O group can be attached or form part of any ofthe 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. 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 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. This preferred class of materials can be referred to as "PVNO".
  • the most preferred polyamine 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.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 1 13.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 :1 to 0.2: 1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinylpyrrolidone (“PVP”) having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, inco ⁇ orated herein by reference.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
  • the detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula:
  • R ⁇ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, 52 mo ⁇ hilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • Rj is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N -2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Co ⁇ oration. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R ⁇ is anilino
  • R2 is N-2-hydroxyethyl-N-2- methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino- 6-(N-2-hydroxye yl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Co ⁇ oration.
  • the brightener is 4,4 l -bis[(4-anilino-6-mo ⁇ hilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Co ⁇ oration.
  • the specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • the combination of such selected polymeric materials (e.g., PVNO and or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA- GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone.
  • exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • Brightener Any optical brighteners or other brightening or whitening agents known in the art can be inco ⁇ orated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5- dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD, available from Hilton-Davis, located in Italy; the 2-(4-sti7l-phenyl)-2H-nap ol[l,2-d]triazoles; 4,4 , -bis- (l,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins.
  • these brighteners include 4-methyl-7-diethyl- amino coumarin; l,2-bis(-venzimidazol-2- yl)ethylene; 1 ,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl- napth-[l,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [l,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein.
  • Abrasives An essential component of many hard surface cleaning compositions is the abrasive material added to facilitate the action of scouring.
  • Abrasive scouring cleansers provide a convenient and useful means for carrying out the sanitizing of bathroom surfaces, including toilet bowls and urinals.
  • the particulate abrasive material within such compositions serves to abrade and loosen soil adhering to hard surfaces and further serves to create more intimate contact between hard surface stain and the surfactant and/or bleaching agents also present in the cleansing compositions.
  • Abrasive cleaners have traditionally contained water-insoluble, relatively hard, particulate mineral material as the abrasive agent.
  • the most common such abrasive agent is finely divided silica sand having particle size varying between about 1 and 300 microns and specific gravity of about 2.1 or higher. While such material is generally very effective in scouring soil and stains from the surfaces being treated, abrasive material of this type tends to be difficult to rinse away from the toilet bowl or urinal surface.
  • abrasive compositions can be realized by utilizing a particular type of expanded perlite abrasive in combination with the surfactants, filler material, urease inhibitors and other optional scouring material ingredients listed herein.
  • the abrasive materials suitable to the present invention are those contained in U.S. Pat. No. 4,051,056, Hartman, issued September 27, 1977 and included herein by reference.
  • compositions herein may be in the form of granules, liquids, bars, and the like, and typically are formulated to provide an in-use pH in the range of 9 to 1 1.
  • Various carriers such as sodium sulfate, water, water-ethanol, sodium carbonate, and the like, may be used routinely to formulate the finished products.
  • Crranules may be produced by spray-drying or by agglomeration, using known techniques, to provide products in the density range of 350-950 g/l.
  • the compositions may also contain conventional perfumes, bactericides, hydrotropes and the like.
  • compositions according to this invention are as follows:
  • Lipase (Lipolase 165 KLU) 0.2 0.1 0.2
  • Nonionic surfactant ofthe present invention comprising one equivalent of Cio linear alcohol derived glycidyl ether and one equivalent of polyethylene glycol mono ⁇ methyl ether have an average ethoxylation of 11.8 as described in Example V.
  • Nonionic surfactant ofthe present invention comprising one equivalent of 2-ethyl- hexyl alcohol derived glycidyl ether and one equivalent of polyethylene glycol mono ⁇ methyl ether have an average ethoxylation of 7.2 as described in Example III.
  • a laundry bar suitable for hand-washing soiled fabrics is prepared by standard extrusion processes and comprises the following: Ingredient % (wt.)
  • Nonionic surfactant of the present invention comprising one equivalent of C j linear alcohol derived glycidyl ether and one equivalent of polyethylene glycol mono-methyl ether have an average ethoxylation of 1 1.8 as described in Example V.
  • a liquid laundry detergent with improved grease/oil si at 70°F (21°C) is as follows.
  • Nonionic surfactant ofthe present invention comprising one equivalent of 2- butyloctyl alcohol derived glycidyl ether and one equivalent of polyethylene glycol mono-methyl ether have an average ethoxylation of 11.8 as described in Example VI.
  • composition is designed for use at 0.39 cup (92.4 mL) in a conventional U.S. top-loading automatic washing machine, or its equivalent.
  • a liquid laundry detergent composition suitable for use at the relatively high concentrations common to front-loading automatic washing machines, especially in Europe, and over a wide range of temperatures is as follows. Ingredient Weight %
  • Oleoyl sarcosinate Na 10.0
  • Nonionic surfactant of the present invention comprising one equivalent of C ] Q linear alcohol derived glycidyl ether and one equivalent of polyethylene glycol mono-methyl ether have an average ethoxylation of 11.8 as described in Example V.
  • Preferred fatty acid is topped palm kernel, comprising 12% oleic acid and 2% each of stearic and linoleic.
  • Amylase from NOVO; percentage at 300 KNU/g.
  • Silane corrosion inhibitor available as Al 130 from Union Carbide or DYNASYLAN TRIAMINO from HOls.
  • nonionic surfactants ofthe present invention can also be used to advantage in hard surface cleaning compositions.
  • such compositions may also comprise the various adjunct ingredients, preferred surfactants, and the in the case of toilet bowl and urinal cleaners various urease inhibitors.
  • such compositions may also comprise various ingredients whose physical properties are especially useful for specific end-uses.
  • EXAMPLE XIII Component Formula No. (Weight %) Isopropanol 6.0 5.4 2.0 Butoxypropanol 3.0 — 3.0 Monoethanolamine 0.50 0.40 0.50 Cocoamidopropylhydroxy sultaine 0.16 — 0.075 Sodium lauryl sulfate 0.02 — — C10PE11.8OCH3 I 0.60 0.90 — 2-butyl-CgPE 1 gOCH 3 2 — 1.0 — Linear alkylbenzenesulfonate — 0.07 — C9 alkylphenolethoxylate — 0.03 — C 6 EO 4 OCH 3 3 — — 0.075 Sodium acetate — — 0.05 Ammonia — 0.10 —
  • Nonionic surfactant of the present invention comprising one equivalent of C j Q linear alcohol derived glycidyl ether and one equivalent of polyethylene glycol mono-methyl ether have an average ethoxylation of 11.8 as described in Example V.
  • Nonionic surfactant ofthe present invention comprising one equivalent of 2- butyloctyl alcohol derived glycidyl ether and one equivalent of polyethylene glycol mono-methyl ether have an average ethoxylation of 11.8 as described in Example VI.
  • Nonionic surfactant of the present invention comprising one equivalent of hexyl alcohol derived glycidyl ether and one equivalent of polyethylene glycol mono ⁇ methyl ether have an average ethoxylation of 4 as described in Example IV.
  • SURFACE WETTING TEST Determination ofthe wetting ability of hard surface cleaners is important due to the short contact time these compounds have with the surfaces to be cleaned.
  • the cleaning composition is applied to the surface needing to be cleaned and then quickly wiped, scoured or scrubbed.
  • Wetting ability on hard surfaces can be measured by comparing a solution containing a surfactant versus distilled water. One drop of each solution is placed onto a hard surface material and the wetting ability is then related to how large a "diameter of spreading" the test solution produces compared to the distilled water control. Comparisons are also made at various surfactant concentrations to find the optimal wetting concentration. Superior wetting is indicated when the diameter ofthe solution drop is greater than 300% that of the pure liquid. The following tests were performed on black glossy porcelain tiles (Villeroy & Boch, Germany) at 24°C using 20% surfactant solutions in distilled water. Wetting diameter were measured 10 minutes after placement of solution drops on tile.
  • Surfactant MPEG glycidyl Solution
  • Surfactant ether ratio appearance solution water diameter ratio
  • the following embodiments ofthe surfactants ofthe present invention were evaluated for their filming and streaking properties using the grading standards listed below. Lack of filming/ streaking on surfaces due to dilute solutions of surfactant represents another desirable property of good hard surface cleaning agents.
  • the solutions described in the table below were diluted 1 :128 with 7 gpg water to simulate actual usage conditions. The dilute solutions were applied in equal concentration to black, clean polyurethane tiles (Mannington checkmate-black 2151) and allowed to dry for 2 hours. Three expert panelists were then asked to grade the filming/ streaking residues left on by the dried surfactant solutions. Comparisons were made versus a high performance benchmark control product (i.e., a product which displays good shine end result properties).. Su ⁇ risingly, the prototypes using surfactants of this invention displayed even better filming/ streaking profiles. TABLE II

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Abstract

L'invention concerne des tensioactifs non ioniques destinés à être utilisés dans des compositions de nettoyage ainsi que des vecteurs destinés à être utilisés dans des compositions de nettoyage non aqueuses et faiblement aqueuses, obtenus à partir d'éthers glycidiliques. Les processus catalysés par acide et par base décrits dans l'invention permettent de disposer d'un éventail élargi de différentes fractions alkyle et aryle ainsi que polyalkylène, pour insertion dans les tensioactifs non ioniques.
PCT/US1996/020776 1995-12-21 1996-12-13 Tensioactifs non ioniques et vecteurs obtenus a partir d'ethers glycidiliques gras WO1997022651A1 (fr)

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WO1999006466A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Compositions renfermant des tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
WO1999006467A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
WO1999006468A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Procede utile pour preparer des tensioactifs a base d'alcool poly(alcoxyle) a coiffe d'ether
WO2000027903A1 (fr) * 1998-11-05 2000-05-18 The Procter & Gamble Company Preparation de tensioactifs a base d'alcools poly(oxyalkyles) a protections ether
WO2000027516A1 (fr) * 1998-11-05 2000-05-18 The Procter & Gamble Company Preparation de tensioactifs a base d'alcools poly(oxyalkyles) a protections ether
WO2000042152A1 (fr) * 1999-01-14 2000-07-20 The Procter & Gamble Company Compositions detergentes comprenant une pectate lyase et un tensioactif non ionique peu moussant
WO2000050549A2 (fr) * 1999-02-22 2000-08-31 The Procter & Gamble Company Compositions nettoyantes contenant des tensioactifs non ioniques selectionnes
WO2004031111A1 (fr) * 2002-10-01 2004-04-15 Basf Aktiengesellschaft Produits issus de la reaction de 2-propylheptanol, de 1-halogene-2,3-epoxypropanes et de 1-hydroxy-2,3-epoxypropane
JP2007063175A (ja) * 2005-08-31 2007-03-15 Nagoya City オリゴエチレンオキシド誘導体及びオリゴエチレンオキシド誘導体の製造方法
US8871699B2 (en) 2012-09-13 2014-10-28 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US9023784B2 (en) 2012-09-13 2015-05-05 Ecolab Usa Inc. Method of reducing soil redeposition on a hard surface using phosphinosuccinic acid adducts
WO2017024110A1 (fr) 2015-08-04 2017-02-09 Isp Investments Llc Polymères dérivés d'éthers d'alcool vinylique à fonction amino et leurs applications
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
WO2017172394A1 (fr) * 2016-03-31 2017-10-05 Rohm And Haas Company Tensioactifs destinés à la prévention des taches dans les compositions de lave-vaisselle automatique
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
CN114276537A (zh) * 2020-09-28 2022-04-05 南开大学 一种环境友好含氟非离子表面活性剂及其制备方法和应用
US11865219B2 (en) 2013-04-15 2024-01-09 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing
EP4253358A4 (fr) * 2020-11-30 2024-06-05 Kao Corporation Composé, composé précurseur de celui-ci, composition de tensioactif et composition de détergent

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DE3144371A1 (de) * 1980-11-13 1982-06-09 Basf Ag, 6700 Ludwigshafen Schaumarme und biologisch abbaubare mit glycerinetherresten endgruppenverschlossene alkoxylierungsprodukte, ein verfahren zu ihrer herstellung und ihre verwendung als tenside in wasch- und reinigungsmitteln
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Cited By (35)

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Publication number Priority date Publication date Assignee Title
WO1999006466A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Compositions renfermant des tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
WO1999006467A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
WO1999006468A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Procede utile pour preparer des tensioactifs a base d'alcool poly(alcoxyle) a coiffe d'ether
US6365785B1 (en) * 1997-08-02 2002-04-02 Therprocter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
US6482994B2 (en) * 1997-08-02 2002-11-19 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
WO2000027903A1 (fr) * 1998-11-05 2000-05-18 The Procter & Gamble Company Preparation de tensioactifs a base d'alcools poly(oxyalkyles) a protections ether
WO2000027516A1 (fr) * 1998-11-05 2000-05-18 The Procter & Gamble Company Preparation de tensioactifs a base d'alcools poly(oxyalkyles) a protections ether
US6495727B1 (en) 1998-11-05 2002-12-17 The Procter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
US6576799B1 (en) 1998-11-05 2003-06-10 The Procter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
WO2000042152A1 (fr) * 1999-01-14 2000-07-20 The Procter & Gamble Company Compositions detergentes comprenant une pectate lyase et un tensioactif non ionique peu moussant
WO2000050549A2 (fr) * 1999-02-22 2000-08-31 The Procter & Gamble Company Compositions nettoyantes contenant des tensioactifs non ioniques selectionnes
WO2000050549A3 (fr) * 1999-02-22 2000-11-02 Procter & Gamble Compositions nettoyantes contenant des tensioactifs non ioniques selectionnes
JP4768264B2 (ja) * 2002-10-01 2011-09-07 ビーエーエスエフ ソシエタス・ヨーロピア ２−プロピルヘプタノールと１−ハロ−２，３−エポキシプロパン及び１−ヒドロキシ−２，３−エポキシプロパンとの反応生成物
JP2006501288A (ja) * 2002-10-01 2006-01-12 ビーエーエスエフ アクチェンゲゼルシャフト ２−プロピルヘプタノールと１−ハロ−２，３−エポキシプロパン及び１−ヒドロキシ−２，３−エポキシプロパンとの反応生成物
US7666903B2 (en) 2002-10-01 2010-02-23 Basf Aktiengesellschaft Reaction products of 2-propylheptanol with 1-halogen-2,3-epoxypropanes and 1-hydroxy-2,3-epoxypropane
WO2004031111A1 (fr) * 2002-10-01 2004-04-15 Basf Aktiengesellschaft Produits issus de la reaction de 2-propylheptanol, de 1-halogene-2,3-epoxypropanes et de 1-hydroxy-2,3-epoxypropane
JP2007063175A (ja) * 2005-08-31 2007-03-15 Nagoya City オリゴエチレンオキシド誘導体及びオリゴエチレンオキシド誘導体の製造方法
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US11859155B2 (en) 2012-09-13 2024-01-02 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US9670434B2 (en) 2012-09-13 2017-06-06 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US9023784B2 (en) 2012-09-13 2015-05-05 Ecolab Usa Inc. Method of reducing soil redeposition on a hard surface using phosphinosuccinic acid adducts
US8871699B2 (en) 2012-09-13 2014-10-28 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US11952556B2 (en) 2012-09-13 2024-04-09 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US10358622B2 (en) 2012-09-13 2019-07-23 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US10377971B2 (en) 2012-09-13 2019-08-13 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US11001784B2 (en) 2012-09-13 2021-05-11 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US11053458B2 (en) 2012-09-13 2021-07-06 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US11865219B2 (en) 2013-04-15 2024-01-09 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing
WO2017024110A1 (fr) 2015-08-04 2017-02-09 Isp Investments Llc Polymères dérivés d'éthers d'alcool vinylique à fonction amino et leurs applications
WO2017172394A1 (fr) * 2016-03-31 2017-10-05 Rohm And Haas Company Tensioactifs destinés à la prévention des taches dans les compositions de lave-vaisselle automatique
US10479959B2 (en) 2016-03-31 2019-11-19 Dow Global Technologies Llc Surfactants for spot prevention in automatic dishwashing compositions
CN108934167A (zh) * 2016-03-31 2018-12-04 罗门哈斯公司 自动餐具洗涤组合物中用于防斑点的表面活性剂
CN114276537A (zh) * 2020-09-28 2022-04-05 南开大学 一种环境友好含氟非离子表面活性剂及其制备方法和应用
EP4253358A4 (fr) * 2020-11-30 2024-06-05 Kao Corporation Composé, composé précurseur de celui-ci, composition de tensioactif et composition de détergent

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