Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/43—Solvents
• • 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
• • 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
• • 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
  • C11D1/825—Mixtures of compounds all of which are non-ionic

Definitions

• This invention relates to liquid detergent compositions for cleaning hard surfaces.
• Such compositions comprise one or more non-ionic surfactants selected from highly ethoxylated Guerbet alcohols.
• the Guerbet ethoxylates are chosen so as to contain no more than about 5% free Guerbet alcohol.
• the hard surface cleaning compositions of this invention provide improved dilute cleaning profiles and better shine end result, particularly on ceramic surfaces. Additionally, a method for providing excellent full strength cleaning and good shine end result on polyurethane surfaces using highly ethoxylated Guerbet alcohols is described.
• compositions containing non-ionic surfactants and in particular, compositions containing surfactants derived from the condensation of ethylene oxide with alkyl phenol.
• Non-ionic surfactants do not strongly interact with charged surfaces, can penetrate and loosen soil effectively, and can emulsify grease.
• the quest for formulations of overall improved performance has therefore centered on the identification of superior non-ionic surfactants.
• Recent work has demonstrated that relatively low molecular weight linear ethoxylates outperform the more popular alkyl phenol ethoxylates.
• poly-dispersed C8-C10 ethoxylates as described in The Journal of the American Oil Chemists Society", Vol. 61, Number. 7, pages 1273-1278 (1984) provide benefits at about 50%-60% ethoxylation levels.
• dilute cleaning performance of linear ethoxylates is still not acceptable, particularly in light of the current trend toward more concentrated products.
• An object of the present invention is to provide detergent compositions which deliver improved cleaning at recommended dilution levels for many typical surfaces, including polyvinyl chloride, polyvinyl chloride coated with polyurethane, ceramic, and enamel.
• detergent compositions particularly concentrated compositions, comprising highly ethoxylated surfactants derived from Guerbet alcohols are effective in removing soils from hard surfaces.
• the surfactants of this invention are highly ethoxylated, having from about 7 to about 30 moles of ethylene oxide (glycol) per mole of Guerbet alcohol and contain no more than about 5% Guerbet alcohol by weight of the Guerbet ethoxylate surfactant or surfactants.
• the high degree of ethoxylation and low Guerbet alcohol content in the ethoxylated surfactant of the invention lead to a number of significant benefits for cleaning hard surfaces, most notably, improved dilute cleaning wherein the concentrated cleaning composition is diluted with water to the recommended dosage, higher cleaning efficiency and better shine end result. Improved efficiency means that less surfactant is required to reach the same clean end result as achieved by compositions previously described in the art. Lower surfactant levels in product also helps improve surface shine end result.
• the relatively high degree of ethoxylation and low Guerbet alcohol content make it easier to formulate concentrated cleaner compositions in particular.
• the compositions of this invention are low in odor and aesthetically appealing.
• the hard surface cleaning compositions of this invention provide a substantial advance over hard surface cleaners known in the art, as will be seen from the disclosures hereinafter.
• R* and R are independently C3.11 alkyl groups; n is from about 7 to about 30, preferably from about 7 to about 25, more preferably from about 9 to about 20; and R 3 is hydrogen or a C1.3 alkyl or hydroxyalkyl group and wherein said Guerbet ethoxylated surfactant contains no more than about 5% free Guerbet alcohol.
• the total number of carbon atoms in R 1 and R 2 is from about 9 to about 14 carbon atoms, preferably comprising a total of from about 9 to about 13 carbon atoms, more preferably comprising a total of from about 9 to about 11 carbon atoms.
• R* and R 2 differ by no more than about 4 carbon atoms.
• R 3 is hydrogen.
• solvents comprise from about 1% to about 10% by weight of said compositions and have molecular weights no greater than about 350, preferably from about 115 to about 250. They are preferably selected from the group consisting of mono-, di- and tri- ethylene glycol, propylene glycol, butylene glycol ethers, and mixtures thereof.
• R 3 is alkyl or hydroxyalkyl the hydrophobicity of the surfactant is increased. Further, it is believed that surfactants wherein R 3 is alkyl or hydroxyalkyl can act to suppress suds during use.
• Guerbet alcohol ethoxylates of the present invention are produced by reacting Guerbet alcohols with ethylene oxide or appropriate ethylene glycol ether mixtures.
• Examples of preferred ethoxylated surfactants derived from Guerbet alcohols of this invention are selected from the group consisting of topped 2-butyl-l-heptanol with an average of 9 moles of ethoxylation, topped 2-butyl-l-octanol with an average of 7 moles of ethoxylation, 2-butyl-l-octanol with an average of 11 moles of ethoxylation, 2-butyl-l-octanol with an average of 19 moles of ethoxylation and 2-butyl-l-decanol with an average of 15 moles of ethoxylation and mixtures thereof.
• topped is defined hereinafter.
• the hard surface detergent compositions can comprise from about 0.5% to about 10% by weight of one or more low HLB non-Guerbet nonionic co- surfactants.
• the low HLB non-Guerbet non-ionic co-surfactants comprise from about 7 to about 15 carbons in the hydrophobic moiety and have an HLB of from about 3.5 to about 8.5.
• Preferred low HLB non-Guerbet non-ionic surfactants are selected from the group consisting of alkyl ethoxylates, alkyl propoxylates, alkyl ethoxy propoxylates, and mixtures thereof.
• HLB is defined hereinafter.
• compositions can also comprise an effective amount of optional, conventional detersive ingredients to assist in the performance of the ethoxylated surfactant.
• Conventional detersive ingredients typically comprising in the range of from 0% to about 20%, by weight of the compositions, can be selected from members consisting of anionic surfactants, polar non-ionic surfactants, zwitterionic surfactants, detergent builders, hydrotropes, thickeners, buffering agents, and mixtures thereof.
• Still another optional ingredient is a suds control agent, typically comprising from 0% to about 4% by weight of the hard surface composition.
• Typical compositions also comprise at least about 40% by weight water.
• compositions can further be concentrated, either thickened or unthickened, and can be packaged in containers designed to make application to hard surfaces more convenient. Hard surfaces are typically cleaned by contacting said surface with a composition of this invention, preferably diluted in water to recommended levels.
• E and ⁇ O are known in the art and are synonymous with “ethoxylate”.
• PO means "propoxylate”.
• highly ethoxylated Guerbet alcohols hereinafter denotes a series of 2-alkyl-l-alkanols that are ethoxylated, as described above, such that the final product contains an average of between about 7 to about 30 moles of ethoxylate per mole of starting material and such that the level of free Guerbet alcohol is no more than about 5% of the ethoxylate raw material or raw material mixtures.
• an effective amount herein is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance cleaning of a soiled surface.
• the highly ethoxylated Guerbet alcohols of this invention comprise at least about 1%, more preferably from about 2% to about 40%, even more preferably from about 2% to about 30% by weight of the hard surface cleaner composition.
• These highly ethoxylated Guerbet non-ionic surfactants represent from about 25% to 100% of the non-ionic surfactants in the composition, more preferably from about 30% to about 90%, even more preferably from about 40% to about 80% of the non-ionic surfactants in said composition.
• the ethoxylated Guerbet alcohols are used in the formulation of concentrated multipurpose cleaners.
• the compositions herein comprise Guerbet alcohol ethoxylates wherein the hydrophobic moiety comprises from about 11 to about 16 carbon atoms, more preferably from about 11 to about 15 carbon atoms, most preferably from about 11 to about 13 carbon atoms. It is believed that Guerbet alcohols comprising less than 11 carbon atoms are substantially more hydrophilic than Guerbet alcohols comprising over 11 carbon atoms, and thus, the benefits of high levels of ethoxylation are significantly reduced. Guerbet alcohol ethoxylates with hydrophobic moieties of greater than 16 carbon atoms are believed to have slower rates of cleaning and are not as effective for hard surface cleaner applications as the
• Guerbet ethoxylates of this invention are ethoxylated, preferably using ethylene oxide, wherein ethoxylation comprises an average from about 7 moles to about 30 moles of ethylene oxide per mole of starting alcohol. More preferably, the ethoxylation comprises from about 7 moles to about 25 moles of ethylene oxide per mole of starting alcohol. Still more preferably, ethoxylation comprises from about 9 moles to about 20 moles of ethylene oxide per mole of starting Guerbet alcohol.
• the Cl 1-16 Guerbet ethoxylates of the invention may also be "topped” meaning that the lower molecular weight ethoxylate and alcohol fractions can be selectively removed by distillation. Topping" is particularly important for Guerbet ethoxylates that contain 5% or more free alcohol incorporated in the Guerbet ethoxylate raw material. It is found that low levels of C 11-16 Guerbet alcohols act to significantly reduce the full strength and dilute cleaning performance of the C 11-16 Guerbet ethoxylates of this invention. Thus, the ethoxylates of this invention contain less than 5%, more preferably less than 3%, most preferably less than 1% free Guerbet alcohol by weight of the Guerbet ethoxylate.
• topping is often not necessary because highly ethoxylated alcohols generally contain only trace levels of free alcohol, the process can be of value to certain samples with ethoxylation levels between about EO7 and about EOI 1.
• neat cleaning performance of "topped" 2-butyl-l-octanol E07 improves over 50% relative to untopped 2-butyl-l-octanol E07 which contains 10% 2-butyl-l-octanol as part of die raw material, and that dilute cleaning also improves about 25%.
• topping may be used to effectively raise average degree of ethoxylation, if desired.
• the Guerbet alcohols from which the surfactants of the present invention are made may be obtained from several suppliers including Condea Chemie, Hamburg, Germany, and Michel Company, New York, USA. Ethoxylation is accomplished by reacting the alcohol with ethylene oxide in the presence of a suitable catalyst. Ethoxylation of Guerbet alcohols is described in The Journal of the American Oil Chemists Society", Volume 67, Number 2, pages 123-131 (1990).
• Suitable catalysts include alkali and alkaline earth metals such as sodium, potassium, magnesium and the like, alkali and alkaline earth metal oxides including sodium oxide, potassium oxide, barium oxide and die like, and alkali and alkaline earth alkoxides such as ones generated by the reaction of a metal hydroxide with an alcohol.
• a preferred alkoxide is one produced by the reaction of a metal or a metal hydroxide with a Cl 1-16 Guerbet alcohol.
• ethoxylation catalyst is considered to be within the scope of a person of ordinary skill in the art.
• Examples of highly ethoxylated Guerbet alcohols of the present invention include, but are not limited to, the condensation product between 2-butyl-l-octanol and an average of about 11 moles of ethylene oxide (i.e., 2-butyl-l-octanol EO11), the condensation product between 2-hexyl-l-octanol and an average of 15 moles of ethylene oxide (i.e., 2-hexyl-l- octanol EO 15) and the condensation product between 2 -butyl- 1 -decanol and an average of 25 moles of ethylene oxide (i.e., 2-butyl-l -decanol EO25). All of the ethoxylate surfactants of the present invention are poly-dispersed, meaning that they are present as distributions of ethoxylates with "ethoxylation level" defining the average level of ethoxylation.
• compositions disclosed herein may be used, for example, as IX products but are more preferably used as "Ultra", 2X or 4X products, that is, products that behave as concentrated cleaners. Concentrated cleaners are often more economical on a "per use” basis because of savings in packaging and improvements in surfactant technology such as described herein.
• Concentrated cleaners that use highly ethoxylated Guerbet alcohols are believed to be more efficient than other conventional alcohol ethoxylates, such as the ones described in "The Journal of the American Oil Chemists Society", Volume 61, Number 7, pages 1273-1278 (1984).
• highly ethoxylated Guerbet alcohols provide a 25%-50% improvement in dilute cleaning efficiency versus the most efficient linear ethoxylates.
• the efficiency of Guerbet ethoxylate surfactants may alternatively be measured by evaluating the level of surfactant necessary to obtain performance equal to that of a reference composition that uses performance-optunized linear ethoxylate surfactants.
• the Guerbet alcohol ethoxylate surfactants herein also display improved shine end result, particularly on surfaces such as ceramic. It is possible that these surfactants act as surface modifiers, much as described in The Journal of Physical Chemistry", Volume 95, Number 4, pages 1679-1681: Surfactant adsorption on the surface occurs in such a manner that the hydrophobic portion of the molecule interacts with the ceramic surface and die ethoxylate head group is oriented away from the surface. Guerbet branching at the carbon ⁇ to the head group ensures enhanced efficiency and effectiveness of adsorption relative to that anticipated for linear ethoxylates. As a result, surface wettability is enhanced and surfactant agglomeration upon drying is reduced. Thus, aesthetically unappealing streaks are minimized.
• Branching at the ⁇ position is also believed to lower the symmetry of the Guerbet ethoxylates relative to linear congeners, thus making the energetics for crystallization less favorable. Less crystalline materials are less reflective to light and therefore show less visible streaks. Additionally, lower levels of active required to match the dilute cleaning efficiency of linear ethoxylates as described above, means a lower level of surfactant on surfaces after recommended dilution, and translates into a smaller non-volatile residue on the surfaces once the cleaiung job is complete. Stated otherwise, highly ethoxylated Guerbet alcohols can be used to promote good shine end result benefits for the consumer.
• ethoxylated Guerbet alcohols described herein are "highly" ethoxylated meaning that the level of average ethoxylation is higher than what is typically employed for conventional alcohol ethoxylates.
• Many non-ionic alcohol ethoxylate surfactants show deteriorating dilute cleaning profiles as a function of increased levels of ethoxylation beyond
• Guerbet alcohol ethoxylate performance improves as ethoxylation is raised to beyond an average of about 7 moles of ethylene oxide per mole of starting alcohol.
• C 11-16 Guerbet alcohols that are ethoxylated to less than about an average of 7 moles of ethylene oxide per starting alcohol show reduced performance and are often unstable emulsions, even in the presence of soiubilizing agents such as 2-ethyl-l-hexyl sulfate and die like.
• soiubilizing agents such as 2-ethyl-l-hexyl sulfate and die like.
• the higher than anticipated average level of ethoxylation for the Guerbet alcohols of this invention is expected to result in competitive chemical costs. Higher levels of ethoxylation for the Guerbet alcohols can reduce costs because ethylene oxide is relatively inexpensive, both on a weight and mole basis, compared to Guerbet alcohols.
• the Guerbet ethoxylates of this invention are "highly" ethoxylated, and as such do not provide suds reduction benefits. Indeed, the compositions herein disclosed are most preferably employed with a separate suds-mediating system. The present invention also does not preferably employ cationic surfactants.
• compositions disclosed herein may optionally but preferably contain from 0.5% to about 10% of one or more low HLB non- Guerbet non-ionic co-surfactants selected from the group consisting of alkyl ethoxylates, alkyl propoxylates, alkyl ethoxy propoxylates, and mixtures thereof.
• These preferred non- Guerbet co-surfactants have the general structure RO(CH 2 CH 2 O) x H, RO(CH 2 - CH(CH 3 )0) x H or RO(CH 2 -CH 2 0)x-(CH 2 -CH(CH3)O)yH respectively, where R is a linear or branched alkyl or alkenyl hydrophobic group containing from about 7 to about 15 carbon atoms and x and y are such that the HLB of these non-Guerbet non-ionic surfactants are between about 3.5 and about 8.5.
• HLB is defined herein as % ethylene oxide or % propylene oxide divided by 5 (e.g., %EO +5).
• HLB is calculated by taking a weighted average of the HLB ratios calculated for the EO and PO groups separately.
• the non-Guerbet non-ionic surfactants may be derived from either a primary or a secondary alcohol by reaction with either ethylene oxide, propylene oxide or a combination of the two gases.
• Preferred non-Guerbet non-ionic co-surfactants for this invention include but are not limited to, the condensation product between a C9-C11 alcohol and 2.5 moles of ethylene oxide, die condensation product between a C14-C15 alcohol and 4 moles of ethylene oxide, die condensation product between a secondary Cl 1 alcohol and 2 moles of ethylene oxide, and die like.
• Suitable ethoxylated and propoxylated alcohols for this invention are available from a wide range of commercial suppliers in Europe and North America including Shell, Henkel and Vista Chemical.
• low HLB non-ionic co-surfactants described above are incorporated into formulations of the present invention depends on several factors, including choice of catalyst for ethoxylation of Guerbet alcohol, average level of Guerbet alcohol ethoxylation, and die presence or absence of co-surfactants.
• low HLB co-surfactants are particularly useful for compositions containing Guerbet ethoxylates wherein ethoxylation comprises on average about 11 moles of EO or higher, more preferably an average of about 15 moles of EO or higher, per mole of starting alcohol.
• low HLB surfactants are believed to assist in soil emulsification or roll-up.
• low HLB co-surfactants constitutes a preferred embodiment of the invention.
• Preferred compositions contain from 0.5% to about 10%, more preferably from about 2% to about 8% of said non-Guerbet co- surfactants.
• the ratio of highly ethoxylated Guerbet alcohol to said low HLB non-Guerbet non-ionic co-surfactants is preferably from about 25: 1 to about 3:1.
• Non-Ionic and Zwitterionic Surfactants - Non-ionic surfactants derived from primary or secondary alcohols by reaction with either ethylene oxide, propylene oxide or mixtures of the two, said surfactants having an HLB greater than about 8.5 may also be used in this invention.
• These surfactants include, for example, the condensation product of a C 13- 15 primary alcohol with an average of 20 moles of ethylene oxide, the condensation product of a C8-10 primary alcohol with 7 moles of ethylene oxide and die condensation product between a Cl 1-15 secondary alcohol with an average of 20 moles of ethylene oxide, and die like.
• These surfactants are commercially available through suppliers including Shell, Henkel and Union Carbide, and may be obtained in either Europe or North America.
• non-ionic surfactants for use in this invention include surfactants obtained from the condensation of hydrocarbons having a reactive hydrogen (i.e., such as on a hydroxyl, carboxyl, amido or amino group) with ethylene oxide under either acidic or basic conditions.
• Such compounds include alkyl phenol ethoxylates and ethoxylated mono or di- amino or amido compounds.
• Suitable alkyl phenol ethoxylates for this invention are commercially available from the Union Carbide Company under die tradename Triton". Most preferred are die C8-C12 alkyl phenols which have from about 3 to about 12 ethoxy groups.
• Amido and amino ethoxylates may be purchased from the Akzo chemical company under die tradenames "Ediomid” and “Ethomeen” respectively.
• Ethoxylated di-amines are sold under die tradename “Ethoduomeen”.
• Fatty acid ethoxylates are also widely available from commercial suppliers.
• Odier suitable non-Guerbet non-ionic surfactants for this invention are semi-polar non- ionics including water soluble amine oxides containing one alkyl or hydroxyalkyl moiety of about 6 to about 16 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups, containing from 1 to 3 carbon atoms which can optionally be joined into ring structures.
• non-ionic surfactants of the present invention are the condensation products of ethylene oxide widi the product resulting from the reaction of propylene oxide and ethylenediamine.
• the hydrophobic moiety of these products consists of the reaction product of ediylenediamine with excess propylene oxide, and has molecular weight of from about 2,500 to about 3,000. This hydrophobic moiety is condensed witii ethylene oxide to the extent that die product contains from about 40% to about 80% by weight of poly-oxyethylene and has a molecular weight from about 5,000 to about 11 ,000.
• Acceptable but not preferred non-ionics are surfactants selected from the group that include fatty acid amides, sorbitan esters and alkyl glycosides. These surfactants may be present in amounts not exceeding about 5% of the composition.
• the present invention allows for the incorporation of zwitterionic surfactants taken from the group of compounds comprising betaines such as alkyl betaines, alkyl amido-propyl betaines, hydroxyalkyl betaines and alkyl sulfobetaines (i.e., sultaines).
• betaines have the structure RN + (CH3) 2 -CH 2 COO" where R is an aliphatic chain containing from about 10 to about 18 carbon atoms.
• Sulfobetaines are zwitterionic surfactants widi the general formula RN+(CH 3 ) 2 -CH 2 -CH(H or OH)CH 2 S0 3 -.
• Anionic Surfactants may optionally be used in conjunction with the highly ethoxylated Guerbet alcohols of the present invention.
• Anionic surfactants are well known in the art and are herein defined as surfactants comprising from about 8 to about 20 carbon atoms and further comprising one or more anionic head groups selected from the group consisting of carboxylates, sulfates, sulfonates and mixtures thereof.
• the hydrophobic moieties may comprise linear, branched or cyclic hydrocarbon groups which may be saturated or unsaturated.
• anionic surfactant counter-ions are selected from the group of water-soluble alkali and alkaline earth metals such as sodium, potassium, magnesium, and die like.
• Anionic sulfonate surfactants useful to the invention include linear and branched C8- C14 alkyl benzene sulfonates, C8-C18 methyl ester sulfonates, C8-C18 alpha-olefin sulfonates, C8-C20 paraffin sulfonates, C10-C18 alkyl isethionates, alkyl N-med-yltaurates, and the like.
• Anionic sulfate surfactants useful to the invention include linear and branched C8-20 sulfates, C12-C18 secondary alcohol sulfates, ethoxylated sulfates, propoxylated sulfates, olefin sulfates such as oleyl sulfate, and die like.
• Anionic carboxylate surfactants of use include C10-C16 alkyl ethoxy carboxylates, C8-C18 ⁇ -hydroxyalkyl carboxylates, C10- C20 alkyl and alkenyl sarcosinates, and die like.
• Di-anionic surfactants which contain similar or dissimilar head groups or dissimilar head groups may also be used.
• Examples include C8-C18 sulfosuccinates and C10-C20 alkyl- ⁇ -sulfo fatty acid disalts.
• the anionic surfactants useful to this invention are available from a large number of suppliers in Asia, North America and Europe.
• Preferred anionic surfactants for this invention are selected from the group consisting of short chain alkyl sulfates and sulfonates, and C14-C 17 paraffin sulfonates.
• Short chain anionic surfactants such as C8 sulfonate are believed to assist full strength cleaning because low surfactant molecular weight and high critical micelle concentrations promote fast kinetics of cleaning.
• the C14-C17 paraffin sulfonates are found to help provide good shine end result, particularly under hard water conditions, i.e., water hardness between about 7 and about 25 grains per gallon. It is believed that this results from efficient complexation of the sulfonates with calcium, leading to species of low molecular symmetry which are not very crystalline.
• die compositions of the present invention further comprise one or more solvents.
• Solvents are broadly defined as compounds that are liquid at temperatures of 20°C-25°C and which are not considered to be surfactants.
• solvents tend to exist as discrete entities rather than as broad mixtures of compounds.
• Solvents of this invention contain from about 8 carbon atoms to about 35 carbon atoms, and contain contiguous linear, branched or cyclic hydrocarbon moieties of no more than about 8 carbon atoms.
• suitable solvents for the present invention include, 2 -methyl pyrrolidinone, benzyl alcohol and morpholine n-oxide.
• die solvents are selected from the group of compounds comprising ether derivatives of mono-, di- and tri-ethylene glycol, propylene glycol, butylene glycol ethers, and mixtures thereof.
• the molecular weights of the preferred solvents are less than about 350, more preferably between about 100 and about 300, even more preferably between about 115 and about 250.
• Examples of preferred solvents include, for example, mono-ethylene glycol n-hexyl ether, mono-propylene glycol n-butyl ether, and tri-propylene glycol methyl ether.
• Ethylene glycol and propylene glycol ethers are commercially available from the Dow Chemical Company under die tradename "Dowanol” and from the Arco Chemical Company under die tradename “Arcosolv”.
• Other preferred solvents including mono- and di-ethylene glycol n-hexyl ether are available from the Union Carbide company.
• Preferred solvents according to this invention are present in from about 1% to about 10%, more preferably from about 2% to about 8%, most preferably from about 3% to about 7%, by weight of the hard surface cleaner composition.
• the ratio of highly ethoxylated Guerbet alcohols to solvent is most preferably from about 10: 1 to about 1 :4.
• hydrophobic low molecular weight solvents promote faster soil softening, thereby improving the ease of cleaning of highly ethoxylated Guerbet alcohols.
• Preferred solvents are particularly effective for improving the full strength (i.e., neat) cleaning performance of the Guerbet ethoxylate surfactants of this invention.
• Guerbet ethoxylates of the present invention have more carbon atoms in the hydrophobic moiety (Cl 1- C16) and a higher average degree of ethoxylation ( ⁇ 60%- ⁇ 90%) than what the literature recommends for peak neat cleaning performance. It has been found tiiat substantial improvements to full strength cleaning of u_e Guerbet edioxylates can be achieved either by topping the surfactant or by addition of selected solvents to the surfactant system.
• topping For Guerbet ethoxylates that contain only slightly more than 60% ethylene oxide, topping often achieves the desired result of restoring neat cleaning to peak levels,as described in the literature (JAOCS, 61 (7), 1273-1278 (1984), but for Guerbet edioxylates containing more than about 75% ethylene oxide, topping is no longer effective.
• use of one or more preferred solvents in preferred ratios can bring about full strengdi cleaning performance comparable to that obtained widi shorter chain length ethoxylates such as C8-C10 E06.
• the large improvements in full strength cleaning mediated by solvent are obtained without significantly altering the Guerbet ethoxylate dilute cleaning advantages described earlier.
• compositions containing 15% 2-butyl-l- octanol EOU, 4% linear C12-C13 EO3 and 5% propylene glycol /.-butyl ether provide a 20% advantage in dilute cleaning efficiency and are fully equivalent in full strength cleaning to compositions containing 20% linear C8-C10 EO6 and 4% linear C12-C13 EO3.
• Hydrophobic solvents, when used in conjunction widi highly ethoxylated Guerbet alcohols of the present invention are shown to improve composition shine end result on poly ⁇ vinyl chloride and poly-urethane surfaces relative to compositions which do not employ said solvents. It is believed that shine end result on these surfaces is improved by compounds having low surface tension and low molecular weights.
• most preferred solvents for shine end result on these surfaces are selected from the group comprising at most about 25 carbon atoms, more preferably from about 6 to about 20 carbon atoms, most preferably from about 6 to about 15 carbon atoms.
• the lower molecular weight solvents provide die largest shine end result benefits.
• shine end result improves widi decreasing number of propylene glycol groups.
• compositions herein are preferably used in combination with suds control agents. While silicone polymers and poly-oxyetiiylene poly- oxypropylene block co-polymers may be used for this purpose, preferred suds control agents are selected from the group consisting of compounds comprising linear or branched alkyl carboxylic acids.
• the suds control agents of the present invention comprise from 0% to about 4%, more preferably from about 0.4% to about 3%, most preferably from about 0.6% to about 1.5% by weight of the composition.
• Preferred alkyl carboxylic acids contain at least about 8 carbon atoms in die hydrophobic moiety, more preferably from about 8 to about 18 carbon atoms, most preferably from about 11 to about 17 carbon atoms.
• these compounds include, for example, 2-butyl-l-octanoic acid, C16-18 "palm" fatty acid and C12-C14 coconut fatty acid.
• Fatty acids produced industrially by saponification of tri-glycerides constitute a particularly preferred class of compounds for suds control. These compounds are usually present as mixtures of C8-C18 or C10-C18 fatty acids and are widely produced and marketed, for example, by the Procter and Gamble Company in North America, and by Henkel in Europe. The fatty acids are quickly neutralized to soaps in alkaline media, and die soaps control suds by acting as builders and precipitating calcium.
• compositions according to the mvention further comprise a minimum of about 40% water, more preferably from about 45% to about 99%, still more preferably from about 50% to about 90% by weight of die composition.
• Product pH is at least about 6, more preferably between about 7 and about 13 and most preferably between about 8 and about 12. Below pH of about 6, it is found that the compositions of die present invention are a lot less effective for full strength cleaning even though dilute cleaning is not adversely affected. Compositions of pH above about 13 are believed to be less safe for consumers and are therefore not preferred.
• Hydrotropes can be added to compositions of the invention, preferably in amounts of from about 1% to about 5%, if needed or desired to decrease die viscosity of the composition or help solubilize surfactants or additives.
• Preferred hydrotropes include die alkali metal, preferably sodium, salts of toluene suifonate, xylene suifonate, cumene suifonate, and sulfosuccinate and 2-ethyl-l-hexyl sulfate.
• the compositions of die invention preferably further comprise up to about 5% by weight builder. Builders assist surfactant cleaning by sequestering calcium and magnesium.
• Examples of conventional builders include, for example, water soluble alkali metal salts of phosphates, pyrophosphates and oithophosphates, tripolyphosphates and higher phosphates.
• Otiier builders suitable for the present invention include poly-carboxylates, silicates and aluminosilicates. More preferred for this invention are the builders selected from the group comprising water soluble alkali metal citrates, carbonates and alkyl carboxylates (i.e., soaps).
• a combination of two or more builders, for example, carbonate and soap, may also be used in the present invention. Many builders leave aesthetically unappealing residues on surfaces upon drying or crystallizing.
• the hard surface cleaner compositions of die present invention may contain, if desired, any of the usual adjuvants, diluents and additives known to those skilled in the art of cleaning. These additional additives, if present, typically comprise in the range of from 0% to about 20% of the cleaning composition.
• compositions include, for example, bleaching agents, perfumes, mild abrasives, enzymes, amino acids, dyes, anti-tarnasbing agents, antimicrobiol agents, and die like, without detracting from the advantageous properties of the compositions.
• Most preferred compositions are without abrasives.
• Cationic surfactants such as quartemary ammonium compounds are not preferred in die present invention. They do not significantiy contribute to either dilute or neat cleaning, and are somewhat detrimental to shine end result benefits in the context of this invention.
• Composition Use and Process The cleaning compositions of this invention can be used for many cleaning tasks including general household cleaners, and general dish detergents. Most preferably the compositions are used for cleaning of hard surfaces, including floors, walls, metals, glass, ceramic, linoleum, parquet and marble.
• the Guerbet alcohols can be formed in any suitable manner, for example, by "Aldol” condensation of two aldehydes followed by reduction to the desired alcohol or alcohols.
• mixtures of 2-propyl-l-octanol and 2-butyl-l-heptahol are obtained as the predominant products by reaction of pentanaldehyde widi hexanaldehyde and subsequent hydrogenation.
• the desired 2-alkyl-l -alkanols may be formed in one step by the so-called "Guerbet” reaction wherein two primary or secondary alcohols are condensed in the presence of catalyst to form ⁇ - alkyl alkanols suitable for this invention.
• Guerbet reaction catalysts are usually either alkoxides, transition metal complexes or berth. Examples of suitable Guerbet catalysts are disclosed in "The Journal of Molecular Catalysis", Volume 33, Number 1, pages 1-14 (1985).
• Guerbet alcohols are typically reacted widi ediylene oxide using established methodologies to produce poly-dispersed ethoxylated surfactants with average degree of ethoxylation from about 7 to about 30. Ethoxylation is performed at experimental conditions which substantially exclude, more preferably, completely exclude water. Excluding water is important since water can react with ethylene oxide to form polyethylene glycol as a side product.
• compositions containing highly ethoxylated Guerbet alcohols may be prepared in any suitable manner, for instance, by simply mixing in the components.
• a convenient method for preparing the compositions involves mixing the Guerbet ethoxylate in water, followed by addition of otiier non-ionic surfactants and tiien anionic surfactants, if any. Solvents and/or hydrotropes, if any, may then be added while stirring the mixture. Suds control agents are then combined into the formulations.
• pH is usually near neutral, and this allows for convenient control of final product via addition of ingredients used for pH adjustment and buffering, such as sodium hydroxide and potassium carbonate.
• the performance of the compositions of this invention are evaluated by means of dilute cleaning, full strength cleaning, and shine end result.
• Outlined below are instructions as to bow each test is conducted.
• the dilute cleaning test requires two days, as test execution should be conducted after the tiles are allowed to age for about 15 to about 18 hours.
• dilute cleaning and neat cleaning tests are demonstrated on poly-urethane surfaces, while foil strength cleaning is demonstrated on enamel.
• the tests methods are applicable to other surfaces such as ceramic, poly-vinylchloride, formica, parquet, and die like. It has been verfied that the choice of surface (e.g., enamel versus ceramic) has little or no impact on the cleaning performance (dilute or neat) of the compositions tested.
• shine end result is surface-dependent.
• the surfaces are chosen so as to best highlight filming and streaking differences among formulations, i.e., die tests are intentionally performed on shiny black surfaces.
• Dilute cleaning method: Sample preparation on dav 1 - Clean four polyurethane coated PVC floor tile panels (Color Tile Nafco ZL-810 No-Wax floor tile cut into 3 x 12 inch panels) with isopropyl alcohol using delicate task wipers and allow than to dry. If ceramic, poly-vinyl chloride or formica tiles are used, the same procedures apply.
• Dilute cleaning test dav 2 - Weigh the soiled floor tile panels; record weight. Test water hardness and record.
• Dilute cleaning test execution - Make up test solution: IX product ⁇ 7.2 g product / 600 g total with desired hardness water corresponds to a 1.2% product concentration, which corresponds to a 1/64 product dilution;
• the reference product is assigned a cleaning "100" index for comparative purposes and is chosen because surfactants similar to linear C8-C10 EO6 are highly recommended in the literature as a primary components of hard surface cleaning compositions.
• Performance of experimental compositions containing highly ethoxylated Guerbet alcohols is dimensioned, on a equal or slightly less than equal weight basis, versus the reference product.
• the molecular weights of the Guerbet ethoxylates of the invention are significantly higher than that of C8-C10 EO6.
• 2-butyl-l-octanol EO11 has an average molecular weight that is nearly 50% greater than that of linear C8-C10 EO6. Since performance in all the cleaning tests (i.e., dilute and neat) is defined in terms of ease of soil removal, that is kinetics of cleaning, surfactant molarity and not weight percent is most relevant to these tests. Thus, the data in examples I- Vm are taken as conservative estimates of the performance of highly ethoxylated Guerbet alcohols.
• experimental prototypes all contain the same 1.0% carbonate/bicarbonate and 0.6% C10-C18 fatty acid as die reference product and are also adjusted to pH 10.
• the following abbreviations are used: "G” for Guerbet alcohol, "/” for linear alcohol, “s” to denote an alcohol located on secondary carbon atoms, "GC12” for 2- butyl- 1-octanol, “T” for topped surfactant, "PnB” for propylene glycol n- butyl ether,
• Dilute cleaning refers to relative cleaning performance of a composition that is diluted using 1 part product to 128 parts water versus that of the reference product (defined above) diluted to the same level.
• “neat” cleaning refers to the relative cleaning performance of undiluted experimental products.
• the contents are heated to 135°C and sodium metal catalyst is added at a 0.35 g level (0.015 mole) and allowed to dissolve under constant stirring conditions.
• 200 g (4.55 mole) ethylene oxide is added at ambient conditions. Dissolution of die ethylene oxide gas allows ethoxylation of 2-butyl-l-octanol to take place.
• the reaction product i.e., poly-dispersed ethoxylate
• the reaction product is a non-volatile liquid so that degree of reaction completion may be determined by differential weight measurements.
• the product is characterized by Gas Chromatography (GC) and determined to contain about 1% unreacted alcohol.
• Dilute cleaning profiles of ethoxylated Guerbet alcohols are compared as a function of average degree of ethoxylation. All indexing is relative to the reference product.
• Example ffl The magnitude of die dilute cleaning benefits obtainable with surfactants of the invention is illustrated.
• Part IQa provides dilute and neat cleaning performance comparisons between the ethoxylated Guerbet alcohols of this invention, a Guerbet alcohol which is outside die claims of the invention, and linear C8-C10 EO6.
• Part IHb. shows differences in performance between highly ethoxylated Guerbet alcohols and other linear or branched surfactants with similar number of carbon atoms in the hydrophobic moiety and level of ethoxylation.
• Example IV The impact of Guerbet ethoxylate topping and solvent incorporation on formulation overall performance is assessed.
• Example Va dimensions cleaning performance of the Guerbet ethoxylates of this invention as a function of product dilution.
• Example Vb. shows the effect of increased product dilution on shine end result on poly-urethane surfaces.
• Example VI The following example illustrates the impact of anionic surfactants on dilute cleaning performance of surfactants of the invention.
• the following example shows dilute cleaning performance of the highly ethoxylated Guerbet alcohols at a range of pH conditions.
• Product pH is controlled using carbonate bicarbonate mixtures, or citrate.
• Example Vm A mixture of Guerbet alcohols of composition shown below is ethoxylated to an average of 15 moles of ethylene oxide per starting alcohols.
• a product is then made containing 20% alcohol ethoxylate mixtures, 4% linear C12-
• Example IX The following hard surface cleaner compositions exhibit good dilute cleaning performance.
• a. 7.5% 2-propyl-l-octanol EO9, 7.5% 2-butyl-l-heptanol EO9, 3.0% diethylene glycol n-hexyl ether, 2.0% linear C8 suifonate, 3.0% C14-C17 paraffin suifonate, 1.5% pottassium carbonate, 1.0% 2-butyl-l-octanoic acid, pH adjusted to 9 and remainder distilled water (to 100%).
• b. 7.5% 2-butyl-l-octanol EO19, 7.5% linear CIO amine oxide, 2.0% linear C12-

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• 1995
  • 1995-12-08 AU AU44231/96A patent/AU4423196A/en not_active Abandoned
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