AU711075B2 - Liquid crystal detergent compositions - Google Patents

Description

I.L

1 IR F1321 LIQUID CRYSTAL

COMPOSITIONS

Field of the Invention This invention relates to a liquid crystal detergent composition containing wood particles and an abrasive. More specifically, it is of a liquid detergent composition in a liquid crystal state which when brought into contact with oily soil is superior to other liquid detergent compositions in detergency and in other physical properties.

Background of the Invention Liquid aqueous synthetic organic detergent compositions have long been employed for human hair shampoos and as dishwashing detergents for hand washing of dishes (as distinguished from automatic dishwashing machine washing of dishes).

Liquid detergent compositions have also been employed as hard surface cleaners, as in pine oil liquids, for cleaning floors and walls. More recently they have proven successful as laundry detergents too, apparently because they are convenient to use, are instantly soluble in wash water, and may be employed in "pre-spotting" applications to facilitate removals of soils and stains from laundry upon subsequent washing. Liquid detergent compositions have comprised anionic, cationic and nonionic surface active agents, builders and adjuvants, including, as adjuvants, lipophilic materials which can act as solvents for lipophilic soils and stains. The various liquid aqueous synthetic organic detergent compositions mentioned serve to emulsify lipophilic materials, including oily soils, in aqueous media, such as wash water, by forming micellar dispersions and emulsions.

Although emulsification is a mechanism of soil removal, it has been only comparatively recently that it was discovered how to make microemulsions which are much more effective than ordinary emulsions in removing lipophilic materials from substrates. Such microemulsions are described in British Patent Specification No.

2,190,681 and in U.S. Patents 5,075,026; 5,076,954 and 5,082.584 and 5,108,643, st of which relate to acidic microemulsions useful for cleaning hard surfaced items.

D l AMENDED

SHIEET

1pEA 'E 2 such as bathtubs and sinks which microemulsions are especially effective in removing soap scum and lime scale from them.

The various microemulsions referred to include a lipophile, which may be a hydrocarbon, a surfactant, which may be an anionic and/or a nonionic detergent(s), a co-surfactant, which may be a poly-lower alkylene glycol tower alkyl ether, e.g., tripropylene glycol monomethyl ether, and water.

Although the manufacture and use of detergent compositions :n microemulsion form significantly improved cleaning power and greasy soil removal, compared to the usual emulsions, the present invention improves them still further and also increases the capacity of the detergent compositions to adhere to surfaces to which they have been applied. Thus, they drop or run substantially less than cleaning compositions of "similar" cleaning power which are in microemulsion or normal liquid detergent form.

Also, because they form microemulsions with lipophilic soil or stain material spontaneously, with essentially no requirement for addition of any energy, either thermal or mechanical, they are more effective cleaners at room temperature and at higher and lower temperatures that are normally employed in cleaning operations than are ordinary liquid detergents, and are also more effective than detergent compositions in microemulsion form.

The present liquid crystal detergent compositions may be either clear or somewhat cloudy or milky (opalescent) in appearance but both forms thereof are stable on storage and components thereof do not settle out or become ineffective, even on storage at somewhat elevated temperatures for periods as long as six months and up to a year. The presence of the cosurfactant in the liquid crystal detergent compositions helps to make such compositions resist freezing at low temperatures.

The present invention relates to a liquid detergent composition containing wood particles which act as an abrasive as well as a surfactant carrier. The compositions are suitable at room temperature or colder, for pre-treating and cleaning materials soiled tlupophilic soil, is in liquid crystal form and comprises synthetic organic surface AMENDED SHEET -T .3 active agents, a cosurfactant, a solvent for the soil, and water. The invention also relates to processes for treating items and materials soiled with lipophilic soil with compositions of this invention to loosen or remove such soil, by applying to the locus of such soil on such material a soil loosening or removing amount of an invented composition. In another aspect of the invention lipophilic soil is absorbed Irom the soiled surface into the liquid crystal.

In recent years all-purpose liquid detergents have become widely accepted for cleaning hard surfaces, painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc.. Such all-purpose liquids comprise clear and opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent builder salts. In order to achieve comparable cleaning efficiency with granular or powdered all-purpose cleaning compositions, use of water-soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids. For example, such early phosphate-containing compositions are described in U.S. Patent Nos. 2,560,839; 3,234,138; 3,350,319; and British Patent No. 1,223,739.

In view of the environmentalist's efforts to reduce phosphate levels in ground water, improved all-purpose liquids containing reduced concentrations of inorganic phosphate builder salts or non-phosphate builder salts have appeared. A particularly useful self-opacified liquid of the latter type is described in U.S. Patent No. 4,244,840.

However, these prior art all-purpose liquid detergents containing detergent builder salts or other equivalent tend to leave films, spots or streaks on cleaned unrinsed surfaces, particularly shiny surfaces. Thus, such liquids require thorough rinsing of the cleaned surfaces which is a time-consuming chore for the user.

In order to overcome the foregoing disadvantage of the prior art all-purpose liquid, U.S. Patent No. 4,017,409 teaches that a mixture of paraffin suffonate and a reduced concentration of inorganic phosphate builder salt should be employed.

However, such compositions are not completely acceptable from an environmental point of view based upon the phosphate content. On the other hand, another 4 alternative to achieving phosphate-tree all-purpose liquids has been to use a major proportion of a mixture of anionic and nonionic detergents with minor amounts of glycol ether solvent and organic amine as shown in U.S. Patent NO. 3,935,130. Again, this approach has not been completely satisfactory and the high levels of organic detergents necessary to achieve cleaning cause foaming which, in turn, leads to the need for thorough rinsing which has been found to be undesirable to today's consumers.

Another approach to formulating hard surfaced or all-purpose liquid detergent composition where product homogeneity and clarity are important considerations involves the formation of oil-in-water microemulsions which contain one or more surface-active detergent compounds, a water-immiscible solvent (typically a hydrocarbon solvent), water and a "cosurfactant" compound which provides product stability. By definition, an o/w microemulsion is a spontaneously forming colloidal dispersion of "oil" phase particles having a particle size in the range oi 25 to 800 A In a continuous aqueous phase.

In view of the extremely fine particle size of the dispersed oil phase particles, microemulsions are transparent to light and are clear and usually highly stable against phase separation.

Patent disclosures relating to use of grease-removal solvents in o/w microemulsions include, for example, European Patent Applications EP 0137615 and EP 0137616 Herbots et al; European Patent Application EP 0160762 Johnston et al; and U.S. Patent No. 4,561,991 Herbots et al. Each of these patent disclosures also teaches using at least 5% by weight of grease-removal solvent.

It also is known from British Patent Application GB 2144763A to Herbots at al, published March 13,1985, that magnesium salts enhance grease-removal performance of organic grease-removal solvents, such as the terpenes, in o/w microemulsion liquid detergent compositions. The compositions of this invention Sdescribed by Herbots et al. require at least 5% of the mixture of grease-removal solvent AMENDED

SHEET

IPEA/EP

Ill I I and magnesium salt and preferably at least 5% of solvent (which may be a mixture of water-immiscible non-polar solvent with a sparingly soluble slightly polar solvent) and at least 0.1% magnesium salt.

The following representative prior art patents also relate to liquid detergent cleaning compositions in the form of o/w microemulsions: U.S. Patents Nos.. 4,472,291 Rosario; 4,540,448 Gauteer et al; 3,723,330 Sheflin; et al.

Liquid detergent compositions which include terpenes. such as d-limonene, or other grease-removal solvent, although not disclosed to be in the form of o/w microemulsions, are the subject matter of the following representative patent documents: European Patent Application 0080749; British Patent Specification 1,603,047; and U.S. Patent Nos. 4,414,128 and 4,540,505. For example, U.S. Patent No. 4,414,128 broadly discloses an aqueous liquid detergent composition characterized by, by weight: from 1% to 20% of a synthetic anionic, nonionic, amphoteric or zwltterionic surfactant or mixture thereof; from 0.5% to 10% of a mono- or sesquiterpene or mixture thereof, at a weight ratio of being in the range of 5:1 to 1:3; and from 0.5% to 20% of a polar solvent having a solubility in water at 15oC in the range of from 0.2% to 10%. Other ingredients present in the formulations disclosed in this patent include from 0.05% to 2% by weight of an alkali metal, ammonium or alkanolammonium soap of a C13-C24 fatty acid; a calcium sequestrant from 0.5% to 13% by weight; non-aqueous solvent, alcohols and glycol ethers, up to 10% by weight; and hydrotropes, urea, ethanolamines, salts of lower alkylaryl sulfonates, up to 10% by weight. All of the formulations shown in the Examples of this patent include relatively large amounts of detergent builder salts which are detrimental to surface shine.

U.S. Patent 5,035,826 teaches liquid crystal compositions but these compositions exhibit thermal stability in the limited temperature range of 19°C to 36 0

C.

j I AMENDED SHEET IPEA/EP W094/05 757 teaches a hard surface cleaner having an abrasive with a particle size in the micron range.

EP Application 0335471A2 teaches a hard surface cleaner having an abrasive in the micron range.

EP Application 0125711A1 teaches a general purpose cleaner requiring the presence of a partially esterified resin.

Summary of the Invention The present invention provides an improved, liquid crystal detergent composition having improved scouring ability. The compositions have improved interfacial tension which improves cleaning hard surface in the form of a liquid crystal which is suitable for cleaning hard surfaces such as plastic, vitreous and metal surfaces having a shiny finish, oil stained floors, automotive engines and other engines. More particularly, the improved S cleaning compositions exhibit good grease soil removal properties due to the 15 improved interfacial tensions and leave the cleaned surfaces shiny without the need of or requiring only minimal additional rinsing or wiping. The latter characteristic is evidenced by little or no visible residues on the unrinsed cleaned surfaces and accordingly, overcomes one of the disadvantages or prior art products.

Surprisingly, these desirable results are accomplished even in the r absence of polyphosphate or other inorganic or organic detergent builder salts and also in the complete absence or substantially complete absence of grease-removal solvent.

In one aspect, the invention generally provides a stable, liquid crystal, hard surface cleaning composition especially effective in the removal of oily and greasy oil. The liquid crystal composition includes on a weight basis: 1% to 15% of an ethoxylated C 8

-C

18 alkyl ether sulfate surfactant; 1% to 30 of a water-mixable cosurfactant having either limited ability or substantially no ability to dissolve oily or greasy soil; 1% to 30% of an ethoxylated nonionic surfactant; 0.98% to 10% of magnesium sulfate heptahydrate or magnesium chloride; 0.6% to 10% of a perfume, essential oil, or water insoluble hydrocarbon having 6 to 18 carbon atoms; 0.1% to 10% of wood particles; and i/I the balance being water, wherein the liquid crystal detergent composition does not contain any sulfonate surfactant, and the liquid detergent composition has a storage modulus equal to or higher than one Pascal (1 Newton/sq. more preferably higher than 10 Pascal at a temperature of 20 0 C to 40 0 C at a strain of 0.1% to 5% second as measured on a Carri-Med CS Rheometer and is thermally stable and exist as a clear liquid crystal in the temperature range from 8°C to 43 0 C, more preferably 4°C to 43 0

C.

In another aspect, the invention generally provides a stable, liquid crystal, hard surface cleaning composition especially effective in the removal of oily and greasy oil. The liquid crystal composition includes, on a weight basis: 1% to 20% of an ethoxylated C 8

-C,

1 alkyl ether sulfate surfactant or sodium lauryl sulfate (SLS); 15 1% to 30% of a water-mixable cosurfactant having either limited ability or substantially no ability to dissolve oily or greasy soil; 1% to 30% of an ethoxylated nonionic surfactant; 0.98% to 10% of a magnesium salt such as magnesium sulfate heptahydrate or magnesium chloride; 0.6% to 10% of a perfume, essential oil, or water insoluble hydrocarbon having 6 to 18 carbon atoms; 0.1% to 10% of an abrasive; and the balance being water, wherein the liquid crystal detergent composition does not contain any sulfonate surfactant, and the liquid 25 detergent composition has a storage modulus equal to or higher than one Pascal (1 Newton/sq. more preferably higher than 10 Pascal at a temperature of 20 0 C to 40"C at a strain of 0.1% to 5% second as measured on a Carri-Med CS'" Rheometer and is thermally stable and exist as a clear liquid crystal in the temperature range from 8 0 C to 43 0 C, more preferably 4°C to 43 0

C.

Throughout this specification, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

Detailed Description of the invention The present invention relates to a stable optically clear liquid crystal detergent composition comprising by weight: 1% to 15% of an ethoxylated alkyl ether sulfate surfactant, 1% to 30% of a cosurfactant, 1% to 30% of an ethoxylated nonionic surfactant, 0.6% to 10% of a water insoluble hydrocarbon, essential oil or a perfume, 0.1% to 10% of wood particles, and the balance being water, wherein the liquid detergent composition does not contain any sulfonate surfactant, and the liquid detergent composition has a storage modulus equal to or higher than one Pascal (1 Newton/sq. more preferably higher than 10 Pascal at a temperature of 20 0 C to 40 0 C at a strain of 0.1% to 5% second as measured on a Carri-Med CS'" Rheometer and is S" thermally stable and exist as a liquid crystal in the temperature range from *:ago: 8 0 C to 43 0 C, more preferably 4 0 C to 43 0

C.

15 The present invention also relates to a stable liquid crystal detergent composition comprising by weight: 1% to 20% of an ethoxylated alkyl ether sulfate or sodium lauryl sulfate (SLS) surfactant, 1% to 30% of a cosurfactant, 1% to 30% of an ethoxylated nonionic surfactant, 0.6% to 10% of a water insoluble hydrocarbon, essential oil or a perfume, 0.1% to 10% of an abrasive, and the balance being water, wherein the liquid detergent composition does not contain any sulfonate surfactant, and the liquid detergent composition has a storage modulus equal to or higher than one Pascal (1 Newton/sq. more preferably higher than 10 Pascal at a temperature of 20 0 C to 40 0 C at a strain of 0.1% to 5% second as measured on S 25 a Carri-Med CS'" Rheometer and is thermally stable and exist as a liquid crystal in the temperature range from 10°C to 45 0 C, more preferably 8°C to 43 0

C.

According to the present invention, the role of the water insoluble hydrocarbon can be provided by a non-water-soluble perfume. Typically, in aqueous based compositions the presence of a solubilizers, such as alkali metal lower alkyl aryl 9 sulfonate hydrotrope, triethanolamme, urea, etc., is required for perfume dissolution, especially at perfume levels of 1% and higher, since perfumes are generally a mixture of fragrant essential oils and aromatic compounds which are generally not watersoluble.

As used herein and in the appended claims the term "perfume" is used in its ordinary sense to refer to and include any non-water soluble fragrant substance or mixture of substances including natural obtained by extraction of flower, herb, blossom or plant), artificial mixture of natural oils or oil constituents) and synthetically produced substance) odoriferous substances. Typically, perfumes are complex mixtures of blends of various organic compounds such as alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils terpenes) such as from 0% to 80%, usually from 10% to 70% by weight, the essential oils themselves being volatile odoriferous compounds and also serving to dissolve the other components of the perfume.

Quite surprisingly although the perfume is not, per so, a solvent for greasy or oily soil, even though some perfumes may, in fact, contain as much as 80% of terpenes which are known as good grease solvents the inventive compositions in dilute form have the capacity to solubilize up to 10 times or more of the weight of the perfume of oily and greasy soil, which is removed or loosened from the hard surface by virtue of the action of the anionic and nonionic surfactants, said soil being taken up into the oil phase of the o/w microemulsion.

In the present invention the precise composition of the perfume is of no particular consequence to cleaning performance so long as it meets the criteria of water immiscibility and having a pleasing odor. Naturally, of course, especially for cleaning compositions intended for use in the home, the perfume, as well as all other ingredients, should be cosmetically acceptable, non-toxic. hypoallergenic, etc.

The hydrocarbon such as a perfume is present in the liquid crystal composition Li 4 n an amount of from 0.6% to 10% by weight, preferably from 0.8% to 8% by weight, SAMENED SHEET

IPEA/EP

especially preferably from 1% to 6% by weight. If the amount of hydrocarbon (perfume) is less than 0.6% by weight it becomes difficult to form the liquid crystal. If the hydrocarbon (perfume) is added in amounts more than 10% by weigh!, the cost is increased without any additional cleaning benefit and, in fact, with some diminishing of cleaning performance insofar as the total amount of greasy or oily soil which can be taken up in the oil phase of the microemulsion will decrease proportionately.

Furthermore, although superior grease removal performance will be achieved for perfume compositions not containing any terpene solvents, it is apparently difficult for perfumers to formulate sufficiently inexpensive perfume compositions for products of this type very cost sensitive consumer-type products) which includes less than usually less than 30%, of such terpene solvents.

Thus, merely as a practical matter, based on economic consideration, the liquid crystal cleaning compositions of the present invention may often include as much as 0.2% to 7% by weight, based on the total composition, of terpene solvents introduced thereunto via the perfume component. However, even when the amount of terpene solvent in the cleaning formulation is less than 1.5% by weight, such as up to 0.6% by weight or 0.4% by weight or less, satisfactory grease removal and oil removal capacity is provided by the inventive compositions.

In place of the perfume in either the microemulsion composition or the all purpose hard surface cleaning composition at the same previously defined concentrations that the perfume was used in either the microemulsion or the all purpose hard surface cleaning composition one can employ an essential oil or a water insoluble organic compound such as a water insoluble hydrocarbon having 6 tc 18 carbon such as a paraffin or isoparaffin such as isoparH, isodecane, alpha-pinene, beta-pinene, decanol and terpineol.

Suitable essential oils are selected from the group consisting of: Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Peru), Basil oil (india), -31ack pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol

DV""

AMENDED 3HEET P E o r~1].

Flakes (China), Camphor oil, White, Camphor Powder synthetic tecnni Cal, Cananga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) SP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove eaf, Coriander (Russia), Coumnann 69C (China), Cyclamnen Aldehyds, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun balsam, Heliotropin, Isobornyl acetate, isolongifolene, Juniper berry oil, L-rrethyl acetate, Lavender oil, Lemon oil, Lemongrass oil, Lime oil distilled, Lrsea Cubeba oil, Longitolene, Menthol crystals, Methyl cedryl ketone, Methyl Chavicol, Methyl salicylate, Musk ambrette, Musk ketone, Musk xylol, Nutmeg oil, Orange oil, Patchouli oil, Peppermint oil, Phenyl ethyl alcohol, Pimento berry oil, Pimento leaf oil, Rosalin, Sandalwood oil, Sandenol, Sage oil, Clary sage. Sassafras oil, Spearmint oil, Spike lavender, Tagetes, Tea tree oil, Vanilin, Vetyver oil (Java), Wintergreen The nonionic surf actant is present in amounts of 1 to 30%, preferably 3% to 18% by weight of the liquid crystal composition and provides superior performance in the removal of oily soil and mildness to human skin.

The water soluble ethoxylated nonionic surfactants utlized in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates and secondary aliphatic alcohol ethoxylates. The nonionic synthetic organic surfactants generally are the condensation products of an organic aliphatic hydrophobic compound and hydrophilic ethylene oxide groups. The length of the polyethenoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.

The nlonionic surfactant class includes the condensation products of a higher alcohol an alkanol containing B to 16 carbon atoms in a straight or branched chain configuration) condensed with 4 to 30 moles of ethylene oxide, for example,, [auryl or myristyl alcohol condensed with 16 moles of ethylene oxide tridecanol condensed with 6 to moles of EC, myristyl alcohol condensed with 10 moles of EO per AMENDED sNEET 1PEAIEP mote of mnyristyl alcohol, the condensation product of EQ with a cut Of coconut fatty alcohol containing a mixture Of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms in length and wherein the condensate contains either 6 moles of EC per mole of total alcohol or 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EC to 11 EOD per mole of alcohol.

A preferred group of the foregoing nonionic surfactants are tne Neodo!TM ethoxylates (Shell which are higher aliphatic, primary alcohol containing 9-15 carbon atoms, such as C 9

-C

1 11 alkanol condensed with 4 to 10 moles of ethylene oxide (NeodolTM 91-8 or NeodorM11 91-5), C 12 13 alkanol condensed with 6.5 moles ethylene oxide (NeodoTM 23-6. C 12 15 alkanol condensed with 12 moles ethylene oxide (NeodoTMI 25-12),

C

1 4 15 alkanol condensed with 13 moles ethylene oxide (NeodoITMI 45-13), and the like. Such ethoxamers have an HLB (hydrophobic lipophilic balance) value of 8 to 15 and give good 01W emulsification, whereas ethoxamers with HLB values below 7 contain less than 4 ethyleneoxide groups and tend to be poor emnulsifiers and poor detergents.

Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available nonionic detergents of the foregoing type are C1 1 -C 15 secondary alkanol condensed with either 9 E0 (TergftolTuA i 5-S-9) or 12 EQ (TergtoITMV 1 5-S- 12) marketed by Union Carbide.

rheoethoxylated alkyl ether sutfate or SLS surfactants which may be used in the detergent of this invention are water soluble such as the triethanolamine sodium, potassium, ammonium and ethano Iammonium salts of an CB-18 ethoxylated alkyl ether sulfate surfactants have the structure: A-(OCHCH2i)nOSo 3

M

wherein n is I to 5 and IR is an alkyl group having 8 to 18 carbon atoms, more I referablly 12 to 15 and natural cuts, for example, C 12-14; Cl1 2-15 and M is an AMENDED HT 13 ammonlium cation or a metal cation, most preferably sodium, The ethoxylated alkyl ether sulfate is present in the composition at a concentration of 1 to 15% by weight, more preferably 2% to 13% by weight.

The ethoxylated alkyl ether sulfate may be made by sulfating the condensation product of ethylene oxide and C8-i 0 alkanol, and neutralizing the resultant product.

The ethoxylated alkyl ether sulfates differ from one another in the number of carbon atoms in the alcohols and in the number of moles of ethylene oxide reacted with one mole of such alcohol. Preferred ethoxylated alkyl ether polyethenoxy sulfates contain 12 to 15 carbon atoms in the alcohols and in the alkyl groups thereof, sodium myristyl (3 EO) sulfate.

Ethoxylated C8.1 8 alkyipheflyl ether sulfates containing from 2 to 6 moles of ethylene oxide in the molecule are also suitable for use in the invention compositions.

These detergents can be prepared by reacting an alkyl phenol with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resultant ethoxylated alkylphenol.

The concentration of the ethoxylated alkyl ether sulfate surfactant is 1 to 8 wt- The major class of compounds found to provide highly suitable cosurtactants for the microemnulsion over temperature ranges extending from 5 0 C to 43"C for instance are glycerol, ethylene glycol, water-soluble polyethylene glycols having a molecular weight of 300 to 1000, polypropylene glycol of the formula HQ(CH3CHCH2Q)flH wherein n is a number from 2 to 18, mixtures of polyethylene glycol and polypropyl glycol (Synatox~m) and mono Ci -C6 alkyl ethers and esters of ethylene glycol and propylene glycol having the structural formulas R(X)nOH and At 1XKnOH wherein R is Cl-C6o alkyl group, R1 is C2-C4 acyl group, X is (OCH2CH2) or (QCH 2 (0H3)CH) and n is a number from 1 to 4, diethylefle glycol, tnethylene glycol, an alkyl lactate, wherein the alkyl group has 1 to 6 carbon atoms, 1 methoxy-2-propall 1 methoxy-3-propanol.

and 1 methoxy 3- or 4-butanol.

Representative members of the polypropylene glycol include dipropylefle glycol 'nd polypropylene glycol having a molecular weight of 200 to 1000, polypropylene 14 glycol 400. Other satisfactory glycol ethers are ethylene glycol mnonobutyl ether (butyl ceilosolve), diethylefle glycol monobutyl ether (butyl carbitol), triethylefle glycol monobutyl ether, mono, di, tri propylene glycol monobutyl ether, tetraethylefle glyWo monobutyl ether, mono, di, tnipropylene glycol mono methyl ether, propylene glycol monomethyl ether, ethylene glycol moriohexyl ether, diethylene glycol monohexyl ether, propylene glycol tertiary butyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethYl ether, ethylene glycol monopropyl ether, ethylene glycol monopentyl ether, diethytefle glycol monomethyl ether, diethylene glycol monoethyl other, diethylefle glycol monopropyl ether, diethylene glycol monoper'lyl ether, triethylene glycol monomethyl ether, triethylefle glycol monoethyl ether, triethylene glycol monopropyl ether, thethylene glycol monopenityl ether, triethytene glycol monohexyl other, mono. di, tripropylefle glycol monoethyl ether, mono, di tripropylefie glycol monopropyl ether, mono, di, tripropylefle glycol monopentyl ether, mono, di.

tripropylene glycol monohexyl ether, mono, di, tributylene glycol mono methyl ether, mono, di, tributyief'e glycol monoethyl ether, mono, di, tributylene glycol monopropyl ether, mono, di, tributylefle glycol monobutyl ether, mono, di, tributylefle glycol monopentyt ether and mono, di, tributylefle glycol monolhexyl ether, ethylene glycol monoacetate and dipropylene glycol propionate. Tripropylene glycol n-butyl ether is the preferred casurfactafit because of its hydrophobic character.

The amount of cosurfactant required to stabilize the liquid crystal composition s will, of course, depend on such factors as the surface tension characteristics of the cosurfactaflt, the type and amounts of the primary surfactants and perfumes, and the type and amounts of any other additional ingredients which may be present in the composition and which have an influence on the thermodynamic factors enumerated above. Amounts of cosurfactant used in the liquid crystal composition is in the range of from 1I% to preferably from 2% to 200/, especially preferably from 3% to 16%, by weight provide stable dilute liquid crystal composition for the above-described levels of .1 AiL~. .1 I "In" L, L I a v; 1. L -LI primary surfactants and perfume9 and any other additional ingredients as described InadiioltoThi eclln capacity for lea ig greasy and oily sois The low p l iui cr ad o ultions a e r x lso t exhibit excellent c lai g perform ance and rem oval Pf soapi rstmand limrmsatins at (undiluted) as well as 'in diluted usage.

T e inap s tmant li mai crystal eae ft c o sitio nis can contain wood particles which are abrasive particles designed to improvetesorn oe fti ntn liquid Crystal detergenlt compositionl. The surtactant in the compositionl is also absorbed on the surface of the wood partices. This Permits the wood particles to act as a surtactant carrier thereby improving the depositing of the surtactant on the soiled surlactant. The wood Particles have a particle diameter ct 200 mifimicrons to 600 millimIcronS, mre preferably 400 millmlCrmns to 500o millimiCrons. Preferred wood particles are Pic" abies having a particle diameter size of 425 millimicrons. The concentration of the wood particles inl the liquid crystal dtrgenlt composition is from o.i to 10 wt, more preferably 0.2 to 6 wt- Thewo~ patilescanbeformed from any time of semi hard or hard wood such as maple, bich, Oak, pine and apple as well as from apricot shell, Walnut shl and corn cob. The apparent density of wood particles is 0.1 10 0.5 g/1, more preferably 0.3 to o.ro and have a particle size of 400 millimiCrons.

The instant liquid crystal compoSiti~fls contain 01 to 2.5 wt. more preferably 0.25 to 2.0 Wt. of an abrasive selected from the group consistinlg of amorphous hydrated silica and polyethylene powder particles and mixtures thereof.

The amorIPhOuS silica (oral grade) used to enhance the scouring9 ability of the liquid cyStSl gel was provided by Zeoftln. Theo mean particles sze of zeoffin'w silica is 8 up to 10 mmn. Its apparent density is 0.32 to 0.37 g/Ml.

An amorphous hydrated silica from rroslield of different particles sizes and 300 MM)9 and same apparent density can also be used.

AMENDED

SHEE

16 The polyethylene powder used in the instant invention has a particle Size Of 200 to 500 microns and a density Of 0.91 to 0.99 g/liter, more preferably 0.94 to 0.96.

In addition to their excellent scouring ability and capacity for cleaning greasy and oily soils, the low pH liquid crystal formulations also exhibit excellent cleaning performance arnd removal of soap scum and lime scale in neat (undiluted) as well as in diluted usage.

The instant composition contains 0.5 to 10 wt. more preferably I to S m. of a magnesium salt such as magnlesium chloride and/or magnesium sulfate and mixtures thereof The final essential ingredient in the inventive liquid crystal compositions having improved interfacial tension propertis is water. The proportion of water in the liquid crystal detergent compositionl generally is in the range of 20% to 97%, preferably to 97% by weight.

A composition of this invention is in a liquid crystal state when it is of lypotropiC structure, is transparent or slightly turbid (opalescent) but no opaque, and has a storage modulus equal to or higher than one Pascal (11 Newton/SQ. more preferably higher than 10o Pascal and most preferably higher than 20 Pascal and when measured at a temperature of 20 to 40C, at a frequency of ten radians per second and at a strain of 0.1 to The rheological behavior of the compositions of this invention were measured at 25 0 C by means of a Carri-Med CSTM Rlheoieter. In making the measurement, a cone and plate are used at a cone angle of 2 degrees: 0 minutes: 0 seconds with a cone diameter of 6.0 cm, measurement system gap of 52.0 micro m and a measurement system inertia of 17.02 micro Nmn sec*.

To make the liquid crystal compositions of the inventioni is relatively simple because they tend to form spontaneously With little need for the addition of energy to promote transformation to the liquid crystal state. However, to promote uniformity of the composition mixing will normally be undertaken and It has been found desirable '/>1rtto mix the surtactants and cosurfactant with the water, followed by admlixinlg of the j% E t 17 lip~h~i copoflent, usually a hydrocarbon (but esters Or mixtures ol h~ydrocarbons and esters Gma also be employed). It is not necessar to employ heat and most mixings are preferably carried out at roomce tbpyatr pouring ont The invented comps~itonls may be applied to such surnacbtping onri bto i them, by application with a cloth or ponge or by vaous othrcnctf9masbtt is preferred to apply them in the form ot a spray by spraying them onto tne substrate from a hand or linger pressure operated sprayer or squeeze bottle. Such application mnay be onto hard surfaces, such as dishes, w alS or floors, from which lipophiliC (i~sull geasy or oily) soj is to be removed, Or may be onto fabrics, such as laundry, (hushuas reO Y benstie with pphilic Soils, Such as motor oil. The invented compositionls may be used as etrgenlts and as such ma behasig fmloo and hae manner in whch liquid detergenlts are normally utilized In swahgIlorndal cleaning and launlderinig, but it is preferred that they be employed as pre-spottiflQ agentS ao.~ h~ pplicationls they are founld to be extremely useful in loseninlg the adesns of0 inowhic siSt ubstrates thereby protiflg much easier clanin~g with applitoofmroftese invented dtrgenlt compositions or by applications of apicaerent cofmre Oa th~erlt saeot0stiofls in liquid bar or particulate forms.

Thfee vamrius deatergent oC th tiof have already been set forth in some detail and will not be repeated here. HoWever it lili bertertedn tt h copo ntioncnb relates to0 the Important discovery that eltective iud~trel opstoScnb made In the liquid crystal state and that beca thyaeiruhsa e h ie e especialy elfective in removinlg lipophilic soils from substrates anid also Br feciei removing from substrates nofl-lip0philic 111tenals. Such desirable properties of the liquid crystal detergenlt Compositions 01 this invention make them ideal for use as pre- Spotting agents and detergenlts for them ideal for use as pre-spotting9 agents and dtergents for removinlg hardt0o-temove soils from substrates in Vaious hard and soft ~*surface cleaning operations.

AMENDED

SHEET

I P ENEP EPA LIft LD)i.IJ~w- The following examples illustrate but do not limit the invention. Unless otherwise indicated, all parts in these examples, in the specification and in the appended claims are by weight and all temperature are in OC.

The following formulas (wt. were made at 25 0 C by simple mixing.

A C I E F G 91~~ -5DbnlA 2 1 12 12 12 12 12 GIAES 2E0l 3 3 3 3- 3 3 Triapylne htcl nbutl eher11.25 11.25 11.25 11.25 11.25 11.25 11.25 7 75 3.75 3.75 3.75 3.75 MgSO4'7HZ0 0.98 0.98 0.9 Picea abies wood pries dons*t 0 0.2 0.5 0.8 1 2 4 Batral. Bal Sa. a. .aiL al. a.! Thermal stflbity OC 18-36 IS-36183r,836 18-36 18-36 18-36 Cleaning easiness index 0 hard tallow 0 0 00603 hairdtallow &5%softbeef -1.33 0 0 0 0 0 0.43 tallow The cleaning performance of the different prototypes was evaluated versus a classical cream cleaner (Cif) as reference.

The Cif formula composition was: anionic 2.9% nlonionic; 1.4% calite soap The results are given in terms of cleaning easiness index: [1 -(strokes number proto/Strokes number ref)l If strokes number proto strokes number ref., then the index is 0 (cleaning equivalence between prototype and reference).

If strokes number proto z strokes number ref. then the index is characterized by a negative value (the more negative the index, the less efficient the prototype).

AMENDED

S"HEET-=

19 The following formulas (wt. O/)were mnade at2C b ipe iig >1/

Claims (8)

1. A liquid crystal detergent composition which includes by weight: 1% to 30% of a nonionic surfactant containing ethylene oxide groups; 0.1% to 10% of wood particles wherein said wood particles having a particle diameter size of 200 millimicrons to 600 millimicrons; 1% to 15% of a water soluble salt of an alkyl sulfate or ethoxylated C 8 18 alkyl ether sulfate surfactant or a C 8 18 alkyl phenyl ether sulfate having 2-6 moles of ethylene oxide; 1% to 30% of a water mixable glycol ether cosurfactant which is a C 1 -C 6 alkyl ether of mono-, di-, tri- or tetra-ethylene or propylene glycol or of mono-, di-, or tri- butylene glycol; 0.6% to 10% of a water insoluble organic compound selected from 15 the group consisting of perfumes, essential oils and water insoluble hydrocarbons having 6 to 18 carbon atoms; 0.98% to 10% of magnesium sulfate heptahydrate or magnesium chloride; and the balance being water, said liquid crystal detergent composition has a storage modulus measured at a temperature between 20 0 C to 40 0 C, at a strain of 0.1% to 5% and a frequency of 10 radians/second of at least one #0

6. :4 Pascal and is one phase at a temperature of 18°C to 36 0 C, said composition does not contain any sulfonate surfactant. C 25 2. The composition of Claim 1, wherein said nonionic surfactant is a condensation product of one mole of a higher fatty alcohol having 9 to 11 carbon atoms with 2 to 6 moles of said ethylene oxide groups. S3. The composition according to Claim 1 or Claim 2 wherein said water soluble salt of said ethoxylated C-C 8 alkyl ether sulfate surfactant has a cation selected from the group consisting of sodium, potassium and ammonium. 4. The composition according to any one of the preceding claims, wherein said water insoluble hydrocarbon is d-limonene, selected from the 21 group consisting of alpha-terpineol, alpha-pinene, and beta pinene and mixtures thereof. The composition according to any one of the preceding claims, wherein said cosurfactant is tripropylene glycol n-butyl ether. 6. A process for treating materials soiled with lipophilic soil to loosen or remove it which includes applying to the locus of such soil on such material a soil loosening or removing amount of a composition according to any one of Claims 1 to

7. A process according to Claim 6 wherein the composition is applied as a pre-treatment to material soiled with hard-to-remove lipophilic soil at the locus thereof on the material, after which application the soil is removed by 15 application of the same or a different detergent composition and water.

8. A liquid crystal detergent composition which includes by weight: 1% to 30% of a nonionic surfactant containing ethylene oxide groups; 1% to 20% of a water soluble salt of an ethoxylated C 8 -C, 1 alkyl -ether sulfate surfactant or alkyl sulfate surfactant or a C 8 1 8 alkyl phenyl ether sulfate having 2-6 moles of ethylene oxide; 0.1% to 5% of an amorphous hydrated silica abrasive having a particle size of 8 to 300 millimicrons; S 25 1% to 30% of a water mixable glycol ether cosurfactant which is a C 1 -C 6 alkyl ether of mono-, di-,tri- or tetra-ethylene or propylene glycol or of mono-, di-, or tri- butylene glycol; 0.6% to 10% of a water insoluble organic compound selected from S" the group consisting of perfumes, essential oils and water insoluble hydrocarbons having 8 to 18 carbon atoms; 0.98% to 10% of magnesium sulfate heptahydrate or magnesium chloride; and the balance being water, said liquid crystal detergent composition has a storage modulus measured at a temperature between 20 0 C to 40 0 C, at a strain of 0.1% to 5% and a frequency of 10 radians/second of at least one Pascal and is one phase at a temperature of 18 0 C to 36 0 C, said composition does not contain any sulfonate surfactant.

9. The composition of Claim 8, wherein said nonionic surfactant is a condensation product of one mole of a higher fatty alcohol having 9 to 11 carbon atoms with 2 to 6 moles of said ethylene oxide groups. The composition of Claim 7 or Claim 8 wherein said water soluble salt of said ethoxylated C,-C, 1 alkyl ether sulfate surfactant has a cation selected from the group consisting of sodium, potassium and ammonium. S.

11. The composition according to any one of claims 8 to 10, wherein said water insoluble hydrocarbon is d-limonene, selected from the group consisting of alpha-terpineol, alpha-pinene, and beta pinene and mixtures 15 thereof. C

12. The composition according to any one of claims 8 to 11, wherein said cosurfactant is tripropylene glycol n-butyl ether.

13. A process for treating materials soiled with lipophilic soil to loosen or remove it which includes applying to the locus of such soil on such material a soil loosening or removing amount of a composition according to any one of claims 8 to 12. SDated this twenty-third day of July 1999. COLGATE-PALMOLIVE COMPANY Patent Attorneys for the Applicant: F B RICE CO