LU87357A1 - LIQUID LAUNDRY DETERGENT COMPOSITIONS, METHOD FOR USING THE SAME, AND METHOD FOR STABILIZING THE SAME - Google Patents

Description

-¾ 88 / b 52,782

ft 7 3 5 / grand-dUCHÉ DE LUXEMBOURG

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. , „„ „„ Minister, September 29, 1988 \ §É & r du ............................... E .__________________________ of Economy and Average Qasses _ a'v î ^ jÊRa- Intellectual Property Service î re e vrê ... jjlggg LUXEMBOURG "

Invention Patent Application -.....-.................................---- --------------- (1) I. Request

The so-called company: COLGATE-PALMOLIVE COMPANY, 300 Park ____________ Avenue, NEW YORK. NY 10022 (United States of America), _________________ ______ represented by Mr. Jacques de Muyser acting in___________ ___________ as agent___________________________________________________________________________________________________________ (3) file (s) this twenty-nine September 1900 eighty-eight__________ (4) at 15_____________________ hours, Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent for an invention concerning: "Liquid laundry detergent compositions, ^^ .............. ..... process ..... to use them and process to stabilize them. " 2. description in language ............., f. £ Ë.îl.9 „§ï§.Ë ---------------- --------------- of the invention in triplicate; 3 .......... 1 ...................................... ................... drawing boards, in triplicate; 4. the receipt of the taxes paid to the Luxembourg Registration Office on ............ September ...... 1988 .......

5. the delegation of power, dated ....................._................... .................................................. ..... the............................................ .................................................. ......; 6. the successor document (authorization); declares (s) assuming responsibility for this declaration, that the inventor (s) is (are): (6) - Hoai Chau CHO, rue des Bruyères 22d, LIEGE (Belgium) - Marie-Christine HOUBEN, rue de Jujpreÿe 317, ALLEUR (Belgium) claims (s) for the above patent application the priority of one (or more) application (s) of (7) patent .............. .................................................. ......................................... filed in (8) in United States of America on (9) ....... 30 ....... September 1987______________________________________________________________________________________________ under N ° (10) ....... 1 ... Q..2 .. ..... 9 2 6___________________________________________________________________________________________________________________________________ on behalf of the inventors __________________________________________________________________________________________________ elects (elect) domicile for him / her and, if designated, for his / her representative, in Luxembourg_________ _____________________________________ 35, Boulevard Royal_____________________________________________________________________ ¢ 2) requests (s) the grant of a patent for the invention for the subject described and represented in the abovementioned appendices, with postponement of this grant to ____________ 8____________________________________________________________________________________________ month. (13) Jîg ^ épOSmt / agent: __________________________________________________________________________________________________________________________________________________________________________________________ (14) f I JL V y y K K. Minutes of deposit

The aforesaid request for a briej ^ Bcie ^ i'ete filed with the Ministry of Economy and the Middle Classes, Service of ^ i Intel Property ^^ elf àLu ^ ftjgb ^ mrg, dated: September 29, 1988 fi / ·] Pr. the Minister of Econcj and the Middle Classes, at -25 ..................... hours \ · d.

v £ .Ns * / The head of the department] at Intellectual Property,

Vv, 7 / A 68007_ / | _ EXPLANATIONS RELATING TO THE DEPOSIT FORM. / d / "Λ A"% (1) if applicable "Request for certificate of addition to the main patent, to the main patent application No ......... (/. of .. .......... ”- (2) enter the surname, first name, profession, (JD address of the applicant, when the latter is an individual or the company name, legal form, address of the head office. the applicant is a legal person - (3) enter V ·, - * "L iy the last name, first name, address of the authorized representative, industrial property attorney, with special powers, if applicable:" represents by ............ acting as agent ''

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, 88 / B 52 782

Λ,, CLAIM OF PRIORITY

of the patent application / utility model • SX IN THE UNITED STATES OF AMERICA OF SEPTEMBER 30, 1987 (No. 102.926) Brief Description filed in support of an application for

PATENT

at

Luxembourg on behalf of: colgate-palmolive company NEW YORK, N.Y. 10022 (United States of America)

For: "Liquid laundry detergent compositions, process for using them and process for stabilizing them." "; k μ

The present invention relates to stabilized non-aqueous liquid suspensions, in particular non-aqueous liquid compositions for the treatment of tissues. More particularly, the present invention relates to non-aqueous liquid laundry detergent compositions which are made stable against phase separation even at relatively low viscosity, and more particularly, which remain stable under both static and dynamic conditions and which are easy to pour, as well as the process for preparing these compositions and the use of these compositions for cleaning soiled tissue.

Non-aqueous liquid detergent compositions for heavy laundering are well known in the art. For example, compositions of this type can include a liquid nonionic surfactant in which particles of a detergency builder are dispersed, as described, for example, in U.S. Patents. N ° 4 316 812, 3 630 929, 4 254 466 and 4 661 280.

Liquid detergents are often considered more convenient to use than dry powder or particulate products and consumers have therefore given them great preference. They are easy to dose, dissolve quickly in the wash water and can be easily applied in concentrated solutions or dispersions to soiled areas of clothes to be washed, and do not cause dust. and usually take up less storage space. In addition, it is possible to incorporate into the formulation of liquid detergents materials which cannot withstand drying operations without degradation, materials which it would often be desirable to employ in the manufacture of particulate detergent products.

Although they enjoy many advantages over solid products in particulate or discrete units, liquid detergents are also often affected by certain inherent disadvantages which must be overcome in order to obtain commercially acceptable detergent products.

Thus, some of these products separate on storage and others separate on cooling and are not easy to redisperse. In some cases, the viscosity of the product changes and it becomes either too thick to be poured, or fluid enough to resemble water. Some clear products cloud and others gel on standing.

The Applicant has largely embarked on a research effort aimed at studying the rheological behavior of systems based on nonionic liquid surfactant containing a particulate matter in suspension. Particular interest has been given to non-aqueous liquid laundry detergent compositions reinforced with detergency builders, and to the problems posed by phase separation and sedimentation of the suspended detergent builders and other laundry additives. These considerations have an impact, for example, on the stability and dispersibility of the products and their suitability for pouring.

It is known that one of the major problems encountered with products, liquid detergents for washing clothes containing detergency builders is that of their physical stability. This problem stems from the fact that the density of the solid particles in suspension is greater than the density of the liquid matrix. As a result, particles tend to deposit according to Stokes' law. In fact, it has been found that non-aqueous liquid suspensions of detergency builder particles, such as polyphosphate type detergency builders, especially sodium tripolyphosphate (TPP), in a nonionic surfactant behave to the point of rheological view, roughly according to Casson's equation:

1. L

= σ02 + node2 Ύ2 20 where γ is the shear rate; 0 is the shear stress;

Oq is the flow limit; and n is "plastic viscosity" (apparent viscosity at an infinite shear rate). The flow limit is the minimum stress necessary to cause plastic deformation (flow) of the suspension. Once the flow limit is exceeded, the network of suspended particles breaks at certain points and the sample begins to flow, but with a very high apparent viscosity. If the shear stress is much greater than the flow limit, the particles are partially deflocculated by shear and the apparent viscosity decreases. Finally, if the shear stress is much greater than the flow limit ft 4 / the particles are completely deflated by shear and the apparent viscosity is very low, as if there were no interaction between. the particles.

Therefore, the higher the flow limit of the suspension / the higher the apparent viscosity at a low shear rate, the better the physical stability of the product.

There are two basic ways to resolve the sedimentation problem: increase the viscosity of the liquid matrix and reduce the particle size of the solid material.

Grinding intended to reduce the particle size / as a means to increase the stability of the products / offers the following advantages: 1. The specific surface of the particles increases and / / / therefore the wetting of the particles by the non-aqueous vehicle (non- liquid ionic) is proportionally improved.

2. The average distance between the pigment particles is reduced with a proportional increase in the interaction between particles. Each of these effects contributes to increasing the gelling resistance at rest and the flow limit of the suspension while / at the same time / the grinding significantly reduces the plastic viscosity.

The U.S. Patent The aforementioned No. 4,316,812 describes the advantages of grinding solid particles / for example detergency builder and bleaching agent / up to an average particle diameter of less than 10 micrometers. However, it has been found that simple grinding to such small particle sizes does not, in turn, provide sufficient long-term stability against phase separation.

*> 5 "

For example, it is known that such suspensions can be stabilized against sedimentation by the addition of thickening agents or mineral or organic dispersants such as / for example / mineral materials with very large specific surface such as finely divided silica / clays / etc./ organic thickeners such as · cellulose ethers / acrylic and acrylamide polymers, polyelectrolytes / etc. However / such increases in viscosity of the suspensions are obviously limited by the need for the liquid suspension to be able to flow and be poured easily / even at low temperature. In addition / these additives do not contribute to the cleaning action of the composition. The U.S. Patent No. 4,661,280 describes the use of aluminum stearate to increase the stability of suspensions of detergency builder salts in liquid nonionic surfactants. The addition of small amounts of aluminum stearate raises the flow limit without increasing the plastic viscosity.

According to the U.S. patent No. 3,985,668 / a scouring abrasive composition in a falsely consisting aqueous fluid is prepared from an aqueous liquid and a suitable colloidogenic material such as a clay or other mineral or organic thickening or suspending agent / in particular smectite-type clays / and a particulate filler material insoluble in water / relatively light which / like the abrasive material / is suspended throughout the falsely consistent fluid phase. The particulate diameters of the light load range from 1 to 250 micrometers and its density is lower than that of the falsely consistent fluid phase. It is suggested in this patent that the incorporation of the relatively light insoluble filler in the falsely consistent fluid phase helps to minimize the separation of the phases, that is to say to minimize the formation of a layer. clear liquid above the falsely consistent abrasive composition # and this # firstly # thanks to its buoyancy which exerts an ascending force on the structure of the colloidogenic agent in the falsely consistent phase by opposing the tendency of the heavy abrasive to compress the falsely consistent structure and to express the liquid. Secondly # 10 the filler acts as a bulking agent by replacing part of the water which would normally be used in the absence of the filler # which means that less aqueous liquid is available to cause the formation and separation of a limpid cou-ehe.

British patent application GB-2,168,377A # published June 18, 1986 # describes aqueous liquid detergent compositions for washing dishes # containing an abrasive # a thickener of the colloidal clay type and a low density particulate filler whose particle sizes range from about 1 to about 250 micrometers and whose density is between about 0 # 01 and about 0 # 5 # which is used at a rate from about 0 # 07% to about 1% by weight in the composition. It is suggested that the filler improves stability by lowering the density of the clay mass # so that it floats in the liquid phase of the composition. The type and amount of the filler is chosen such that the density of the final composition corresponds to that of the clear fluid (i.e. the composition without clay or abrasive). The low density particulate fillers mentioned on page 4, lines 33-35 # of this British patent application can also be used as low density fillers in

Λ V

k 7 the composition of the present invention.

It is also known to include an insoluble mineral thickening or dispersing agent with a very large specific surface such as finely divided silica with an extremely small particle size (for example a silica with particle diameters between 5 and 100 nm as sold under name Aerosil) or other very bulky support mineral materials; as described in the U.S. patent

10 No. 3 630 929.

It has been known for a long time that colloidal clays swelling in water # such as clays of the bentonite and montmorillonite types # can be modified by exchange of metallic cationic groups for organic groups # to thus transform hydrophilic clays into organophilic clays. The use of these organophilic clays as gelling clays has been described in the US patent.

No. 2,531,427. Improvements and modifications to organophilic gelling clays are described # for example # in U.S. patents.

N ° 2 966 506, 4 105 578, 4 208 218, 4 287 086, 4 434 075 and 4 434 076 # all sold to the company NL Industries # Inc. # previously called National Lead Compa-25 ny. According to these patents # these organophilic clay gelling agents are advantageous to use in lubricating greases # drilling muds. Oil-based, oil-based packer fluids. # Paints # paint strippers # varnishes and 30 lacquer # adhesives # sealants # inks, polyester gel coats, etc. However, their use as stabilizers in non-aqueous liquid detergent compositions for laundering fabrics has not been suggested.

Furthermore, the use λ m 8 of clays has been described in combination with quaternary ammonium compounds to impart fabric softening properties to laundering compositions. For example, mention may be made of British patent application GB-2,141,152A published on December 12, 1984, and the numerous patents cited therein relating to fabric softening compositions based on organophilic clays using quaternary ammonium.

According to the U.S. Patent No. 4,264,466 mentioned above, the physical stability of a dispersion of particulate matter, such as detergency builders, in a non-aqueous liquid phase is improved by the use, as the main suspending agent, of a clay of the impalpable catenary structure type, including sepiolite, attapulgite and polygorskite clays. This patent declares and shows by comparative examples that the other types of clays, such as a montmorillonite (for example Bentolite L), a hectorite (for example Veegum T) and a kaolinite (for example Hydrite PX), are not as poor suspending agents, even when used in conjunction with a suspending aid, including cationic surfactants which include quaternary ammonium compounds. This patent refers to the use of other clays as suspending aids and cites the U.S. patents as examples. Nos. 4,049,034, 4,005,027 (both relating to aqueous systems), 4,166,039, 3,259,574, 3,557,037 and 3,549,542, and United Kingdom patent application 30, 2,017,072.

The U.S. patent application simultaneously pending No. 063,199 filed June 12, 1987, assigned to the Applicant, describes the incorporation, in non-aqueous liquid compositions for the treatment of tissue, of amounts up to about 1% in b S * 9 weight of an organophilic swellable water clay of the smectite type, modified by a cationic nitrogenous compound comprising at least one long-chain hydrocarbon group having approximately 8 to approximately 22 carbon-5 atoms, to form a network or an elastic structure throughout the suspension to raise the flow limit and increase the stability of the suspension.

Although the addition of organophilic clay improves the stability of the suspension / other improvements are still desirable./ especially for suspensions of particles having relatively low flow limits / in order to optimize the distribution and dispersion during use.

In the simultaneously pen-15 dante patent application No. 073 653 filed July 15, 1987 / assigned to the Applicant / entitled "Stable Non-Aqueous Cleaning Composition Containing Low Density Filler and Method of Use" / the use of '' a low density filler to stabilize liquid suspensions of finely divided solid particulate matter in a liquid phase against phase separation / by equalizing the densities of the dispersed particle phase and the liquid phase . These modified liquid suspensions exhibit excellent phase stabilization when left for long periods of time of up to 6 months or more / or even when subjected to moderate shaking. However / it was. recently observed that when suspensions modified by a low density load are subjected to strong vibrations / as can happen during transport by rail / truck / etc./ the homogeneity of the dispersion degrades and a portion of the low density filler migrates to the upper surface of the liquid suspension.

\ Μ 10

Further improvements were therefore still desirable with regard to the stability of the nonaqueous liquid tissue treatment compositions.

This wish was satisfied by the discovery by the Applicant that / by adding a small amount / limited to about 1% by weight / of an organophilic clay to a liquid suspension of finely divided functionally active particles / containing a small amount of charge at low density / the charge -1-0 and the other functional particles in suspension interact in such a way that there is obtained / essentially / a suspension of composite particles whose density is substantially equal to the density of the liquid phase continues / and this results in a more solid network structure / which is thus effective in inhibiting the tendency of suspended functional particles / for example a detergency builder / a bleaching agent / an antistatic agent / etc./ to deposit and, conversely / to inhibit the rise of the charge at low density or the formation of a clear liquid phase / when the composition is subjected to inter n its vibrational forces. Consequently / it is described / in the patent application of the E.ü.A. simultaneously pending No. 073 551 filed July 25, 1987, assigned to the Applicant, a liquid cleaning composition consisting of a suspension of functionally active particles in a liquid nonionic surfactant, the composition comprising an amount of filler at low density sufficient to increase the stability of the suspension when at rest and when shaken, and an amount of organophilic clay sufficient to improve the stability of the composition when subjected to intense vibrational forces .

However, although the stability of the nonaqueous suspension is significantly improved by the stabilizing system consisting of low density filler / organophilic clay / certain drawbacks have appeared. Firstly, it has been observed that as time passes / the viscoelastic structure imparted by the organophilic clay weakens / this weakening manifested by a constant decline in the flow limit. Consequently, it may happen, within the limits of the shelf life foreseen for the product, a time when the flow limit will have dropped below the level required to maintain the stability of the load. at low density, especially when intense vibrational forces are applied.

A second unfavorable consequence of the stabilizing system of the prior art comes from the fact that the incorporation of the filler at low density, for example microspheres, increases the plastic viscosity of the product and correlatively reduces its ability to e-20 flow.

According to the present invention, it has now been discovered that the problem of the higher viscosity of the nonaqueous suspension stabilized by a low density filler and the problem of the variation in flow rate over time for the suspension non-aqueous stabilized by an organophilic clay, can each be substantially resolved by incorporating, in the liquid cleaning composition stabilized by an organophilic clay and / or a filler at low density, a small, but effective, quantity of certain phosphoric esters. The addition of phosphoric esters • decreases the plastic viscosity of the compositions containing a filler at low density and stabilizes the flow limit of the compositions containing an organophilic clay during their aging.

* Μ 12

It is therefore an object of the present invention to provide liquid tissue treatment compositions which are suspensions of insoluble tissue treatment particles in a non-aqueous liquid and which are stable in storage over time and can be easily poured and dispersed in cold / lukewarm or hot water.

Another object of the present invention is to provide aimsoelastic nonaqueous suspensions of insoluble tissue treatment particles which can retain their rheological properties over time even when subjected to intense vibrational forces.

Another object of the present invention is to formulate strongly reinforced non-aqueous detergent compositions for large laundering jobs / based on liquid nonionic surfactant / which resist sedimentation of solid particles in suspension or separation of the phase. liquid and which can flow easily.

A particular object of the present invention is to provide a reinforced nonionic liquid non-aqueous detergent composition reinforced for heavy laundry work / which comprises a nonaqueous liquid 25 consisting of a nonionic surfactant / solid particles of treatment of fabrics in suspension in the nonaqueous liquid / at least one of a low density filler in an amount limited to about 10% by weight to substantially equalize the density of the continuous liquid phase and the density of the particulate phase in suspension / which comprises the low density filler and other suspended particles such as detergency builder particles / and an organophilic modified clay in an amount / limited to about 1% by weight / which is suitable for preventing "e *" 13 loss of homogeneity of the product, even when the composition is subjected to intense vibrational forces, and of lecithin, a glycol phosphate, a polyglycol phosphate or a phosphate e of glycerol, in an amount effective to reduce the plastic viscosity and stabilize the flow limit of the composition.

A more particular object of the invention is to provide a process for improving the stability and reducing the viscosity of a nonaqueous suspension of 10 functionally active solid particles, stabilized by a low density filler and an organophilic clay.

In another aspect, the invention provides a method for cleaning soiled tissue by contacting soiled tissue with the nonionic liquid laundry detergent composition described above.

In yet another aspect of the invention there is provided a method for stabilizing a suspension of a finely divided particulate first active solid substance in a continuous liquid phase serving as a carrier, the suspended solid particles having a density greater than the density of the liquid phase, this process comprising adding to the suspension of solid particles a finely divided charge having a density less than the density of the liquid phase in an amount such as the density of the solid particles dispersed in association with the charge is similar to the density of the liquid phase, said charge also increasing the plastic viscosity of the suspension, an organophilic clay, in a small amount suitable for enhancing the structural cohesiveness of the suspension and suppressing the tendency of the charge to rise at the surface of the composition when the composition is subjected to intense vibrational forces, as during% * 14 a transport / and a lecithin / a. glycol phosphate / polyglycol phosphate or glycerol phosphate in a small amount suitable for effectively reducing the plastic viscosity of the suspension and maintaining its structural cohesiveness.

The phosphoric ester used in the present invention to reduce the viscosity and stabilize the flow limit is preferably a lecithin.

Pure lecithin is a fatty acid-killed phosphatidylcholine; corresponding to the general structural formula: ch2or rJ-O-C-H o I If 0 15 CH20P0CH2CH2N (CÜ3) 3 0-

In practice, however, lecithin is rarely available in pure form and / generally the term "lecithin" refers to a complex natural mixture of phosphatides, triglycerides / carbohydrates / sterols and other minor ingredients.

Lecithin is generally obtained from vegetable oil / soybean oil as the main source. Other sources of lecithin include egg yolk / milk and animal brains. The phosphatides that are present in lecithin are similar / except that their proportions vary. Likewise, the other minor components of lecithin vary depending on the particular source.

The following table gives typical fatty acid profiles of commercially available lecithins: 35% “15

Comparative profiles of fatty acids (% by weight)

Number of atoms Lecithin Lecithin Lecithin carbon and commercial soybean trade double bonds _ _ oil free 5 Saturated C16: 0 9 15 19 C18: 0 5 5 5

Total 14 20 24

Unsaturated 10 cia * l 26 17 10 C18: 2 53 55 59 C18: 3 7 8 7

Total 86 80 76

A typical composition of soy lecithin, the most common commercial product / is as follows:%

Phosphatidyl-choline (I) 20

Phosphatidyl-ethanolamine (II) 15 2Q Phosphatidyl-inositide (III) 20

Phosphatic acids and other phosphatides 5

Carbohydrates, sterols 5

Triglycerides 35 with 25 O H2C-O-CO-R1 * · 1

I = R2— CO — CH O

'"0 H 2C-0-P-0-CH 2CH 2N (CH 3) 3 - 0 H2C-O-CO-R1" »II" R2 — C— 0 — CH 0

IN A

H2C-0-P-0-CH2ch 2NH3 35 0- * 4 * 16

__ „OH HO

O H2Ç-O-CO-R1 _. Oh

in “r2-c-o-ch / K

5 H2C-O-P— 0 ^ _ 0- oh oh

Rl 'R2 = C16: 0' C18: 0 / C18: l, C18: 2 / C18: 3

All of these natural forms of lecithin can be used in the present invention. In addition, lecithin does not have to be pure, and all qualities of lecithin which are generally mixtures of phosphititylcholine, phosphatidylethanolamine, phosphatidylinositol (phos-15 phatides) and triglycerides can be used as a viscosity reducing stabilizer. regardless of the source, for example egg yolk, soy, etc. However, it is generally preferable to use a form of twice bleached lecithin in order to minimize any background odors that may possibly be present in natural products.

Other useful phosphoric esters include phosphates from glycols, polyglycols and glycerol. As glycols, there can be mentioned, for example, ethylene glycol, propylene glycol, buty-lene glycol and glycol ethers such as diethylene glycol monomethyl ether, monoethylene diethylene ether -glycol, etc. Polyglycols can have up to about 20 repeating oxyethylene or oxypropylene units, preferably up to about 10 30 oxyethylene units. As glycerols, mention may be made not only of glycerol itself, but also of alkyl or alkenyl substituted glycerols, for example glycerols having up to about 20 carbon atoms, preferably up to about 10 carbon atoms, such as 1,3-butane-triol, 1,2,3- *. * 17 pentane-triol, 1/2/3-decane-triol / l / 2/3-hex-2-ene- triol / etc. The unphosphated hydroxyl group of the glycol esters and at least one of the unphosphated hydroxyl groups of the glycerol esters are esterified with a long chain fatty acid.

Suitable phosphoric esters / which include the active phosphatidylcholine or lecithin which are preferred / can be represented by the following general formula (I) or (II):

HC— O-Rl O

\ h2C - / - O — P — O — R (I) 15 "0

rO

"HC-O-R3 HC-O-R2 Ο (II) 20 '" _ _

H2c-O-P-O — R

t

O

wherein R represents a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms and which may be substituted by an amino group of formula -NR4Rj- where R4 and R ,, are each independently hydrogen or an alkyl group of 1 to 4 carbon atoms / or by a quaternized nitrogen atom of formula -NR4R ^ Rg where 30 r4 and R ^ are as defined above and Rg is hydrogen or an alkyl group of 1 to 4 atoms carbon;

Rq is hydrogen or lower alkyl or lower alkenyl 33 is an acyl residue of a long chain fatty acid; 1 * 2 is hydrogen or an acyl residue of a long chain fatty acid; is hydrogen or an acyl residue of a long chain fatty acid; provided that R2 and R3 are not both hydrogen at the same time; and n is a number from 1 to 10.

As used herein / the expression "lower alkyl" or "lower alkenyl" denotes an alkyl or alkenyl group having 1 to 5 / preferably 1 to 4, carbon atoms # such as methyl # ethyl # propyl # butyl # isobutyle # propenyl, etc. The expression "long chain fatty acid" refers to saturated or unsaturated fatty carboxylic acids having approximately 8 to 22 carbon atoms # preferably 10 to 18 carbon atoms # and in particular 12 to 18 carbon atoms # including mixtures such fatty acids. The acyl residue of the fatty acid corresponds to the formula -C-R.

20 5

The preferred phosphoric esters have a structure similar to that of lecithin # in particular of phosphatidyl-choline # namely the structure of an alkylamine- # alkenylamine- # alkylammonium- or alkenyl-ammonium-phosphate of glycol # polyglycol or glycerol of which the molecule has at least one ester group of long chain fatty carboxylic acid.

The stabilizing additive # reducing the viscosity # is used in an effective amount to lower the plastic viscosity of the composition to less than about 800 mPa.s # preferably to less than about 600 mPa.s # for example at around 400 mPa.s. In general # amounts of about 0 # 1 to 3% by weight # based on the total composition # give viscosities within the desired range.

19 "*

In the preferred embodiment, which is given particular interest here, the liquid phase of the composition of the present invention consists mainly or wholly of a liquid synthetic nonionic organic detergent. Part of the liquid phase may, however, consist of organic solvents which can enter, in the composition as dissolving or non-dissolving carriers of one or more of the particulate solid ingredients, as there are for example in enzyme suspensions, perfumes, etc. Additionally, as described in detail below, organic solvents such as alcohols and ethers can be added as viscosity control and anti-gelling agents.

The non-ionic synthetic organic detergents used in the practice of the invention can be any of a wide variety of such compounds which are well known and are for example extensively described in Surface Active Agents by Schwartz, Perry and Berch, Vol. II, published in 1958 by Interscience Publishers, and in McCutcheon's Detergents and Emulsifiers, 1969 annual, the relevant descriptions of which are incorporated here by these 25 references. Generally, nonionic detergents are lipophilic compounds polyalkoxylated by lower alkoxy groups, wherein the desired hydrophilic-lipophilic ratio is obtained by adding a hydrophilic poly (lower alkoxy) group to a lipophilic moiety. A preferred class of the nonionic detergent used is that of the higher alkanols polyalkoxylated by lower alkoxy groups where the alkanol has 10 to 22 carbon atoms and where the number of moles of lower alkylene oxide (2 to 3 35 atoms of carbon) is 3 to 20. Among these materials, it is preferable to use those in which the higher alkanol is a fatty alcohol higher than 10 to 11 or 12 to 15 carbon atoms and which contain 5 to 18 / preferably 6 to 14 lower alkoxy groups per. mole. Of

VS

preferably / the lower alkoxy group is the ethoxy group but, in certain cases / it can be advantageously mixed with the propoxy group, if it is present / often only constitutes a minor proportion (less than 50%). Representative examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per molecule / for example Neodol 25-7 and Neodol 23-6.5 which are products manufactured by Shell Chemical Company / Inc. The first is a condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 carbon atoms / with about 7 moles of ethylene oxide / and the second is a corresponding mixture where the number of carbon atoms of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present is on average about 6.5. Higher alcohols are primary alkanols. Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9 which are both secondary linear alcohol ethoxylates manufactured by Union Carbide Corporation. The first is the mixed ethoxylation product of a secondary linear alkanol of 11 to 15 carbon atoms with seven moles of ethylene oxide and the second is a similar product but where nine moles of ethylene oxide reacted .

5. Higher molecular weight non-ionic over-components are also useful in the present compositions as components of non-ionic detergent, such as Neodol 45-11, which are similar products of condensation of ethylene oxide on alcohols. higher fatty acids, the higher fatty alcohol having 14 to 15 * 21 carbon atoms and the number of ethylene oxide groups being approximately 11 per molecule. These products are also manufactured by Shell Chemical

Company. Another preferred class of useful nonionic surfactants is represented by the well known class in the trade of nonionic surfactants which are the product of the reaction of a higher linear alcohol and a mixture of ethylene oxides and propylene, containing a mixed chain of ethylene oxide and propylene oxide terminated by a hydroxyl group. Examples are the non-ionic surfactants sold under the trademark Plurafac from BASF / such as Plurafac RA30, Plurafac RA40 (a fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide) / Plurafac D25 (a fatty alcohol in C ^ -C. ^ Condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide) / Plurafac B26 and Plurafac RA50 (a mixture in equal parts of Plurafac D25 and Plurafac RA40 ).

70 - In general, when low foaming characteristics are desired, it is advantageous to use the fatty alcohol condensation products with an ethylene oxide-propylene oxide mixture which are represented by the general formula

25 R ° ‘C3H60) p (C2H40) qH

in which R is a primary or secondary residue of straight or branched aliphatic hydrocarbon, preferably an alkyl or alkenyl group, and better still, an alkyl group containing 6 to 20, preferably 10 to ΟΛ 18 and, better still, 12 to 18 carbon atoms, p is a number from 2 to 8, preferably 3 to 6, and q is a number from 2 to 12, preferably 4 to 10. In addition, these surfactants offer the advantage of low gelation temperatures .

35 • * 22

Another class of liquid nonionic surfactants is commercially available from Shell Chemical Company / Inc./ under the trade name Dobanol: Dobanol 91-5 is a C 5 -C 4 fatty alcohol ethoxylated with an average of 5 moles of ethylene oxide and Dobanol 25-7 is a C 1 -C 4 fatty alcohol ethoxylated with an average of 7 moles of ethylene oxide; etc.

In higher alkanols polyalkoxylated with preferred lower alkoxy groups / to obtain the best ratio between hydrophilic and lipophilic moieties / the number of lower alkoxy groups is usually 40% to 100% of the number of carbon atoms present in the higher / preferred alcohol 40 to 60% of this number / and the nonionic detergent often contains at least 50% of this preferred polyalkoxylated higher alkanol.

The higher molecular weight alkanols and various other normally solid detergents and surfactants may contribute to the gelation of the liquid detergent and / / / are therefore preferably omitted or incorporated in limited amounts in the present compositions / although minor proportions can be used for their cleaning properties / etc. With respect to both preferred and less preferred nonionic detergents / the alkyl groups present therein are generally linear although a low degree of tree structure can be tolerated / for example at the atomic level. carbon contiguous to the terminal carbon atom / or distant from two positions of the terminal carbon atom / of the straight chain and opposite of the alkoxy chain / provided that the length of this alkyl branch does not exceed three carbon atoms. Normally the proportion of carbon atoms in such a branched configuration should be minor and rarely exceed 20% of the total number of carbon atoms in the alkyl group. Likewise, although the linear alkyl groups which are joined by the terminal carbon atom to the al-kylene oxide chains are greatly preferred and are considered to give the best combination of detergency, biodegradability and characteristics non-gelling, it can appear in the chain a middle or secondary junction with alkylene oxide.

There is normally only a minor proportion of such alkyl groups, generally less than 20%, but this proportion may be greater, as is the case with the Tergitol mentioned. Furthermore, when propylene oxide is present in the lower alkylene oxide chain, it generally constitutes less than 20%, and preferably less than 10%.

If larger proportions of alkanols whose alkoxylation is not terminal are used, alkanols polyalkoxylated by lower alkoxy groups containing propylene oxide and non-ionic detergent with lower hydrophilic ratio - lipophilic, and if other nonionic detergents are used in place of the preferred nonionic surfactants listed herein, the resulting product may not have as good detergency, stability, viscosity and non-gelling properties as preferred compositions, but the use of viscosity control and antifreeze compounds may also improve the properties of detergents based on such nonionic surfactants. In some cases, for example when using a higher alkanol polyalkoxylated by lower alkoxy groups, of higher molecular weight, often for its detergency, its proportion can be adjusted or limited according to the results of road tests. * .tine to obtain the desired detergent power / while the product still remains non-gelling and of desired viscosity. It has also been found that it is only rarely necessary to use higher molecular weight nonionic surfactants for their detergent properties since the preferred nonionic surfactants described here are excellent detergents and allow further to achieve the desired viscosity of the liquid detergent product without gelation at low temperature.

Mixtures of two or more of these liquid nonionic surfactants can also be used and, in some cases, benefits can be derived from the use of such mixtures.

Another preferred class of non-ionic surfactants is the ethoxylated C12-C13 secondary fatty alcohols having relatively narrow ethylene oxide contents in view of their low gelation temperatures and low dropping points. the range of 7 to 9, and in particular approximately 8, moles of ethylene oxide per mole of fatty alcohol, and the alcohols in Cg-C ^, in particular in C ^ q, ethoxylated by about 6 moles of ethylene oxide.

Furthermore, in the compositions of the present invention, it may be advantageous to include an organic solvent or diluent which can act as a viscosity adjusting and gelling inhibiting agent toward surfactants non-ionic liquids. For this purpose, lower aliphatic alcohols and glycols (C1-C6) such as ethanol, isopropanol, ethylene glycol, hexylene glycol and the like have been used. Polyethylene glycols, such as PEG 400, are also useful diluents. Alkylene glycol ethers, such as compounds 35 sold under the trade names Carbopol and • * 25

Carbitol which have relatively short hydrocarbon chain lengths (C2 ~ Cg) and a low ethylene oxide content (about 2 to 6 EO units per molecule) / are particularly useful solvents for viscosity control and anti-gelation. in the compositions of the present invention. This use of alkylene glycol ethers is described in the U.S. patent application. simultaneously pending N ° 687,815 filed on December 31, 1984 / assigned to the Claimant.

• * • 0 The appropriate glycol ethers can be represented by the following general formula:

R0 (CH2CH20) nH

where R is an alkyl group in Pr®f®rence in C2 ~ C ^ / and n is a number of approximately 1 to 6 / preferably * • 5 rence 1 to 4 / on average.

Particular examples of suitable solvents include monoethylene ethylene glycol ether (C2Hçj-0-CH2CH2OH) / diethylene glycol monobutyl ether (C4Hq-0- (CH2CH20) 2H) / mono-octyl ether tetraethylene glycol (CgH ^ -0- (CH2CH20) ^ H), etc. Diethylene glycol monobutyl ether is particularly preferred.

Another useful antifreezing agent which can be incorporated as a minor component in the liquid phase is a linear aliphatic dicarboxylic acid or monocyclic aliphatic acid / for example the alkyl and alkenyl derivatives of succinic acid or maleic acid and the corresponding anhydrides / or a monocyclic aliphatic dicarboxylic acid. The use of these compounds as anti-gelling agents in in detergent compositions is described in US-A 4,744,916.

35 * 9 "ι · 26

Linear aliphatic dicarboxylic acids have at least about 6 carbon atoms in their aliphatic portion which may be an alkyl or alkenyl group with up to about 14 carbon atoms / a preferred range being from about 8 to 13 carbon atoms, and better still, from 9 to 12 carbon atoms. One of the carboxylic acid groups (-COOH) is preferably linked to the terminal carbon atom (alpha) of the aliphatic chain, and the other carboxyl group is preferably linked to the immediately adjacent carbon atom ( beta) ·, or it can be spaced two or three carbon atoms from the alpha position, that is, be attached to the gamma or delta carbon atoms. Preferred aliphatic dicarboxylic acids are alpha, beta-dicarboxylic acids and the corresponding anhydrides, and particularly preferred are derivatives of succinic acid or maleic acid, which have the general formula: 20 - ^ 0 ^ 0 R1-C-Ct ^ R1 — C — C "^ ^ ° H or

I ^ 0 / -O

C-CQ c-c.

^ OH ^ 0 27 * * in which is an alkyl or alkenyl group of approximately 6 to 12 carbon atoms / preferably 7 to 11 carbon atoms, and better still 8 to 10 carbon atoms.

The alkyl or alkenyl group can be straight or branched. Particularly preferred are straight chain alkenyl groups. R · * "need not represent a single alkyl or alkenyl group / and mixtures of different carbon chain lengths may be presented depending on the starting materials used to prepare dicarboxylic acid.

The monocyclic aliphatic dicarboxylic acid may have a penta- or hexagonal ring with one or two linear aliphatic groups bound to ring carbon atoms. The linear aliphatic groups must have / in total / at least about 6, preferably at least about 8 / and more preferably / at least about 10 carbon atoms / and at most about 22, preferably at most about 18, and more preferably , at most about 15 carbon atoms. When there are two aliphatic carbon atoms attached to the aliphatic ring, they are preferably arranged in the para position with respect to each other. Thus, the preferred aliphatic cyclic dicarbo-xylic acids can be represented by the following structural formula:

T

R3- / \ _R2_cooh

^ - vOOH

Wherein -T- represents -CH2-, -CH =, -CH2 ~ CH2- or -CH = CH-; 2 R represents an alkyl or alkenyl group of 3 to 12 carbon atoms; and 3,28 R represents a hydrogen atom or an alkyl or alkenyl group of 1 to 12 carbon atoms / provided that the total number of carbon atoms 2 3 in R and R is from about 6 to about 22 .

Preferably, -T- represents -CHg-CHg- or -CH = CH-, and in particular -CH = CH-.

2 3 R and R are each preferably alkyl groups of approximately 3 to approximately 10 carbon atoms, in particular approximately 4 to approximately 9 carbon atoms, 2 3 10 the total number of carbon atoms in R and R being from about 8 to about 15. The alkyl or alkenyl groups can be straight or branched, but their chain is preferably straight.

The amount of nonionic surfactant is generally in the range of about 20 to about 70%, especially about 22 to 60%, for example 25%, 30%, 35% or 40% by weight of the composition. The amount of solvent or diluent, if any, is generally limited to 20%, preferably 15%, or for example from 0.5 to 15%, preferably 5.0 to 12%. The weight ratio of the nonionic surfactant to the alkylene glycol ether used as a viscosity control and antifreeze agent, when the latter is present as is the case in the preferred embodiment of the invention , is generally in the range of about 100: 1 to 1: 1, preferably about 50: 1 to about 2: 1, i.e., for example about 10: 1, 8: 1, 6: 1 , 4: 1 or 3: 1.

The amount of dicarboxylic acid gelling inhibitor, if used, depends on factors such as the nature of the liquid nonionic surfactant, for example its gelling point, the nature of the dicarboxylic acid, the other ingredients of the composition which can influence the temperature of gelation, and the conditions of use envisaged * 29 ((for example with hot or cold water / the geographical climate, etc.). In general, it is possible to lower the gelation temperature to a value not greater than about 3 ° C, preferably not greater than about 0 ° C, with amounts of dicarboxylic acid gel inhibitor located in the range of from about 1% to about 30%, preferably from about 1.5% to about 15%, by weight based on the weight of the liquid nonionic surfactant, although in any particular case , the optimal amount can easily be determined by routine experimentation.

The detergent compositions of the invention, according to the preferred embodiment, also comprise as essential ingredient adjuvant detergency salts soluble in water and / or dispersible in water. Suitable typical detergency builders include, for example, those described in U.S. patents. No. 4,316,812, 4,264,466, 3,630,929, 20 and many others. Water soluble alkaline mineral detergent builder salts which can be used alone with the detergent compound or in admixture with other detergency builders are carbonates, bicarbonates, borates, phosphates, polyphosphates, and metal silicates alkaline (it is also possible to use ammonium or substituted ammonium salts). Particular examples of these salts are sodium tripolyphos phate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphos phate, hexametaphosphate sodium, sodium sesquicarbonate, sodium mono- and di-orthophos-phates and potassium bicarbonate. Sodium tripolyphosphate (TPP) is particularly preferred when ingredients containing phosphate

A A

30 are not prohibited on grounds relating to environmental protection. The alkali metal silicates are useful detergency builder salts which also act by making the composition anti-corrosive to parts of the washing machine.

The preferred sodium silicates have Na 2 O / SiO 2 ratios of 1.6 / 1 to 1 / 3.2, in particular approximately 1/2 to 1 / 2.8. It is also possible to use potassium silicates having the same ratios.

Another class of detergency builders is that of water-insoluble aluminosilicates, of the crystalline type or of the amorphous type. Various crystalline zeolites (i.e., aluminosilicates) are described in British Patent No. 1,504,168, the U.S. Patent. No. 4,409,136 and Canadian Patent Nos. 1,072,835 and 1,087,477, which are all incorporated herein by reference with respect to these descriptions. An example of amorphous zeolites useful here can be found in Belgian Patent No. 835,351, and this patent is also incorporated herein by this reference.

The zeolites correspond to the general formula: (M20) x. (Al203) y. (Si02) z.wH20 in which x is 1, y ranges from 0.8 to 1.2 and is preferably 1, z ranges from 1 , 5 to 3.5 or more and preferably 2 to 3, w is 0 to 9 and preferably 2.5 to 6, and M is preferably sodium. A typical zeolite is a zeolite of type A or of similar structure, type 4A being particularly preferred. Preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or more, for example 400 meq / g.

Examples of sequestering alkaline organic detergent builder salts which can be used alone with the detergent or in admixture with other very organic and mineral detergency builders 31 * * are aminopolycarboxylates of alkali metals, ammonium or substituted ammonium, for example sodium and potassium ethylenediaminetetraacetate (EDTA), potassium and sodium nitriloacetates (NTA), and triethanolamine N- (2-hydroxyethyl) nitrilodiacetas. Mixtures of these aminopoly-carboxylates are also suitable.

Other suitable organic type detergency builders include carboxymethylsucciates, tartronates, glycolates and polyacetal carboxylates. Polyacetal carboxylates and their use in detergent compositions are described in U.S. patents. Nos. 4,144,226, 4,315,092 and 4,146,495. Other patents relating to similar detergency builders are the U.S. Patents. No. 4,141,676, 4,169,934, 4,201,858, 4,204,852, 4,224,420, 4,225,685, 4,226,960, 4,233,422, 4,233,423, 4,302,564 and 4,303,777. Patent applications European No. 0 015 024, 0 021 491 and 0 063 399 are also relevant.

The proportion of detergency builder in suspension, relative to the total of the composition is generally in the range of about 10 to 60 percent by weight, especially from about 20 to 50 percent by weight, for example 25 to 40 percent by weight of the composition.

According to an embodiment of the invention, the physical stability of the suspension of the detergent builder compound (s) and any other finely divided solid particulate additive, such as a bleach, pigment, etc., in suspension in the liquid vehicle is greatly improved by the presence of a low density filler, such that the density of the continuous liquid phase is approximately the same as the density of the dispersed particulate solid phase including the low density filler.

The low density filler can be any mineral or organic particulate matter which is insoluble in the liquid phase and any solvents used in the composition and which is compatible with the various components of the composition. In addition, the filler particles must have sufficient mechanical strength to withstand the shear stress which is likely to be encountered during the preparation, packaging, transportation and use of the product.

Suitable particulate fillers which meet the above general criteria have densities, measured at room temperature, in the range of about 0.01 to 0.50, preferably about 0.02 to 0 , 50, and more preferably at most about 0.20, in particular 0.02-0.20, and particle diameters in the range of about 1 to 300 micrometers, preferably 4 or 5 to 200 micrometers, the average particle diameters being between about 20 and 100 micrometers, preferably between about 30 and 80 micrometers.

The types of mineral and organic fillers which have such low bulk densities are generally hollow microspheres or microbeads or at least a very porous solid particulate matter.

For example, mineral or organic microspheres are preferred, such as microspheres of various organic polymers or glass bubbles. Particular, non-limiting examples of organic polymeric material in microspheres include polyvinylidene chloride, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyurethanes, polycarbonates, polyamides and the like. More generally, one can use in the nonaqueous compositions of the present invention one

OC

any of the low density specific gravity fillers described in the aforementioned application GB-2,168,377A on page 4, lines 43-55 / including those referred to by reference to the patents of Moorehouse et al. and Wolinski et al. Apart from hollow microspheres, other low density mineral fillers can also be used / for example aluminosilicate zeolites / spray-dried clays / etc.

However / according to a particularly preferred embodiment of the invention / the light filler consists of a water-soluble material. This has the advantage that / when using the composition for washing soiled fabrics in an aqueous washing bath / the water-soluble particles dissolve and therefore do not settle on the fabrics subjected to washing. On the other hand, the water-insoluble filler particles can more easily adhere or be adsorbed on the fibers or the surface of the fabrics subjected to washing.

As a particular example of such a light filler which is insoluble in the non-aqueous liquid phase of the composition of the invention, but which is soluble in water, there may be mentioned a glass of sodium borosilicate, such as microspheres creu-25 ses available under the trademark Q-Cell, in particular Q-Cell 400, Q-Cell 200, Q-Cell 500, etc. These materials offer the additional advantage of bringing silicate ions into the washing bath which act as anti-corrosion agents.

30

As examples of water-soluble organic materials suitable for the production of low density particles in hollow microspheres, mention may be made, for example, of starch, hydroxyethylcellulose, polyvinyl alcohol and polyvinylpyrrolidone, the latter also providing functional properties by exerting, for example, the function of an agent for suspending soiling when it is dissolved in the aqueous washing bath.

The amount of the low density filler added to the nonaqueous liquid suspension is such that the average / statistically weighted density of the suspended particles and the low density filler is the same as / or little different from, the density of the liquid phase (which includes non-ionic surfactant and other solvents / liquids and dissolved ingredients). In practical terms / this means that the density of the total composition, after the addition of the filler at low density / is the same or about the same as the density of the liquid phase alone / and also that the density of the dispersed phase alone.

Consequently, the amount to be added of low density filler depends on the density of the filler, the density of the liquid phase alone and the density of the total composition except for the filler at low density. For any particular starting liquid dispersion, the required amount of low density filler increases as the density of the filler increases and, conversely, a smaller amount of low density filler is required to achieve a given reduction in density of the final composition as the density of the filler decreases.

The amount of low density charge that is required to equalize the densities of the liquid (known) phase and the dispersed phase can be calculated theoretically using the following equation which is based on the assumption of perfect mixing low density filler and non-aqueous dispersion: M dd -d .. ms _ ms o liq 35 M- d. . d -d J f liq o ms 35 * * OÙ μ Μ

ms represents the mass fraction of M

f low density filler (for example microspheres) to be added to the suspension 5 to make the density of the final composition equal to the density of the liquid; dms = density / for the displacement of liquid, of the load at low density; d ^^ = density of the liquid phase of the sus-1Q pension; dQ = density of the starting composition (that is to say of the suspension before addition of the filler); = mass of the final composition (that is to say after addition of the filler); and

Mms = load mass to be added.

In general, the amount of low density filler which is required to equalize the density of the dispersed phase and the density of the liquid phase is in the range of about 0.01 to 10% by weight, preferably d about 0.05 to 6.0% by weight, based on the weight of the non-aqueous dispersion before the addition of the filler.

Although it is preferable to make the density of the liquid phase equal to the density of the dispersed phase, that is to say d. ^ / Ds £ = 1/0 / to obtain the most high degree of stability, small differences in density, with for example d .. / d ^ = 0.90 to 1.10, especially 0.95 to 1.05 (where d ^ liq sf sf is the final density of the dispersed phase after addition of the charge) still give acceptable stabilities in most cases, which is generally manifested by the absence of phase separation, i.e. the absence of appearance of '' a clear liquid phase, for at least 3 to 6 months or more.

As described above, adding Λ * 36 to the nonaqueous liquid suspension of finely divided solid tissue treatment particles of a quantity of low density filler sufficient to give a statistically weighted density of solid particles and charge particles which is similar to the density of the phase, continuous liquid has the effect of stabilizing the suspension against phase separation. However / the mere fact that the statistically weighted average density of the dispersed phase is similar to the density of the liquid phase does not appear to explain in itself how or why the low density filler exerts its stabilizing influence / since the final composition still includes the relatively dense dispersed solid particles of tissue processing (eg phosphates) which would normally settle while the low density charge would normally rise in the liquid phase.

Although the Applicant does not wish to be bound by any particular theory / it is assumed / and experimental data and microscopic observations seem to confirm it / that the dispersed solid particles of detergent additive / such as the adjuvant particles of detergency / bleach / etc / are positively attracted to and adhere to low density filler particles by forming one or more layers of dispersed particles surrounding the low density filler particles / which forms composite particles which / in fact / behave like isolated unit particles. These composite particles can then be considered to have a density which closely approximates a volume weighted average of the densities of all the individual particles constituting the composite particles: »* 37 d + Zb.

dH + V dB

Π d = -

CP V

1 + rfi

5 VH

where d = density of the composite particle; dH = density of the dispersed phase (heavy particle); dß = charge density (light particle); 10 νβ = total volume of phase particles dispersed in the composite; Vß = total volume of the charge particle in the composite.

However / for the density of the composite particle to be similar to that of the liquid phase / it is necessary that a large number of dispersed particles interact with each of the charge particles τ for example / according to the relative densities / it several hundred to several thousand thousands of the dispersed (heavy) particles must associate with each of the low density filler particles.

Therefore / to obtain all the advantages of the present invention, the average particle diameter of the low density filler must be larger than the average particle diameter of the particles of the dispersed phase / such as a detergency builder / etc. / in order to admit a large number of particles dispersed on the surface of the charge particle. In this regard / it has been found that the ratio of the average particle diameter of the low density filler particle to the average particle diameter of the dispersed particles should be at least 6: 1 / for example from 6: 1 to 30: 1 / in particular from 8: 1 to 20: 1, the best results being obtained with a ratio of approximately 10: 1. Generally satisfactory results cannot be obtained at diameters less than 6: 1 / although some improvement in stability may occur depending on the relative densities of the dispersed particles and the filler particles and the density of the liquid phase.

Consequently / in the preferred range of average particle diameters of 20 to 100 micrometers / in particular from 30 to 80 micrometers / for the low density filler particles / the particles of the dispersed phase must have average particle diameters of approximately 1 to 18 micrometers / in particular from 2 to 10 micrometers. These particle sizes can be obtained by appropriate grinding / as described below.

Although the incorporation of the filler at low density greatly reduces any tendency of the dispersed phase in suspension to settle or to rise or any tendency to the formation of a clear liquid layer at the top of the composition / 20 charging at low density also has the effect of increasing the "plastic viscosity" (knot) of the suspension. Although this increase in viscosity is not necessarily disadvantageous / in many circumstances / nonetheless / the impression and the preference of the consumer requires giving the product a better flowability / i.e. reducing the viscosity plastic. However, this reduction in plastic viscosity should not be achieved at the cost of lowering the flow limit of the non-aqueous suspension / as physical stability would be adversely affected.

According to the present invention / reduction of the plastic viscosity without appreciably lowering the flow limit is achieved by the incorporation of lecithin or other additive of the phosphoric ester /% 39 type as described above. For example, in the absence of the viscosity reducing additive, non-aqueous suspensions containing a low density filler have plastic viscosities in the range of about 500 to 5000 mPa.s. By the addition of lecithin or other phosphoric ester, the viscosity can be reduced by as much as 50% or more, for example to about 200 to 3000 mPa.s, preferably 250 to 1000 mPa.s, and more preferably , 300 to 10,600 mPa.s. The exact amount of additive necessary to reduce the plastic viscosity to a particular value cannot be precisely defined, and it depends on factors such as the initial plastic viscosity, the particular additive and the particular ingredients of the suspension. not aqueous. In general, the desired results are obtained with quantities of the additive reducing the viscosity of approximately 0.1 to 3% by weight, preferably approximately 0.3 to 2% by weight, in particular from 0.5 to 1.5% by weight, relative to the weight of the total composition.

The incorporation of organophilic clay into the non-aqueous suspension of finely divided tissue treatment particles suspended in a liquid non-ionic surfactant, as described in U.S. Patent Application 25. simultaneously hanging N ° 063 199, produces a visco-elastic network which also improves the physical stability of the nonaqueous suspension. The incorporation of lecithin or other phosphoric ester defined above in the amounts indicated provides a further improvement in the physical stability of the non-aqueous suspension.

In the preferred embodiment of the invention, the non-aqueous suspension of tissue treatment additive contains both the low density filler and an organophilic clay. In this preferred embodiment, the incorporation of lecithin or other phosphoric ester within the limits of the amounts specified above reduces the plastic viscosity and helps maintain the visco-elastic network structure imparted by the organophilic clay.

Considering this preferred embodiment, it has been found that under conditions of transport where the compositions containing a low density filler are subjected to the intense and repetitive vibrational forces normally encountered in a rail or truck journey, for example , the filler at low density tends to rise to the upper surface of the composition, while the functionally active solid particles in suspension deposit in a corresponding degree towards the bottom of the container in which the composition is contained.

Although the reason for the adverse effect of the intense vibrational forces has not been fully determined, it can be assumed that the vibrational forces are powerful enough to overcome the weak attraction between the low density charge and the functionally active particles in composite particles as previously described. According to another theory, it is possible that intense vibrational forces cause localized disturbances where the shear stress is greater than the flow limit of the suspension, thereby causing destabilization .

However, regardless of the mechanism by which the low density filler migrates to the upper surface of the liquid suspension, the homogeneity of the liquid suspension composition can be preserved, even under the application of intense vibrational forces, by incorporating into the component, before, during or after the introduction of the low density filler, * * 41 a small amount / generally limited to about 1% of the weight of the composition / of an organophilic modified clay.

The useful organophilic modified clays form a visco-elastic network structure in the composition and it is assumed, although the Applicant does not want to be bound by any particular theory of the mode of action, that this visco-elastic network structure is capable of absorbing intense vibrational forces thereby stabilizing the suspensions, even under these unfavorable conditions, and it is more particularly presumed that the organophilic clay raises the flow limit of the suspension, so that the stress of shear resulting from vi-15 bration does not exceed the flow limit.

In the present compositions, any of the swelling organophilic modified clays with high gelling power which are described in U.S. Patent Applications 20 can be used. simultaneously pending N ° 063 199, filed on June 17, 1987, and N ° 073 551, filed on July 15, 1987.

The modified organophilic clay can be based on a swelling clay modified so as to exhibit a strong gelling power in the liquid organic vehicle. As examples of such swelling clay materials which can be used (after an appropriate modification as described below), there may be mentioned clays of the smectite type, in particular bentonites, for example sodium bentonites and lithic; montmorillonites, for example sodium and calcium montmorillonites; saponites, for example sodium saponites; and hectorites, for example sodium hectorites. Other very representative clays include beidellite 1 * 42 and stevensite. Particularly preferred are clays of the hectorite type, the swelling capacity of which is remarkable.

The aforementioned smectite-type clays are three-layer clays characterized by the ability of the laminated structure to increase its volume by several times by swelling or expansion when it is in the presence of water to form a thixotropic gelatinous substance. There are two main classes of smectite-type clays: in the first class, aluminum oxide is present in the crystal lattice of the silicate; in the second class, magnesium oxide is present in the crystal lattice of the silicate. Atomic substitution with iron, magnesium, sodium, potassium, calcium, etc., can be found within the crystal lattice of smectite clays. It is customary to distinguish clays according to their predominant cation. For example, a sodium clay is a clay of which sodium is the predominant cation. Aluminum silicates in which sodium is the predominant cation are preferred, such as, for example, clays of the bentonite type. Among the bentonites, particular preference is given to those which come from Wyoming (generally called bentonites from the western United States of America or from Wyoming).

The preferred blowing bentonites are sold as industrial bentonites under the trademark Minerai Colloid by Benton Clay Com-30 pany, a subsidiary of Georgia Kaolin Co. These materials, which are the same as those formerly sold under the trademark THIXO-JEL , are bentonites selectively extracted and enriched, and those which are considered to be the most interesting to use are available under the designations Mineral Colloid No. 101, * * 43 etc., corresponding to the products THIXO-JEL No. 1, 2, 3 and 4. These materials have pHs (at a concentration of 6% in water) ranging from 8 to 9.4, maximum free moisture contents of about 8% 5 and densities of about 2.6, and, for sprayed quality, at least 85% (and preferably 100%) of the material passes through a sieve with a mesh size of 0.074 mm. Preferably, the bentonite is such that almost all of its particles (i.e. at least 10 90%, preferably more than 95%, of the particles) pass through a sieve with a mesh opening of 0.044 mm, and better again, all of the particles pass through such a sieve. The swelling capacity of bentonite in water is usually in the range of 2 to 15 ml / gram, and its viscosity, at a concentration of 6% in water, is usually about 8 to 30 mPa.s.

Instead of using a THIXO-JEL or Colloid Ore bentonite, pro-20 products can be used, a minimum of 95% of which is finer than 0.044 mm in diameter (particle size in the dry state) and a minimum is thinner than 0.074 mm in diameter (particle size in the wet state), for example those sold by the American Colloid Company, Industrial Division, under the reference General Purpose Bentonite

Powder-325 mesh. Such hydrated aluminum silicate consists mainly of montmorillonite (at least 90%), with smaller proportions of feldspar, biotite and selenite. A typical analysis, on an "anhydrous" basis, shows 63.0% of silica, 21.5% of alumina, 3.3% of ferric iron (expressed as Fe2 ° 3) '0.4% of ferrous iron ( expressed in FeO), 2.7% magnesium (expressed in Mg), 2.6% sodium and potassium (expressed in Na20), 0.7% calcium (expressed in CaO), 35 5.6% d water of crystallization (expressed as H2O) and “” 44 0.7% of trace elements.

Although bentonites from the western United States of America are preferred, it is also possible to use other bentonites, such as those which can be manufactured by processing bentonites from Italy or analogues, containing relatively low proportions of exchangeable monovalent metals (sodium and potassium), by alkaline substances such as sodium carbonate in order to increase the cation exchange capacities of these products. It is believed that the Na2O content of the bentonite should be at least about 0.5%, preferably at least 1%, and more preferably at least 2%, for the clay to be properly swelling . Preferred inflating bentonites of the types described above are sold under the trademarks Laviosa and Winkelmann, for example Laviosa AGB and Winkelmann G-13. Other examples include Veegum F and Laponite SP, both of which are sodium hectorites, Gelwhite L, a calcium montmorillonite, Gelwhite GP, a sodium montmorillonite and Barasym LIH 200, a lithic hectorite.

The clayey materials of the smectite type as described above are hydrophilic in nature, that is to say that they exhibit swelling characteristics in aqueous media. Conversely, they are organophobic in nature and do not swell in nonaqueous or essentially nonaqueous systems.

Consequently, the organophobic nature of the clayey materials of the smectite type is converted into an organophilic nature. This conversion can be accomplished by exchanging the metal cation of the clay for example Na, K, Li, Ca, etc., for an organic cation, at least on the surface of the clay particles, for example by mixing together l clay, organic cation and water, preferably at a temperature in the range of 20 to 100 ° C / for a period of time sufficient for the organic cation to interpose with the particles of clay, on the surface at least, and then by filtration, washing, drying and grinding. For further details, reference may be made to any of the E.U.A. Nos. 2,531,427, 2,966,506, 4,105,578, 4,208,218, 4,287,086, 4,424,075 and 4,434,076 mentioned above, the descriptions of which are incorporated herein in their entirety by these references.

The cationic organic substance is preferably a quaternary ammonium compound, in particular such a compound having surfactant properties denoting the presence of at least one long-chain hydro-carbonaceous group (for example from approximately 8 to approximately 22 carbon atoms), although surface-active or other tissue-beneficial properties are not required, nor is it essential that the cationic modifier in itself acts as a suspension.

However, any of the cationic surfactant compounds described as useful suspending aids in the U.S. Patent can be used. No. 4,264,466 mentioned above, in columns 23-29, 25 the description of which is incorporated here in its entirety, for modifying the clay material of the smec-tite type in order to make it organophilic. It is also possible to use favorably the cationic nitrogenous organic compounds described in the aforementioned patent No. 2,531,427, or those mentioned in any one of the aforementioned patents, assigned to NL Industries, No. 2,966,506, 4,105,578, etc. ., the descriptions of which are incorporated herein by these references.

The preferred modifiers are the quaternary ammonium compounds corresponding to the formula: il * 46 [r1r2r3r4n] + X “in which R ^ / R £ / R ^ and R4 are each independently hydrogen or a hydrophobic organic radical of the type alkyl / aryl, aralkyl, alkaryl or alkenyl, containing 1 to 3 carbon atoms / preferably 1 to 22 carbon atoms / at least two R groups preferably having 1 to 6 carbon atoms and at least one R / group preferably at most two R / groups having 8 to 22 carbon atoms; X is an anion which may be mineral / such as a halide anion / for example chloride or bromide / sulfate / phosphate / hydroxide or nitrate / or organic such as a methyl sulfate / ethyl sulfate anion or fatty acid residue / for example acetate / propionate; laurate / myristate / palmitate / 15 oleate or stearate.

Examples of preferred organophilic modifiers are quaternary ammonium compounds containing one or two long chain alkyl groups (for example in cg-ci8 'especially in cio - (' 18 ^ * ExamP -'- are representative of tensio compounds - quaternary ammonium assets with a single long chain include stearyl trimethylammoniura chloride / (tallow alkyl) chloride - trimethylammonium / benzyl stearyl dimethylammonium chloride / benzyl chloride 25 (hydrogenated tallow alkyl) ) -dimethylammonium / benzyl-ketyl-dimethylammonium chloride / and the bromides / iodides / sulphates / methosulphates / acetates and corresponding salts of the other anions previously mentioned. Typical representative examples of quaternary ammonium compounds with two chains include dimethyl distearyl ammonium chloride / dimethyl diketyl ammonium chloride / dimethyl stearyl ketyl ammonium chloride / dimethyl di (tallow alkyl) chloride / ammonium chloride dimethyl myristyl ketylammonium loride / and bromides / - * * 47 iodides, sulfates, methosulfates, acetates and corresponding salts of the other anions mentioned above. Other representative compounds include octadecylammonium chloride # 5-hexadecyl ammonium acetate etc. Dimethyl-alkylarylammonium salts are the most preferred quaternary ammonium compounds having regard to their high polarity.

Aside from quaternary ammonium compounds # other organic cations containing tarnisable nitrogen can also be used to form the organophilic clay particles. For example # there may be mentioned imidazolinium compounds such as # for example, l- (2-hydroxyethyl) -2-dodecyl-1-benzyl-2-imidazolinium chloride, and compounds containing a nitrogen heterocycle such as pyrrolidones # pyridines # morpholines # etc. # substituted by a long-chain hydrocarbon radical # for example N # N-octadecyl-morpholinium chloride.

The rate of substitution with the organi-20 cation must only be sufficient to give the clay the organophilic property required to obtain the best stabilizing characteristic desired. In general # depending on the nature of the organic substituent # this rate can range from approximately 10 to 100% # of pre-25 ference 20 to 100% # or for example from 30% # 40% # 50% or 60% # of the useful base exchange capacity that the clay material has. Usually # and preferably # an amount of the organic compound is used that is at least sufficient to cover or coat the surface of the clay particles.

Suitable organophilic clays which can be used in the present invention are commercially available, such as, for example, the products sold under the trademark Bentone by NL Indus-35 tries # New York # New York, such as Bentone 27 which is * * 48 a clay of the hectorite type (magnesium montmorillonite) modified by benzyl-dimethyl chloride (hydrogenated tallow alkyl) -ammonium, and Bentone 38 ′ which is a clay of the hectorite type modified by chlo- 5 dimethyl-dioctadecylammonium rure. Other suppliers of organophilic clays include / for example: Sud-Chemie / Munich / R.F.A.; Laviosa / Livorno / Italy; Laporte / France; and Perchem / UK.

Organophilic clays are used only in minor amounts / generally less than 1/0% by weight / preferably less than 0/7% by weight / relative to the weight of the total composition. Normally / amounts of at least about 0/1% by weight / preferably 0/2% by weight / such as for example 0/25% 0/3% / 0/35% or 0/4% by weight / produce slightly thixotropic / stable / non-aqueous liquid suspensions / detergency builder or other water-soluble / finely divided tissue treatment agent.

on The modified organophilic clay can be incorporated into the nonaqueous liquid dispersion of the particulate ingredients in suspension / either directly in the powder state / or after having been previously dispersed in a part of the liquid vehicle of the suspension / for example liquid nonionic surfactant, the latter method being preferred. In addition, whether it is added to the suspension directly in the form of powder or in pregelified form in a part of the liquid vehicle, the organophilic clay can be added to the suspension before or after grinding the suspension up to a particle size of not more than 15 micrometers, preferably not more than 10 micrometers, and more preferably between 1 and 10 micrometers, and more preferably between 4 and 8 microns.

4 * 49

In a preferred embodiment, the organophilic clay is firstly dispersed in a part of the liquid nonionic surfactant constituting the main liquid vehicle, or in a different nonionic surfactant, or in a solvent or diluent as described previously, or in any suitable mixture of one or more surfactants and / or solvents and / or diluents. The previously dispersed clay suspension may, if necessary, be subjected to grinding in a mill which exerts a strong shear to form an organophilic clay pre-gel. Separately, the remaining particulate solid is suspended in the liquid nonionic surfactant and optional diluent (s) and / or solvents, and is also subjected to grinding. This clay pre-gel and the suspension of particulate material can be ground to the desired final average particle size before mixing together, or the pre-gel and suspension can be mixed and then subjected to a new grinding. In the latter case, the particulate matter in suspension can contribute more to the attrition of organophilic clay particles.

An additional advantage of this pre-fered embodiment of the present invention in which the organophilic clay is subjected to a milling step is that the incorporation of lecithin or other phosphoric ester reduces the viscosity of the suspension of clay previously dispersed, with or without other particulate solid matter. Thus, the grinding step is greatly facilitated and the use of processing aids or the execution of a heating step no longer becomes necessary.

In all the previous embodiments where the organophilic clay is subjected to A * 50 grinding so as to form an organophilic clay gel, the clay is added separately from the filler at low density because this the latter must not be subjected to intense crushing or shearing forces. In addition, it is preferable that the low density filler be added as the last component of the composition, and under conditions which minimize the shear forces applied to the low density filler while still ensuring uniform distribution of the charge throughout the composition. To achieve this, it has been found convenient to mix all of the ingredients, including organophilic clay when used as described above, with the exception of the low density filler, and form a thickened suspension. , then subject the suspension to a mixing operation under low shear using a vane mixer of the helical type rotating at a speed of 2000 to 5000 rpm, so as to create a cavity (vortex) at center of the mixing container, and then add the low density filler near the top of the vortex to ensure that the filler disperses evenly throughout the composition.

In addition to the initial benefits that lecithin provides as a viscosity reducing agent and rheological stabilizer, its use, in particular, provides several other benefits. For example, due to its amphoteric nature, lecithin can interact with the nonionic surfactant constituting the liquid phase to enhance the detergent power of the nonionic surfactant. Lecithin, which has two fatty acid radicals and a quaternary ammonium group, can also improve the flexibility of the treated tissue in its presence. Leci-35 thine can also serve as a sequestering agent for 4 * 51 heavy metals and can therefore act as a bleach stabilizer. These other advantages can make lecithin and other phosphoric esters useful additives for use in the nonaqueous suspensions of solid particles of functionally active additive for laundry / even if these suspensions contain no charge at low density / nor organophilic clay.

Since the compositions of the present invention are generally very concentrated and can therefore be used in relatively low doses / it is often advantageous to supplement any detergency builder of the phosphate type (for example sodium tripolyphosphate) with an adjuvant secondary determination such as a polymeric carboxylic acid having a strong calcium binding power in order to inhibit encrustation which could / if not / be caused by the formation of an insoluble calcium phosphate. Such secondary detergency builders are also well known in the art. For example / one can mention Sokolan CP5 which is a copolymer of an approximately equal number of moles of methacrylic acid and maleic anhydride / completely neutralized to form its sodium salt. The amount of the secondary detergency builder is generally limited to approximately 6% by weight / or for example from 0/25 to 4% / as 1%, 2% or 3% / relative to the total weight of the composition . Obviously the present compositions can be prepared without any phosphate-type detergency builder in cases where this is required by constraints aimed at environmental protection.

Aside from detergency builders / various other detergent builders or additives may be present in the detergent product / to provide it with additional desired properties, whether functional or aesthetic. Thus, it is possible to include in the composition minor amounts of anti-deposition agents, for example polyvinyl alcohol, fatty amides, sodium carboxymethylcellulose or hydroxypropylmethylcellulose, generally in quantities limited to 10% by weight. ; optical brightening agents, such as brightening agents for cotton, polyamide and polyester fabrics, for example compositions based on stilbene, triazole and benzidine-sulfone, in particular a substituted triazinyl-stilbene sulfone, a naphtotriazole- stilbene sulfone, a benzidine sulfone, etc., the most preferred being the combinations of stilbene and triazole. Typically, the optical brightener can be used in an amount limited to about 2% by weight, preferably 1% by weight, such as 0.1-0.8% by weight.

Brightening agents such as ultramarine blue may also be used enzymes, preferably proteolytic enzymes such as subtilisin, bromelain, papain, trypsin and pepsin, as well as amylase-like enzymes, enzymes of the lipase type, and mixtures thereof; bactericides, for example tetrachlorosalicylanilide and hexachloro-prene; fungicides; dyes; pigments (dispersible in water); preservatives; ultraviolet absorbing agents; anti-rejuvenation agents such as sodium carboxymethylcellulose, a C] _2-C22 alkyl alcohol complex with a C] _2-C18 alkyl sulfate, pH enhancers and pK buffers; color preserving bleaches; a perfume ; and defoamers or foam suppressants, for example silicon compounds.

Bleaching agents are broadly classified, for convenience, as chlorine bleaching agents 4 ″ 53 and oxygen bleaching agents. Chlorine bleaches are typically represented by sodium hypochlorite (NaOCl) / potassium dichloroisocyanurate (59% active chlorine) and trichloroisocyanuric acid (95% active chlorine). Oxygen bleaches are preferred and are represented by co-compounds which release hydrogen peroxide in solution. Preferred examples include sodium and potassium perborates, percarbonates and perphosates, and potassium monopersulfate. Perborates / in particular sodium perborate monohydrate / are particularly preferred.

The peroxygen compound is preferably used in admixture with an activator for this compound. Suitable activators which can lower the effective action temperature of the peroxidized bleach are described / for example / in the U.S. Patent. No. 4,264,466, or in column 1 of the U.S. patent. No. 4,430,244. Polyacylated compounds are preferred activators; of these / compounds such as tetraacetylethylenediamine (TAED) and penta-acetylglucoses are particularly preferred.

Other useful activators include / for example / acetylsalicylic acid derivatives / ethylidene benzoate-acetate and its salts, a carboxy-late-ethylidene acetate and its salts / an alkyl- or alkenyl-succinic anhydride / tetraacetylglycourile (TAGU) / and derivatives of these activators. Other useful classes of activators are described / e.g. 30 pie, in U.S. patents. N ° 4 111 826, 4 422 950 and 3 661 789.

The bleach activator usually interacts with the peroxygen compound to form a bleaching peroxyacid in the wash water. It is preferable to incorporate a sequestering agent of high complexing power to inhibit any undesirable reaction between this peroxyacid and hydrogen peroxide in the washing solution in the presence of metal ions. The preferred sequestering agents are capable of forming a complex with the 2+ Cu ions in such a way that the stability constant (pK) of the complexation is equal to or greater than 6, at 25 ° C. in water having a force. ionic of 0/1 mole / liter / the pK being conventionally defined by the formula: pK = -log K, where K represents the equilibrium constant. Thus / for example / the pK values for the complexation of the copper ion with nitrilotriacetic acid (NTA) and ethylene diamine tetraacetic acid (EDTA) under the conditions specified are 12/7 to 18 respectively. / 8. Suitable sequestering agents include / for example / in addition to those mentioned above / the compounds sold under the trademark Dequest / such as / for example / diethylene triamine pentaacetic acid (DEPTA) / diethylene triamine acid -pentamethylene phosphonic (DTPMP) and ethylene diamine-tetramethylene phosphonic acid (EDITEMPA).

In order to avoid loss of the bleaching peroxide / for example sodium perborate / as a result of an enzymatic decomposition / for example under the effect of a catalase type enzyme / the compositions may additionally contain an inhibiting compound enzyme / ie a compound capable of inhibiting the enzymatic decomposition of bleaching peroxide.

Suitable inhibitors are described in the U.S. Patent. No. 3,606,990.

As particularly interesting inhibitory compounds, mention may be made of hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred nonaqueous compositions of the present invention, appropriate amounts of the inhibiting hydro-xylamine salts may be as low as about 0/01 to 0/4%. However / in general / appropriate amounts of enzyme inhibitors are limited to about 15%, or for example from 0/1 to 10%, relative to the weight of the composition.

Although this is not essential to obtain an acceptable stability of the product, it is also within the scope of the present invention to include other suspension stabilizers / rheological additives and antifreeze agents. For example / it is possible to add aluminum salts of higher fatty acids / in particular aluminum stearate / to the composition as described in the patent of 1 5 E.ü.A. No. 4,661,280 / the description of which is incorporated herein by this reference / for example in an amount of 0 to 3% by weight / preferably from 0 to 1% by weight.

Another potentially beneficial stabilizer for use in conjunction with the low density filler is an acidic organic phosphorus compound having an acidic -POH group as described in U.S. patent application. simultaneously pending 'No. 781 189 filed September 25, 1985 / assigned to the Plaintiff / whose description is incorporated here by this reference. The organic phosphorus acid compound can be / for example / a partial ester of phosphoric acid and an alcohol such as an alkanol having a lipophilic character due to the fact that it has / for example, more than 5 carbon atoms , for example 8 to 20 carbon atoms. A particular example is a partial ester of phosphoric acid and of a ci6 ci8 ci * ErnPhiphos 5632 Marchon is a product consisting of about 35% monoester and 65% di-ester. Amounts limited to about 3%, preferably 1%, of the acidic phosphoric compound are sufficient if used.

As described in the U.S. patent application. simultaneously pending N ° 926 851 deposited on November 5, 1906 / whose description is incorporated here by this reference / can be incorporated into the composition / to further improve its rheological properties / a nonionic surfactant having been modified / so as to convert a free hydroxyl group · in a fragment comprising a free carboxyl group / being for example a partial ester of a nonionic surfactant and of a polycarboxylic acid. For example / sufficient quantities of such an acid-terminated nonionic surfactant are limited to 1 part per part of the nonionic surfactant or, for example, from 0/1 to 0/8 part.

Suitable ranges for the amounts of these optional detergent additives are as follows: enzymes - 0 to 2% # including 0/1 to 1/3%: 20 corrosion inhibitors - about 0 to 40% / preferably 5 to 30% ; anti-foaming agents and foam suppressants - 0 to 15% / preferably 0 to 5% / for example 0/1 to 3%: thickening and dispersing agents -0 to 15% / for example 0/1 to 10%, preferably 1 25%; anti-redeposition or suspension agents for soiling and anti-yellowing agents - 0 to 10% / preferably 0/5 to 5%; colorants / perfumes / brighteners and brighteners · - in total 0 to about 2% / preferably 0 to about 1%; pH modifiers and 50 pH buffers - 0 to 5% / preferably 0 to 2%; bleaching agent - 0 to about 40% / preferably 0 to about 25% / for example 2 to 20%; bleach stabilizers and bleach activators - 0 to about 15% / preferably 0 to 10% / 55 for example 0/1 to 8%; enzyme inhibitors - 0 to 57 1 * 15%, for example 0/01 to 15%, preferably 0.1 to 10%; sequestering agent with high complexing power - at most about 5%, preferably 0.25 to 3%, for example 0.5 to 2%. The additives will be chosen to be compatible with the main constituents of the detergent composition.

In a preferred embodiment of the invention, as described above, the mixture of the liquid nonionic surfactant and the solid ingredients (other than the low density filler) is subjected to grinding, for example grinding sand or ball grinding. Grinders of the attrition type are particularly useful, such as those sold by Wiener or Netzsch, in which the particle sizes of the solid ingredients are reduced to less than about 18 micrometers, for example to an average particle size of 2 to 10 micrometers or even lower (for example, 1 micrometer). Preferably, less than about 10%, and especially less than about 5%, of all of the suspended particles have particle sizes greater than 15 microns, preferably 10 microns. In view of the fact that the energy cost increases as the particle size decreases, it is often preferable that the average particle size is at least 3 micrometers, in particular about 4 micrometers. Compositions with dispersed particles of such a small size have improved stability against separation or sedimentation during storage. Other types of mills can also be used, such as tooth mills, pin mills, and the like.

In the grinding operation, it is preferable that the proportion of solid ingredients is high enough (for example at least about 40%, such as about 50%) for the solid particles to settle. are in contact with each other and are not substantially isolated from each other by the liquid nonionic surfactant. Grinders which use grinding balls (ball mills) or similar movable grinding elements have given very good results. So we can use a laboratory mill operating by attrition working by loads / containing grinding balls in steatite of 8 mm in diameter.

10 For an operation on a larger scale / one can use a mill operating in continuous mode in which there are grinding balls of 1 mm or 1.5 mm in diameter working in a very small gap formed between a stator and a rotating rotor at a relatively high speed (for example a CoBall mill), when using such a mill, it is advantageous to first pass the mixture of non-ionic surfactant and solid ingredients through a mill which does not run not such a fine grinding (for example a colloid mill) in order to reduce the particle size to less than 100 micrometers (for example to about 40 micrometers) before the grinding step to an average particle diameter of less than about 18 or 15 micrometers which takes place in the ball mill 25 operating in continuous mode.

Alternatively, the solid particles in the pulverulent state can be finely ground to the desired size before mixing with the liquid matrix, for example in a fluid jet mill.

The final compositions of the present invention are non-aqueous liquid suspensions, generally having non-Newtonian flow characteristics. The compositions, after the addition of the filler at low density, are often slightly thi-xotropic, that is to say that they exhibit reduced viscosity under applied stress or shear and behave from a rheological point of view substantially according to Casson's equation. The final compositions are characterized by a flow limit of between 5/5 and 45 pascals / more commonly between 10 and 35 pascals / such as 15/20 or 25 pascals. In addition / after the addition of lecithin or phosphoric ester / the compositions have viscosities at room temperature / measured using an LVT-D viscometer with a spindle No. 4 at 50 rpm / ranging from '' about 200 to 3000 mPa.S / ordinarily about 250 to 1000 mPa.S / and they can flow easily / without generally requiring the application of forces or jolts. Thus, the compositions of the present invention can be conveniently packaged in normal containers / such as vials / jars or other rigid or flexible glass or plastic containers / and be dispensed directly from these containers into the aqueous bath. of washing / for example in an automatic washing machine / in usual doses such as 1/4 to 1/2 cup / for example 1/2 cup / per load of laundry to be washed (weighing for example 1.4 to 6, 8 kg), usually in 30 to 68 liters of water. The preferred compositions remain stable (the liquid phase separation not being greater than 1 or 2 mm, and generally zero) when they are left to stand for periods of 3 to 6 months or more / even when being subjected to tremors.

It is to be understood that the term "non-aqueous" / as used in this specification means an absence of water, but however, small amounts of water, for example limited to about 5%, of prefe about 2%, can be tolerated in the f * 60 compositions and, therefore, "nonaqueous" compositions can include these small amounts of water, whether added directly or as a carrier or solvent for the composition. one of the other ingredients 5 of the composition.

The liquid tissue treatment compositions of the present invention can be packaged in conventional glass or plastic containers, and also in disposable packaging, such as "pods" and disposable sachets which are described in the US patent application simultaneously pending N ° 063 199 filed on June 17, 1987, assigned to the Applicant, the description of which is incorporated here by this reference. The invention will now be described by means of the following nonlimiting Example in which all the proportions and percentages are expressed by weight, unless otherwise indicated. In addition, the pressure used is atmospheric pressure, unless otherwise indicated.

Example

A reinforced non-aqueous liquid detergent composition according to the invention is prepared by mixing and finely grinding up to approximately 4 micro-25 meters the following ingredients, with the exception of the Q-Cell filler, in the following approximate quantities, then adding the Q-Cell charge to the resulting dispersion with stirring. To add the light load, the ground dispersion is mixed under low shear, using a vane agitator of the helical type rotating at around 3500 rpm to generate a cavity (vortex) in the center of the mixing container, and the Q-Cell filler particles are added near the top of the vortex to cause the filler particles to disperse uniformly throughout the composition while keeping the shear forces which could cause the hollow microspheres to rupture. A composition I is thus obtained. A composition II serving as a control is prepared by proceeding in the same manner as described above / except that the lecithin is omitted. A second control composition II-1 is prepared by proceeding in the same manner as for control composition II, except that the Bentone - * - 0 27 is added afterwards to the remaining ingredients in the same mixing container as the Q-Cell charge particles. A control composition III is prepared by proceeding in the same manner as for, composition I, except that the Q-Cell 400 and the lecithin are omitted.

Quantity (% by weight) (I) II (control)

Non-ionic surfactant (1) 36.45 36.3

Diethylene glycol monobutyl ether 8.8 9.8 20 Sodium tripolyphosphate (hydrated) 28.70 29.1

Sokolan HC 9786 (2) 2.0 1.9

Bentone 27 (3) 0.3 0.3

Sodium perborate monohydrate 10.5 10.6 Tetraacetylethylenediamine 4.5 4.3 25 Carboxymethylcellulose 1.0 1.0 DEQUEST 2066 (4) 1.0 1.0

Enzyme (amylase and proteolytic mixed) 0.55 0.5 Q-Cell 400 (5) 4.0 4.0

Perfume 0.5 0.5 30 T1O2 (rutile) 0.4 0.4

Optical brightener 0.3 0.3 Soy lecithin 1.0 100.00 100.00 35 Viscosity (mPa.s) 400 800 * - * 62 (1) -Supplied by BASF ï mixed condensate of propylene oxide (4 moles) and ethylene oxide (7 moles) on a fatty alcohol containing 13 to 15 carbon atoms 5 (2) Copolymer of methacrylic acid and maleic anhydride (3) Hectorite clay , modified by dimethylbenzyl chloride (hydrogenated tallow alkyl) -ammonium with 35% of exchanged cations, supplied by NL Industries (4) Diethylene triamine-pentamethylene phosphonic acid (5) Hollow microspheres of sodium borosilicate glass - particle size interval, 10-200 micrometers; average particle size, 75 micro-15 meters; effective density, 0.16-0.18.

The compositions I, II and II-1 are stored overnight in a transparent plastic container. At the end of the first day, and after aging for 7 days, 15 days, 30 days and 60 to 20 days, the flow limit and the plastic viscosity of each composition are measured. The results are given respectively in Table I and Table II.

Table I

FLOW LIMIT (Ba) WITH AGING

25 Composition _Duration of aging (days) 1 7 15 30 60 I 11.3 12.2 12.2 12.7 II 8.9 7.8 7.0 5.4 4.2 II-l 10.8 9, 4 7.6 6.2 30 35 1 # 63

TABLE II

PLASTIC VISCOSITY (mPa.s) WITH AGING Composition Duration of aging (days) 1 7 15 30 60 5 ---- - I 390 400 400 420 II 750 800 800 830 870 II-l 600 600 650 700 III 200 230 250 270 270 10 From the above results / it can be seen that the incorporation of 1% lecithin into the nonaqueous suspension stabilized by the low density filler / organophilic clay strongly stabilizes the aged composition while maintaining / and even by slightly elevating it / its flow limit / and lowering the plastic viscosity by about 50%.

Although the Applicant does not wish to be bound by any particular theory concerning the mode of action / it is assumed that the lecithin acts in such a way as to stabilize firmly the flow limit of the composition by strengthening / thanks to the phosphate group, the connections established between Bentone platelets (organophilic clay). In addition, it appears that the quaternary ammonium group (-N ^ CH ^ g) of the constituent phosphatidyl-choline is substituted or fixed on Bentone platelets.

Thus, it can be seen that the addition of small amounts of lecithin or of phosphoric esters of analogous structure, in particular the compounds in which the phosphoric ester fragment comprises a terminal quaternary ammonium nitrogen atom, linked to the phosphate group by through 1 or more carbon atoms, preferably 2 to 6 carbon atoms, to a non-aqueous suspension containing at least one of a low density filler and an organophilic clay,

* AT

64 significantly improves the physical stability of nonaqueous suspensions / even under energetic vibrational forces, while reducing the plastic viscosity so that the suspension can flow easily.

5 If the Example above is repeated, similar results are obtained by replacing the 4% of Q-Cell 400 with 1% of Expancel (polyvinylidene chloride microspheres; particle size range, 10 to 100 micrometers; particle size average, 40 micrometers; density, 0.03). Likewise, similar results are obtained by replacing the nonionic surfactant with Plurafac RA20, Plurafac D25, Plurafac RA50, Dobanol 25-7 or Neodol 23-6.5. Similar results are obtained by repeating the Example above, except that in place of Bentone 27, Bentone 28 (hectorite-type clay, modified with dimethyl-diocta-decylammonium chloride) is used.

If, in composition I, the amount of lecithin is reduced to 0.3% by weight, the plastic viscosity that amounts to 500 mPa.s, which corresponds to a product which can still be poured easily.

"

Claims (21)

1. A non-aqueous liquid tissue treatment composition / characterized in that it comprises (a) a non-aqueous liquid comprising a nonionic surfactant, (b) solid particles of functionally active bleaching additive, suspended in said non-aqueous liquid, at least one of (c) and (d), namely (c) a low density filler in an amount sufficient to make the density of the continuous liquid phase substantially equal to the density of the phase of suspended particles which includes the low density filler and the functionally active solid particles in suspension, thereby inhibiting the deposition of suspended particles when the composition is at rest, and (d) an organophilic clay in an amount suitable to inhibit phase separation when the composition is subjected to intense vibrational forces, and (e) lecithin or a phosphoric ester of glycol, polyglycol, glycerol or substituted glycerol, to reduce vi scosity and further stabilize the rheological properties of the composition. 2. Composition according to claim 1, characterized in that the component (e) is a lecir thine. 3. Composition according to Claim 1, characterized in that the component (e) is a phosphoric ester corresponding to the formula (I) or (II): / R ° \ 30. HC ~ Oj-Rl 0 \ h2C - / - OPOR (I) "O 35 4 4b 66 R0 HC-0-R3 HC-0-R9 Ο (II) 5. n H2c-0 - P- 0— R 0 in which R represents a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms and which may be substituted by an amino group of formula -NR4Rj where R ^ and R ^ are each independently hydrogen or a group alkyl of 1 to 4 carbon atoms / or by a quaternized nitrogen atom of formula 4. Composition according to claim 3/30 characterized in that the component (c) is present there. 5. Composition according to claim 3, characterized in that the component (d) is present there. 6. Composition according to claim 3, characterized in that the components (c) and (d) are both present. 4 and 67 7. Composition according to claim 1 / characterized in that the quantity of component (e) is sufficient to reduce the plastic viscosity of the composition to a value situated in the range from approximately 200 to approximately 1000 mPa.s. 8. Composition according to claim 1 / characterized in that the quantity of component (e) is sufficient to reduce the plastic viscosity of the composition to a value situated in the range from approximately 300 to approximately 600 mPa.s. 9. Composition according to claim 6, characterized in that the low density filler consists of hollow glass or plastic microspheres, the density of which is in the range of about 0.02 to 0, 5. 10. Composition according to claim 9, characterized in that the low density filler consists of water soluble borosilicate glass microspheres. 11. Composition according to claim 6, characterized in that the organophilic clay consists of a swelling clay of the smectite type, modified with a nitrogenous compound containing at least one long-chain hydrocarbon group having approximately 8 to approximately 22 carbon atoms. 12. Composition according to claim 7, characterized in that said nitrogenous compound is a quaternary ammonium compound. 13. Composition according to Claim 12, characterized in that the quaternary ammonium compound is a compound corresponding to the formula: [Rir2r3r4n] + X ~ in which R2, R3 and R4 are each independently hydrogen or a group alkyl, alkenyl, aryl, aralkyl or alkaryl having 1 to 22 carbon atoms, "68 * Has two at least from R4 having 1 to about 6 carbon atoms and two at most from R ^ to R ^ having about 8 to about 22 carbon atoms; and X is a mineral or organic anion. 14. Composition according to claim 1, characterized in that the non-aqueous liquid constitutes approximately 30% to approximately 70% by weight of the composition and the solid particles in suspension constitute approximately 70% to approximately 30% by weight of the composition. 15. Composition according to claim 14, characterized in that the non-aqueous liquid constitutes approximately 40% to 65% by weight of the composition and the solid particles in suspension constitute approximately 60% to 35% by weight of the composition. 15 -NR.RcR ^ - where R „and Rr are as defined above and 4 5 6 4 5 Rg is hydrogen or an alkyl group of 1 to 4 carbon atoms; Rq is hydrogen or lower alkyl or lower alkenyl; 16. Composition according to claim 1, characterized in that it comprises, by weight: approximately 30 to approximately 50% of nonionic surfactant of the alkoxylated fatty alcohol type î approximately 0 to approximately 20% of alkylene glycol ether as a viscosity control and antifreeze agent; about 15 to about 50% of detergency builder particles; about 0 to about 50% in total of one or more optional detergent additives selected from the following: enzymes, enzyme inhibitors, corrosion inhibitors, foam suppressants, soil suspending agents, anti-yellowing agents, colorants , perfumes, optical brighteners, brighteners, pH modifiers, pH buffers, bleaches, bleach stabilizers and sequestering agents 7 about 0.01 to about 10% low density microsphere filler hollow, based on the weight of the composition before the addition of the filler 7 4 Ä 69 about 0.2 to about 0.7-% of organophilic modified clay; and about 0.1 to 3% lecithin or an alkyl-5 amine-, alkenylamine-, alkylammonium- or alkenylammonium- glycol phosphate, polyglycol, glycerol or substituted glycerol the molecule of which contains at least one acid ester group long chain fatty carboxylic. 17. Reinforced thickened nonaqueous liquid detergent composition for large laundering works, characterized in that it comprises, by weight: approximately 3 to -about 40% of a liquid nonionic surfactant which is a mixed condensation product of ethylene oxide and propylene oxide on a fatty alcohol having about 12 to about 18 carbon atoms; about 25 to about 40% of an alkaline metal phosphate-type detergency builder salt; about 5 to about 12% of a solvent of the alkylene ether glycol type as a viscosity control and antifreezing agent -, about 2 to about 20% of a peroxide bleach; about 0.1 to about 8% of a bleach activator: up to about 2% of enzymes; up to about 10% of agents for suspending soil, anti-deposition and anti-yellowing r 30 up to about 5% of a sequestering agent with high complexing power ï up to about 2% of one or more selected ingredients among dyes, perfumes and optical brightening agents; The solid components of said composition having an average particle size in the range of about 2 to 10 microns / not more than about 10% of the particles having a particle size greater than 10 microns; About 0.05 to about 6% of mineral or organic filler particles having a density of about 0.01 to 0.50 and an average particle diameter of about 20 to 80 microns; about 0.2 to about 0.7% of an organophilic modified smectite-type clay, in which about 10 to 100% of the base-exchange capacity of smectite-type clay has been replaced by a compound cationic organic nitrogen having at least one long chain hydrocarbon group of about 8 to about 22 carbon atoms; said composition, after the addition of said filler particles, having a viscosity in the range of about 500 to 5000 mPa.s; and about 0.1 to 3% lecithin, so that the viscosity of the composition is reduced to a value in the range of about 200 to 1000 mPa.s. 18. Composition according to claim 17, characterized in that the filler particles are · constituted.by hollow glass microspheres of 25 sodium borosilicate. 19. A method for cleaning soiled tissue, characterized in that it involves bringing the soiled tissue into contact with the liquid tissue treatment composition of claim 1, in an aqueous washing bath. 20. The method of claim 18, characterized in that the contacting is carried out in an automatic washing machine. R 1 is an acyl residue of a chain fatty acid; R2 is hydrogen or an acyl residue of a long chain fatty acid; R3 is hydrogen or an acyl residue of a long chain fatty acid; provided that R2 and R3 are not both hydrogen at the same time; and n is a number from 1 to 10. 21. Method for stabilizing a suspension of a dispersed phase of finely divided solid particles ^ 4 71 divided in a non-aqueous liquid phase against the deposition of said solid particles whose densities are greater than the density of the liquid phase / characterized in that it consists in adding to the suspension of said solid particles a finely divided charge whose density is less than the density of the liquid phase / in an amount such that the density of the solid particles dispersed together with said charge is substantially equal to the density of the liquid phase / an organophilic modified clay in an amount suitable for imparting a visco-elastic network structure to the suspension thereby inhibiting phase separation from suspended solid particles or filler particles / even when the 15 composition is subjected to vigorous vibration / and lecithin or an alkylamine- / alkenylamine- / alkylammonium- or alkenylamm onium-phosphate of a glycol / polyglycol / glycerol or substituted glycerol, the molecule of which contains at least one ester group of long-chain fatty carboxylic acid ester 20 / so as to reduce the plastic viscosity of the suspension and to stabilize the structure of visco-elastic network of the suspension.