AU623859B2 - Concentrated softening compositions - Google Patents

Abstract

A concentrated, liquid, water-soluble softening composition for textiles contains: a) from 10 to 50 % by weight of at least one softening agent A chosen from the quaternary ammonium salts having at least two long C8-C22 alkyl chains, if necessary interrupted by an ester, ether, or amide group; imidazolinium salts; and the reaction products of fatty acids with polyamines chosen from the group of hydroxyalkalenediamines and dialkylenetriamines, in which the alkyl and alkylene groups contain from 1 to 3 carbon atoms, b) from 0,1 to 1 % by weight of at least one cationic compound B chosen from the cationic compounds whose solubility in aqueous or aqueous-alcoholic medium is greater than that of the softenig compound A, c) from 2 to 35 % by weight of at least one solvent C, d) if necessary, adjuvants and/or other classic additives, and e) water for the complement, the content of solvent C being greater than 10 % by weight when the content of compound A is between 10 and 20 % and the content of compound B is between 0.1 and 5 %. Application to the washing of textiles.

Description

AU-A 19625/88 ORGANISATION MONDIAL3 DEi LA PR011RltM INTUiLECTUCiLIX B~ureau interflinioiml PCT 0 DEMANDE INTERNATIONALE PUl3L1EI EN VERTU DU TRAITE DEI COOPERATION EN MATIERE DE BRCVETS (PCT) (51) Classification Inteornationale dcs brcvcts 4 (1 Ninir Ic 5 Nu.o 0W 88/10294 CUIID 1/645, 3/43 Al (3 nod~pbyto~tj' 29 d&cembrc 1988 (29,12.88) (21) Nuin(ro do la deinande Internationale: PCT/FR88/00318 (74) Mandatalre: CABINH T GERMAIN ET MVAUREAU; (22) Date do d~p6t International: I6juin 1988 (16.06.88) B.PNo301 -92LynCdx3(F) (31) Nunro dc la dernando prioritalre: 87/08378 (1 tt fins U P S (32) Date dc priorlt6: 16 juin 1987 (16,06.87) Pubike (33)Pay deprioit FR A vec rapport de rechierche interuationale, (71) Dilposant (pour lous les Etats d~sign~s satif US): CO- TELLE S.A. [FR/FR]; 122, avenue du G~n~ral-Leclerc, F-92 103 Bou logne- Bill ancou rt A..J .1 A 3 (72) Inventeurs; et 1nventeurs/Diposants (US seuletnent) CHARPIN, Da- ASRLA niel [FR/FR]; D'HERBOMEZ, Isabelle [FR/FR]; 63, ASRLA avenue Gambetta, F-94 100 Saint-Maur (FR1). ROZAT, I N18 Mich~1e [FR/FR]; 14, rue Gaston-Monmousseau, F-19JN98 94200 Ivry-sur-Seine (FR1). T C (54) Title: CONCENTRATED SOFTENING COMPOSITIONS (54)Tltre: COMPOSITIONS ADOUCISSANTES CONCENTREES (57) Abstract A concentrated, liquid, water-soluble softening composition for textiles contains: a) from 10 to 50 %by weight of at least one softening agent A chosen from the quaternary ammonium salts having at least two long C 8

-C

22 alkyl chains, if necessary interrupted by an ester, ether, or amide group; imidazolinium salts; and the reaction products of fatty acids with polyamines chosen from the group of hydroxyalkalenediamines and dialkylenetriamines, in which the alkyl and alkylene groups contain from I to 3 carbon atoms, b) from 0,1 to I by weight of at least one cationic compound B chosen from the cationic compounds whose solubility in aqueous or aqueous-alcoholic medium is greater than that of the softenig compound A, c) from 2 to 35 by weight of at least one solvent C, d) if necessary, adjuvants and/or other classic additives, and e) water for the complement, the content of solvent C being greater than 10 by weight when the content of compound A is between 10 and 20 and the content of compound B is between 0.1 and 5 Application to thle washing of textiles.

(57) Abrig6 L'invention concerne une composition concentr~e d'adoucissant pour textiles, liquide et diluable di leau. Cette composition contient: a) de 10 Ai 50 en poids J'au momns un agent adoucissant A choisi parmi les sels d'ammontium quaternaire ayant au moins deux chaines alkyle tongues en C 8

-C

22 6ventuellement interrompues par un groupe ester, 6ther ou amide; les sels d'imidazolinium,' et les produits de reaction des acides gras avec des polyamines choiisies dans le groupe des hydroxyalkylalkyl~inediamines et des dial kyl~netriami nes, dans lesquelles les groupes alkyle et alkyl~nes contiennent de I At 3 atonies de carbone, b) de 0,1 Ai I 6/ en poids d'au momns tin compos6 cationique B choisi parmi les composes cationiques dont la solubilit6 en milieu aqueux ou hydroalcoolique est sup~rieure Ai la solubillt6' du compos6 adoucissant A, c) de 2 At 35 en poids d'ati momns un solvant C, d) 6ventuellement des adjuvants et/ou autres additifs classiques, et e) de Ileau pour le compl~ment, la teneur en solvant C e6tant sup~rieure A 10 en poids lorsqu'on a simultanement une teneur en compose A comprisa entre 10 et 20 et une teneur en compos6 B comprise entre 0,1 et 5 Application au lavage du lingo, 4 I 1 F "Concentrated softening compositions" The present invention relates to fabric-softening compositions, in particular aqueous compositions containing relatively large quantities of softeners of the cationic type, intended to be used in the rinsing cycle of laundry operations. More specifically, the invention relates to concentrated aqueous compositions of cationic softeners whose viscosity is adjustable and which are clear and capable of being diluted with water, the viscosity of the diluted compositions obtained being adjustable. The concentrated compositions have a viscosity which is low, making it possible to pour them, and durable, and are capable of being diluted, especially with tap water, which water may have any temperature. The diluted compositions thus obtained have a viscosity which is acceptable to the housewife and greater than that of the concentrated composition.

Concentrated compositions of cationic softeners which can be diluted with water are already known.

French document A-2,451,960 describes compositions containing a softening agent which is a dialkyldimethylammonium chloride or a dialkylmethylethoxyammonium chloride mixed with a non-softening agent which is an alkyldimethylbenzylammonium chloride, and containing isopropyl alcohol and water. This document states that the compositions contain the non-softening agent in a concentration which is higher than 33% by weight and the softening agent in a concentration which is lower than the concentration of the non-softening agent. The compositions described contain from 25% to 12.5% of dialkyldimethylammonium chloride or 12.5% of softening dialkylmethylethoxyammonium chloride and from about 33% to 50% of non-softening alkyldimethylbenzyl- Sammonium chloride. The purpose aimed at according to this publication is to obtain transparent compositions.

However, such compositions are expensive and have a limited efficiency, because they contain a large quantity of non-softening cationic agent.

French document A-2,540,901 describes compositions containing from 15 to 50% of dialkyldimethylammonium salts, i rii I

I

2 from 10 to 50% of hydrophilic solvents, the weight ratio between the solvents and the dialkyldimethylammonium salts being between 0.7 and 2.3.

These compositions may optionally contain solubilizing aids which are, for example, hydrophilic nonionic surfactants. The compositions are intended to be diluted with water.

The purpose aimed at according to this document is to obtain concentrated softener compositions which can be diluted with cold or luke-warm water. In the examples it is always mentioned that such compositions contain a nonionic hydrophilic solubilizing agent.

However, the concentrated compositions described in these publications have the disadvantage that, by dilution, they provide compositions which are very fluid and scarcely viscous.

French document A-2,523,606 describes concentrated fabric-softening compositions comprising from 8 to 20% of I a softener of the imidazolinium type and from 0.5 to 5% of i 20 an either conventional or dicationic quaternary ammonium compound. These compositions are presented as being stable even at low or high temperatures. They may optionally be supplemented by secondary proportions, namely of between i 0.5 and 10%, of other ingredients, among which are lower alkanols. The compositions of this type are not clear and have a viscosity which increases with time, during storage.

i European document A-60,003 describes concentrated I fabric-softening compositions comprising from 8 to 22% of a cationic softener, from 0.6 to 3% of at least one watersoluble polyalkoxylated ammonium salt and from 0.2 to 5% of y a fatty acid ester of a polyol. The object aimed at is to obtain stable compositions whose viscosity does not substantially vary, even at high temperature and over long periods of storage. The thus formed compositions are not clear.

European document A-199,382 describes softening compositions which, so as not to lose their effectiveness when they are brought into contact with the anionic or nonionic r 3 detergents contained in washing products, comprise from 3 to 35% of a mixture of: 10-92% of the product of the reaction of higher fatty acids with a selected polyamine, 8-90% of cationic nitrogenous salts having a single long acyclic aliphatic chain having from 15 to 22 carbon atoms, and 0-80% of cationic nitrogenous salts having at least two chains of this type or one chain of this type and an arylalkyl ring.

French document A-2,295,122 describes concentrated fabric-softening compositions which are stable with regard to temperature, do not jellify and have a disinfectant action. These compositions comprise from 30 to 60% of a cationic softening agent, from 5 to 20% of a cationic disinfectant, from 5 to 20% of a nonionic dispersing agent and from 15 to 40% of lower alkanols. It is expressly stated that the presence of nonionic dispersing agents is essential for the concentrated product to disperse properly in cold water.

European document A-40,562 describes concentrated softener compositions containing a cationic softening agent and nonionic agent in a ratio of between 10/1 and 3/2, alcohol and water; the object is to obtain concentrated softener compositions which are capable of being diluted with cold or luke-warm water.

Housewives who dilute such concentrated compositions with tap water in order to prepare diluted compositions to be stored prior to use prefer to obtain diluted compositions having a viscous appearance. But the temperature of the tap water varies. Thus, it may vary between +5 and +25 0 C. It has been found that, when the water temperature is of the order of +5 0 C, the viscosity of the diluted compositions is too high and when the housewife pours the diluted composition into a trough provided for this purpose in an automatic washing machine, the diluted composition, due to its high viscosity and its tendency to form flocculates, may block the duct taking the softening composition to the rinsing trough. Moreover, the dispersion of the diluted compositicn in the rinsing water is more difficult when the

I

V4 concentrated composition is diluted with cold water, for example having a temperature of about +5 0

C.

The invention is aimed at overcoming these drawbacks.

The problems to be solved are as follows: Obtaining a softening composition with concentrated softening agents which: is clear and stable during storage between -15 and 0

C,

is capable of being diluted with town water, even when cold, contains the lowest possible quantity of alcohol, has a viscosity which is low, allowing it to be poured, and durable, and provides a diluted composition which is stable during storage and whose viscosity is acceptable to the housewife and higher than that of the concentrated composition.

None of the prior art documents has described or hinted at this viscosity problem of the diluted compositions, high enough to be accepted by the user, but low enough to be able to flow through the pipes of washing machines, which compositions have a homogeneous physical structure and do not form agglomerates which may block the pipes, and are readily dispersable in the rinsing water.

I The present invention provides concentrated, clear fabric-softening compositions which may be diluted with i cold water without forming particles or agglomerates capable of blocking the small-diameter pipes and which are stable during storage, both in the concentrated and in the diluted state.

The invention relates to a concentrated textilesoftening composition capable of being diluted with water, characterized in that it contains: a) from 10 to 50% by weight of at least one softening agent A, selected from among quaternary ammonium salts having at least two long alkyl chains having from 8 to 22 carbon atoms, possibly interrupted by an ester, ether or amide group; imidazolinium salts; and products from the i reaction of fatty acids with polyamines selected from the i

S'

4a group of hydroxyalkylenediamlnes and dialkylenetriamlnes wherein the alkyl and alkylene groups contain from 1 to 3 carbon atoms; b)from 0,1 to 10% by weight of at least one catlonic compound B selected from among quaternary ammonlum salts and polyammonium salts, said compound comprising a single long alkyl chain having from 8 to 22 carbon atoms, the weight ratio A/B being greater than 1, i I o.*

I-

group-ef-hydr-oxyalya-lkylened-i-amines-and-ialkyen triamines wherein the alkyl and alkylene groupsg ontn from 1 to 3 carbon atoms, b) from 0.1 to 10% bw g t of at least one cationic compound B, se -t from among cationic compounds whose soblt y in an aqueous or hydroalcoholic medium is greater -a-e-sey--te f-tenng-ompound-A c) from 2 to 35% by weight of at least one solvent C, d) optionally adjuvants and/or other conventional additives, and e) water to complement the composition, the proportion of solvent C being greater than 10% by weight Swhen there is at the same time a proportion of compound A of between 10 and 20% and a proportion of compound B of between 0.1 and The compositions preferred according to the invention are such that they contain from 20 to 50% of softening compound A, from 0.1 to 10% and more advantageously still from 0.1 to 3% of compound B and from 10 to 30% by weight of solvent C.

The cationic softening agents A of the compositions according to the invention are described specifically in the article "Cationic Surfactants in Laundry Detergents and Laundry Aftertreatment Aids" Vol. 61, No 2 (February 1984), and may be selected from among compounds having the following general formulae: R (I)A R R 3 N X R2 R4 wherein R1 and R 2 may be similar or different and are selected from among alkyl or alkenyl groups having from 8 to 22 carbon atoms, which may be branched and which may be substituted by ether, ester or amide groups, R3 and R 4 may be similar or different and are selected from among alkyl groups having from 1 to 3 carbon atoms, benzyl groups which may be substituted, or groups -(CnH 2 nO)xH ^n 2 x *A4m 6 wherein n 2 or 3 and x 1 to X being a quaternization anion. It may be selected, for example, from the group of halides, methylsulfate, ethylsulfate, acetate, phosphate, carbonate, lactate.

Examples of the compound of formula are dimyristyldimethylammonium chloride, distearyldimethylammonium chloride, distearyl-2-hydroxypropylmethylammonium methylsulfate and oleylstearyldimethylammonium ethylsulfate; (II) N. CH 2 C 2

R

5 -C SN- CH

R

6

C

2

H

4 -N _C-R X

I

R

7 0 wherein R 5 and R8 are similar or different and are selected from among alkyl and alkenyl groups having from 8 to 22 carbon atoms,which may be branched,

R

6 is selected from substituted or non-substituted alkyl groups having from 1 to 4 carbon atoms, R7 is selected from among hydrogen or a substituted or non-substituted alkyl group having from 1 to 4 carbon atoms, X- is a quaternization anion. It may be selected, for example, from the group of halides, ethylsulfate, methylsulfate, acetate, phosphate, carbonate, lactate; (III) N__CH

R-C

N CH 2 12

C

2 H -N-C N 2 X R I CH -CH 2 11 2 2 ~1 :_1^-~1111_~1 wherein R 9 and R12 are similar or different and are selected from among alkyl or alkenyl groups having from 8 to 22 carbon atoms, which may be branched, Ri0 and R11 are similar or different and are selected from substituted or non-substituted alkyl groups having from 1 to 4 carbon atoms, X is a quaternization anion. It may be selected, for example, firoii the group of halides, methylsulfate, ethylsulfate, acetate, phosphate, carbonate, lactate.

(IV) O H R14 H O

R

1 3

-C-N-C

2

H

4

-N-C

2

N-C-R

5

X

CH

3 -iJ wherein R13 and R15 are similar or different and are selected from among alkyl or alkenyl groups having from 8 to 22 carbon atoms, which may be branched, R14 is selected from hydrogen, methyl or ethyl groups and the group -(CnH 2 nO)xH wherein n is equal to 2 or 3 and x is between 1 and and X is a quaternization anion selected, for example, from the group of halides, methylsulfate, ethylsulfate, acetate, phosphate, carbonate, lactate.

Examples of compounds of formula (II) are the methylsulfate of l-tallow-amidoethyl-2-tallow-imidazolinium, of l-methyl-l-oleylamidoethyl-2-oleyl-imidazolinium, l-methyl-l-palmitoleylamidoethyl-2-palmitoleyl-imidazolinium, l-methyl-l-tallow-amidoethyl-2-tallow-imidazolinium, 1-methyl-l-hydrogenated tallow-amidoethyl-2-hydrogenated tallow-imidazolinium.

Examples of compounds of formula (III) are the methylsulfate of 1-ethylene-bis(2-stearyl-l-methylimidazolinium), 1-ethylene-bis(2-oleyl-l-methylimidazolinium), 1-ethylene-bis(2-tallow-l-methylimidazolinium).

8 Examples of compounds of formula (IV) are: the methylsulfate of di(2-hydrogenated tallow-amidoethyl)-hydroxyethylammonium, of di(2-hydrogenated tallow-amidoethyl)dimethylammonium and of methyl-di( 2 -palmitylamidoethyl)hydroxyethylammonium.

The agents B according to the invention are selected in practice from among quaternary ammonium salts and polyammonium salts, which compounds may optionally contain a single long alkyl chain having from 8 to 22 carbon atoms.

The agents B are preferably selected from among salts of quaternary mono- or poly-ammonium or imidazolinium compounds, which may be bactericides, or a mixture thereof.

Thus, the cationic compounds B according to the invention may be selected from among compounds having the following general formulae: 1 6 (V)N Y R17 (VI) R R 19 R8- N -CH2 Y R wherein R is an aliphatic or hydroxyalkoxy group having from 1 to 4 carbon atoms, which may be polyoxyalkylated,

R

16 is selected from among alkyl or alkenyl groups having from 8 to 22 carbon atoms and preferably from 8 to 10 carbon atoms, which may be branched and which may be substituted by ether, ester or amide groups, R17 is selected from among alkyl or alkenyl groups having from 1 to 4 carbon atoms, which may be branched, R18 is selected from among alkyl or alkenyl groups having from 8 to 18 carbon atoms, and preferably from 12 to 16 carbon atoms, 9 R19 and R20 are selected from hydrogen or a halogen, Y is a quaternization anion. It may be selected, for example, from the group of halides, methylsulfate, ethylsulfate, acetate, phosphonate, carbonate, lactate.

Examples of agents B of formulae or (VI) are: lauryldi.methylbenzylammonium chloride, alkyldimethylbenzylammonium chloride wherein the alkyl radical has from 12 to 18 carbon atoms, trimethyldodecylbenzylammonium chloride, methyl-bis(2-hydroxyethyl)-oleylammonium chloride, methyl-1-capryl-2-caprylamido-3-ethylimidazolinium methylsulfate.

The cationic compounds B may also be selected from among compounds having the following general formula: (VII) R R 22 22 21-N (CH+2 n N R22 X iR R R22 22 m wherein R21 is an aliphatic group having from 8 to 22 carbon atoms, which may be branched and which may be unsaturated, R22 is selected from among hydrogen, alkyl, hydroxyalkyl and hydroxyalkoxy groups having from 1 to 4 carbon atoms, n is an integer ranging between 1 and 6, m is an integer ranging between 1 and X is a quaternization anion. It may be selected, for example, from the group of halides, methylsulfate, ethylsulfate, acetate, phosphate, carbonate, lactate.

Examples of agents B of formula (VII) are: A1 1 N-(tallow derivative)-N,N,N ,N -tetramethyl-1,3-propanediammonium dimethosulfate, N-(tallow derivative)-N ,N1-trimethyl-1,3-propanediammonium dimethosulfate, i 35 N-oleyl-N,NN ,N LN -pentamethyl-1,3-propanediammonium dimeth o.sulfate, n 1 1 N-(tallow derivative)-N,N,N ,N ,N -pentamethyl-1,3-propanediammonium dimethosulfate, 11 N-stearyl-NN,N ,N ,N -pentamethyl-1,3-propanediammonium dimethosulfate, N-stearyloxypropyl-N N1-tri(3-hydroxypropyl)-1,3propanediammonium diacetate.

Agents B preferred according to the invention are coco-bis(2-hydroxyethyl)methylammonium chloride, for example ETHOQUAD 0/12, containing 25% of isopropanol and manufactured by AKZO, or oleyl-bis(2-hydroxyethyl)methylammonium chloride, for example ETHOQUAD 0/12, containing 25% of isopropanol and manufactured by AKZO.

The compounds B according to the invention may also be selected from among compounds having the general formulae (III) and (IV) mentioned above, wherein R5 and R 8 g

R

9 and R 12 R13 and R15 are selected from among alkyl or alkenyl groups having from 6 to 14 carbon atoms, which may be branched.

The solvents C according to the invention may be selected from among hydroxylated solvents or mixtures thereof, for example alcohols, polyols, polyol ethers, polyol polyethers; the preferred solvents are isopropanol, isobutanol, n-propanol, 2-methyl-2,5-pentanediol, 1,2-propyleneglycol and the monomethyl ether of monopropyleneglycol.

According to a preferred embodiment of the invention, the softening agent is l-oleyl-amidoethyl-2-oleylimidazolinium methosulfate, for example dissolved in isopropanol or dissolved in 1,2-propyleneglycol in a proportion of of softener and 25% of alcohol.

Such preferred compounds are marketed by REWO under the trade names REWOQUAT W 3690 and REWOQUAT W 3690/PG.

Another preferred compound is di-tallow-2-hydroxypropylmethylammonium chloride sold under the name PRAEPAGEN WKL by HOECHST.

Without wanting to be tied down to any theory, it is believed that compound B makes it possible, in combination with solvent C, to fluidify the composition and make it clear; moreover, the inclusion of compound B makes it possible to reduce the proportion of solvent C, but only to a certain extent, for too large a proportion of compound B

SI

11 would have the undesirable effect of lowering the viscosity of the diluted composition.

To prepare the compositions according to the invention, one can simply: in the case of ingredients which are liquid at ambient temperature, mix these cold in any order, in case one of the ingredients is not liquid at ambient temperature, heat this ingredient to cause it to melt and add the other ingredients to the molten mass obtained, observing the precautions of use, and preferably adding the solvent C first and water last.

The invention makes it possible to achieve the objects set out above.

The viscous and stable diluted compositions which can be obtained with the present invention may be prepared by diluting the aforesaid concentrated compositions with town water, even when cold; the dilution ratio is preferably between 1:2 and 1:10 and advantageously 1:4 for a concentrated composition containing about 20% of active cationic softening material A.

The compositions according to the invention, used in suitable quantities in the final rinsing cycle following the washing of loads of laundry in a household washing 4machine, confer an entirely adequate suppleness to the laundry.

The invention will be described in greater detail in the following examples, which do not limit it in any way. In these examples, all percentages are given by weight in relation to the weight of the total composition. The percentages given refer to the active material, without taking S into account the solvents usually present in the commercial products containing them.

12 Comparative example The following composition is prepared: DSIM-MS(*) LDMBAC(**) 0% Isopropanol 14% Perfume 1% Water quantity enough for 100% An unstable gel is obtained.

DSIM-MS: l-tallow-amidoethyl-2-tallow-imidazolinium methylsulfate.

LDMBAC lauryldimethylbenzylammonium chloride.

Example 1 The following composition is obtained by mixing: Agent A: DSHPMAC(*) 18.35% Agent B: ODHMAC(**) 1.65% Solvent C: Isopropanol 15 Perfume 0.77% Dye solution) 0.6 Water quantity enough for 100% di-tallow-2-hydroxypropylmethylammonium chloride sold under the name PRAEPAGEN WKL by the Company HOECHST.

i oleyl-bis(2-hydroxyethyl)-methylammonium chloride, sold under the name ETHOQUAD 0/12 by the Company AKZO.

The composition obtained is fluid and clear. Its vis- I 25 cosity (measured on a Brookfield viscosimeter with a No 1 rotor, at 6 rpm) is 35 mPa.s. After adding three times its volume of tap water to this composition, a diluted composition is obtained whose viscosity (measured under the same conditions) is 210 mPa.s after 1 week and 480 mPa.s after 2 months.

The concentrated composition is stable at ambient temperature and at 40°C for more than a year. At -15 0 C, the concentrated composition assumes the consistency of a gel, which is however rather fluid and which disappears to revert i 35 to a completely fluid composition after returning to ambient temperature.

Example 2 The following composition is prepared by mixing: DSHPMAC 20 ODHMAC 2.04% Isopropanol 7.10% Dipropyleneglycol 18 Perfume 0.97% Dye solution) 0.6 Water quantity enough for 100% The composition thus obtained is fluid and clear. It is stable and has a viscosity (measured on the Brookfield viscosimeter with a No 2 rotor, at 12 rpm) of 50 mPa.s after 1 day and still the same after 1 month.

After adding three times its volume of tap water to this composition, a stable diluted composition is obtained whose viscosity (measured on the Brookfield viscosimeter with a NO 1 rotor, at 6 rpm) is 203 mPa.s after 1 day and 486 mPa.s after 1 month.

Example 3 The following composition is prepared by mixing: DSHPMAC 20 ODHMAC 2.04% Isopropanol 7.10% Monomethyl ether of monopropyleneglycol 14 Perfume 0.97% Dye solution) 0.6 Water quantity enough for 100% The composition obtained is fluid and clear. It is stable and has a viscosity (measured on the Brookfield viscosimeter with a No 2 rotor, at 12 rpm) of 40 mPa.s after 1 day and 30 mPa.s after 1 month. After adding three times its volume of tap water to this composition, a stable diluted composition is obtained whose viscosity (measured on the Brookfield viscosimeter with a N° 1 rotor, at 6 rpm) is 549 mPa.s after 1 day and 900 mPa.s after 1 month.

14 Example 4 The following composition is obtained by mixing: DOIMMS(*) 50 ODHMAC 10 Isopropanol 3.34% Perfume 0.97% Dye solution) 0.8 Water quantity enough for 100% l-oleylamidoethyl-2-oleylimidazolinium methosulfate sold under the name REWOQUAT W-3690 by the Company REWO.

The composition obtained is fluid and clear. Its viscosity (measured on the Brookfield viscosimeter with a NO 2 rotor, at 12 rpm) is 30 mPa.s after 4 days. After adding nine times its volume of tap water to this solution, a diluted composition is obtained whose viscosity (measured on the Brookfield viscosimeter with a N o 1 rotor, at 6 rpm) is 132 mPa.s after 4 days.

Example The influence of the temperature of the water with which a concentrated composition is diluted on the viscosity of the diluted composition is studied.

The following compounds are mixed: DOIMMS ODHMAC 2% Isopropanol Perfume 1% Water quantity enough for 100% This concentrated composition is diluted with three times its volume of water. The viscosities are measured with a Brookfield viscosimeter with a No 1 rotor, at 6 rpm.

As a function of the temperature of the diluting water, diluted compositions are obtained whose viscosities are given in Table 1.

1:

'I

S:;

r~ t' 1 Table 1 Temperature of Viscosity of the diluting water 0 C) diluted compositions (mPa.s) 180-200 20 75-100 25- 15- It can be seen, therefore, that the compositions according to the invention have a viscosity greater than 100 mPa.s for temperatures of diluting water of less than Now, a viscosity higher than 100 mPa.s, preferably 100-200 mPa.s, is a viscosity which is seen by the housewife as the mark of an effective product.

Example 6 The influence of the weight ratio between the quantity of softening agent A and the quantity of non-softening cationic compound B is studied.

The following compositions are prepared:

DOIMMS

ODHMAC

Isopropanol Perfume 1% Water quantity enough for 100% The quantities of agent A, agent B and isopropanol are varied, the quantity of perfume always being equal to 1% by weight of the composition.

These compositions are diluted with water of 20 0 C to obtain diluted compositions containing 5% by weight of softening agent A. The viscosities of the diluted compositions thus obtained are measured on the Brookfield viscosimeter with a No 1 rotor, at a speed of 6 rpm. The following results are obtained (cf. Table 2): 16 Table 2 3b 3c 3d 3e 3f 3g Example 3a A 15 15 20 20 30 30 B 17 0.1 11 2 32 0.1 0.1 C 5 20 6.7 17 10 15 Ratio A/B 0.88 150 0.90 10 0.93 300 400 mPa.s 0 160 0 100 0 130 140 Viscosity of the diluted composition It can be seen, therefore, that when the percentage by weight of non-softening compound B is greater than the percentage by weight of softening compound A, the viscosity of the diluted composition containing 5% of softening compound is low. In contrast, when very little non-softening agent B has been added, for example 100 to 400 times less for the quantity of softening agent A, the viscosities of the diluted compositions containing 5% by weight of softener A are between 100 and 160 mPa.s.

Example 7 The influence of a cationic non-softening agent in an aqueous composition of softening agent is studied, at equal concentrations, compared to the influence of a nonionic agent.

a) The following concentrated composition is prepared: 16% of N-methyl-N,N-di(P-C 14

-C

18 acyloxyethyl)N-phydroxyethylammonium methylsulfate sold under the name STEPANTEX Q 185 by the company STEPAN EUROPE, 11% of isopropyl alcohol 4% of a mixture of nonionic surfactant and likewise nonionic emulsifier, 1% of perfume, quantity enough for 100% of water.

The composition obtained has a viscosity allowint it to be poured. This composition is diluted with three times its volume of water, the water having a temperature of 10 0

C

or 20°C. A diluted composition is thus obtained which forms lumps and whose viscosity is very high: L J 17 1000 mPa.s (measured on the Brookfield viscosimeter, with a No 1 rotor, 6 rpm).

b) The following concentrated composition is prepared: 16% of DOIMMS, 4% of ODHMAC, 11% of isopropanol, 1% of perfume, quantity enough for 100% of water.

This composition is diluted with three times its volume of water, the temperature of the diluting water being 10 0

C.

The viscosity of the diluted composition is 10 mPa.s (measured in the same manner as for Example 4a).

Thus, it can be seen that the technical function of the non-softening cationic agent is different from the technical function of the nonionic agent. Depending on the quantity of cationic non-softening agent in the concentrated composition, the viscosity of the diluted composition can be adjusted to a value which is acceptable to the housewife (preferably between 50 and 900 mPa.s).

In fact, examples 3b and 4b show that, for a composition containing approximately 15% of softening agent A and 0.1% of non-softening agent B, the viscosity of the diluted composition is 160 mPa.s, whereas for a composition containing 4% of non-softening agent B, the viscosity of the diluted composition is 10 mPa.s.

Moreover, when the diluted compositions 4a and 4b obtained from the concentrated compositions are dispersed in cold water, it is seen that the diluted composition 4a is dispersed with great difficulty and that it is necessary to stir by hand for several dozen seconds to obtain a good dispersion in water. In contrast, the diluted composition 4b is dispersed very easily in water at 10 0 C (in less than seconds).

18 Example 8 The following composition is prepared: of DSHPM-AC, 2% of ODHMAC, 13% of 1,2-propyleneglycol, !i 11% of isopropanol, 1% of perfume, quantity enough for 100% of water.

This composition is diluted with three times its volume of water. The temperature of the diluting water is 100C.

A stable diluted composition is obtained whose viscosity, measured in the same manner as in the previous j examples, is 260 mPa.s.

i

Claims (9)

1. 2. Composition according to claim 1, characterised in that it contains from 0.1 a to 3% by weight of compound B.
2. 3. Composition according to either of claims 1 and 2, characterised in that it contains from 10 to 30% by weight of solvent C.
3. 4. Composition according to any one of claims 1 to 3, characterised in that the softening agents A are selected from among compounds having the following general formulae: ii Ri il AT 0 i'J I wherein R 1 and Ra may be the same or different and are selected from among alkyl or alkenyl groups having from 8 to 22 carbon atoms, which may be branched and which may be substituted by ether, ester or amide groups, R 3 and R 4 may be the same or different and are selected from among alkyl groups having from 1 to 3 carbon atoms, benzyl groups which may be substituted, or groups (CnH2nO)xH wherein n 2 or 3 and x 1 to X- being a quaternization anion; N CH 2 R C24-N C-R a X 0 R 7 o S" wherein Rs and Ra are the same or different and are selected from among alkyl and alkenyl groups having from 8 to 22 carbon atoms which may be branched, Re is selected from among substituted or non-substituted alkyl groups having from 1 to 4 carbon atoms, R 7 is selected from among hydrogen or substituted or non-substituted alkyl groups having from 1 to 4 carbon atoms, X- is an anion having the same meaning as in formula N C J (III) R -c N _CH I C\ -2 10 C 2H -N-C 2 ,2 X R 11 "2-C2 I I 21 wherein R9 and R 12 are the same or different and are selected from among alkyl or alkenyl groups having from 8 to 22 carbon atoms which may be branched, Rio and R 11 are the same or different and are selected from among substituted or non- substituted alkyl groups having from 1 to 4 carbon atoms, SX is an anion having the same meaning as in formula (IV) 0 I i H 0 i3 I II RI3-C-'-CH4-N-CK.H 4 N-C-,3 X- Ii- wherein R 13 and R 15 are the same or different and are selected from among the group formed by alkyl or alkenyl radicals having from 8 to 22 carbon atoms which may be branched, R 14 is selected from the group formed by hydrogen, the radicals methyl, ethyl and (CnH2nO)xH wherein n is equal to 2 or 3 and x is between 1 and and X- is an anion having the same meaning as in formula Composition according to any one of claims 1 to 4, characterised in that the *:softening agent A is 1-oleyl-amidoethyl-2-oleylimidazolinium methosulfate. S6. Composition according to any one of claims 1 to 4, characterised in that the softening agent A is methyl-bis(tallow-amido ethyl)-2-hydroxyethylammonium .methosulfate.
4. 7. Composition according to any one of claims 1 to 4, characterised in that the softening agent A is di-tallow-2-hydroxypropyl methylammonium chloride.
5. 8. Composition according to any one of claims 1 to 7, characterised in that compound B is selected from among compounds of the following general formulae: S 1 7 R W L I 22 (VI) 19 R I 20 wherein R is an aliphatic or hydroxyalkoxy radical having from 1 to 4 carbon atoms, which may be polyoxyalkylated, R 16 is selected from among alkyl or alkenyl groups having from 8 to 22 carbon atoms and preferably from 8 to 10 carbon atoms, which may be branched and which may be substituted by ether, ester or amide groups, R 17 is selected from among alkyl or alkenyl groups having from 1 to 4 carbon atoms, o which may be branched, R 18 is selected from among alkyl or alkenyl groups having from 8 to 18 carbon atoms and g j preferably from 12 to 16 carbon atoms, R 19 and R 2 o are selected from among hydrogen or a halogen, Y- is an anion having the same meaning as in formula Rom 1 2 2 wherein Ral 21 is an aliphatic radical having from 8 to 22 carbon atoms, which may be branched and which may be unsaturated, R 22 is selected from among hydrogen, alkyl, hydroxyalkyl, hydroxyalkoxy groups having from 1 to 4 carbon atoms, n is an integer ranging from 1 to 6, 23 m is an integer ranging from 1 to X- is an anion having the same meaning as in formula
6. 9. Composition according to any one of claims 1 compound B is lauryldlmethylbenzylammonium chloride. Composition according to any one of claims 1 compound B is coco-bis(2-hydroxyethyl)-methylammonium
7. 11. Composition according to any one of claims 1 compound B is oleyl-bis(2-hydroxyethyl)-methylammonium to 8, characterised in that to 8, characterised in that chloride. to 8, characterised in that chloride. S. S 0O S S S. S. S 0O S
8. 12. Composition according to any one of claims 1 to 11, characterised in that the solvent C is selected from among hydroxylated solvents or mixtures thereof, alcohols, polyols, polyol ethers and polyol polyethers.
9. 13. Composition according to any one of claims 1 to 12, characterised in that the solvent C is selected from among isopropanol, isobutanol, n-propanol, 2-methyl-2,4- pentanediol, 1,2-propylene glycol and the monomethyl ether of monopropyleneglycol. Dated this 2nd day of March, 1992. COTELLE SA. WATERMARK PATENT TRADEMARK ATTORNEYS FLOOR 2, "THE ATRIUM" 290 BURWOOD ROAD, HAWTHORN, VICTORIA 3122 AUSTRALIA. 0 0 0 0 "l or ;i. i 1 i i i i ii ij i t I .r ii -1 Hi i i i ii S:i i: r I i:i i:i 6 ii INTERNATIONAL SEARCH REPORT T/R88/00 PCT/FR88/0038International Application No International Application No I I I. CLASSIFICATION OF SUBJECT MATTER (If several classiication symbols apply, Indicate all) According to Internatlonal Patent Classllcatlon (IPC) or to both National Classification and IPC Int.Cl C 11 D 1/645;C 11 D 3/43 II, FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classification Symbols Int.Cl 4 C 11 D Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched a III.DOCUMENTS CONSIDERED TO BE RELEVANJT' Category Citation of Document, t1 with Indication, where appropriate, of the relevant passages 12 Relevant to Claim No. 13 X R,A,2523606(COLGATE-PALMOLIVE)23 September 1-4,8,9,13, 1983,see the whole document 14 cited in the application X EP,A,0060003(PROCTER &GAMBLE)15 September 198; 1-4,8,9,13, see examples;claims, cited in the applica- 14 tion X EP,A,0199382(PROCTER GAMBLE)29 October 1986, 1-4,7,8,9, see the whole document,cited in the appli- 13,14 cation X FR,A,2295122(HOECHST)16 July 1976,see the 1-4,8,10,13, whole document,cited in the application 14 A GB,A,1165007(MILLMASTER ONYX)24 September 1965 1 see examples;claims A EP,A.0165138(STEPAN EUROPE)18 December 1985, 1 see examples;claims A EP,A,0059502(PROCTER GAMBLE)08 September,see 1 examples; claims Special categories of cited documents: 10 later ument published after the international filing date document defining the general state of the art which is not or PriorILy date and not in conflict with the application but cona:Jared to be of particular relevance cited to understand the principle or theory underlying the r tinvention earlier document but published on or after the International document of particular relevance the claimed Invention filing date document of particular relevance; the claimed invention cannot be considered novel or cannot be considered to L" document which may throw doubts on priority claim(s) or involve an Inventive step which i cited to establish the publication date of another document of cular relevance;' the claimed nvention citation or other special reason (as specified) Y" documet of particular relevance the claimed Invention cannot be considered to Involve an inventive step when the document referring to an oral disclosure, Use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skillr document published prior to the international filing date but In the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Sear.. Date of Mailing of this Internatlo,. Search Report 16 September 1988(16.09.88) 07 October 1988(07.10.88) International Searching Authority Signature of Authorized Officer European Patent Office Form PCT/ISA/210 (second sheet) (January 1985) ANNEX TO T14E INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO- FR 8800318 SA 23011 This annex lists the patent family members relating to the patent documents cited in the above-mentloncd international search report. The members arc as contained in the European l'atnt Office ED1' rle on 29/09/88 The European Patent office is in no way liable for these particulars which are merely given for the purpose of information. IPatent document Publication Patent family Publication cited in scarch report date member(s) date I FR-A- 2523606 2-09-83 S-A- 8046 3-09-83 GB-A,B 2118221 26-10-83 NL-A- 8301026 17-10-83 AU-A- 1267683 29-09-83 OE-A- 3309569 27-10-83 US-A- 4442013 10-04-84 ICA-A- 1200658 18-02-86 GB-A,B 2167092 21-05-86 CH-B- 663962 29-01-88 EP-A- 0060003 15-09-82 JP-A- 57205581 16-12-82 US-A- 4422949 27-12-83 CA-A- 1192005 20-08-85 IEP-A- 0199382 29-10-86 AU-A- 5535486 02-10-86 GB-A- 2174423 05-11-86 IJP-A- 61275475 05-12-86 US-A- 4661269 28-04-87 577009 08-09-88 KF-A- 2295122 1-07-76 NL-A- 7514462 18-06-76 BE-A- 836689 16-06-76 DE-AC 2459354 24-06-76 LU-A- 74010 11i-11-76 GB-A- 1538866 24-01-79 AT-B- 345948 10-10-78 I.CH-A- 617456 30-05-80 GB-A- 1165007 24-09-69 Aucun hiEP-A- 0165138 18-12-85 FR-A,B 2564495 22-11-85 'FR-A,B 2578559 12-09-86 EP-A- 0059502 08-09-82 JP-A- 57205580 16-12-82 CA-A- 1206705-- 01-07-86 zw For more details about this annex :see Official Journal of the European Patent Office, No. 12/82 'K RAPPORT DE RECHERCHE INTERNATIONALE Demand. InItrnatIonatIeNPCT/FR 88 /00318 1, CLASSIMINT DE L'INVENTION (41 plusteurs SYM0otes do classfleation sont applicables, Iint nduer tousll $#ion is clossiricalionl internationala dos brevets (CIB) ou A Ia tots solon Is classifcation national* it la CIB CIB 4: C 11 D 1/645; C 11 D 3/43 11, oOMAINIS SUR LESQUILS LA RECHERCHE A PORTE Documentation minimal# consuitA. Systilm. do classitation ISyMbolic do classification Documentation consulide autre qua Ia documentation minimal. dans la mesure 06 do tils documents font Pant@ des domainis sur lesquils III recherchei ports Ill. DOCUMENTS CONSIOERS COMME PIERTINENTS 10 Catilgarl. I dentirication des documents ctt*S, 1 I ac Indication, III nicesaire, IN, des revendications S Ides passagvs perlinents 12 "1 got 3 1 X FR, A, 2523606 (COLGATE-PALMOLIVE) 1-4,8,9,13, 23 septembre 1983, voir le document 14 en entier cit6 dans la demande X EP, A, 0060003 (PROCTER GAMBLE) 1-4,8,9,13, septembre 1982, voir exemples; 14 revendications cit6 dans la dernande X EP, A, 0199382 (PROCTER GAMBLE) 1-4,7,8,9, 29 octobre 1986, voir le document en 113,14 entier cit6 dans la demande X FR, A, 2295122 (HOECHST) 16 juillet 1976, 1-4,8,10, voir le document en entier 13,14 cite dans la dernande A GB, A, 1165007 (MILLMASTER ONYX)1 24 septernbre 1969, voir exemples; r eve nd icat ions Cat~gorles ap6ciales do documents citos: a T )l document ultifieur oublit postkriourement hlaIada dep6t A P ocuentd~fnissnt tatg~nraldo l tehniuenoninternational ou A ta data da oriorite it n'apoirtenant Pas cosdvi Aom a docuikrment pertinent h 1'tat dona I& technique, nope~atdl acnoa rtinent, mcis cili pour comorandre cmeatcuiretprlnn, lePrincipe ou la ttioorie constituent Ii base do linvention sE a document antilriour, mats publih h Ia date do d6p6t interns- a X w document patticuli~roent pertinent: I'invention revandi. tional ou apras colts date dude no Pout tre considiris comm. nouvelle ou comma Li* document pouvant latar un doute sur une revendicition do impliquant une activit* inventive priorit6 ou cibA Pour determiner I&at atd, Publication d'une d Y document parlicuikriment partinent: l'invention revert- auita citation ou pour une raison special* (tolh qu'indiquie) dfqute ne Paul ftre considr#9 comma imotiouant une 0 x docu ment so r~f~rant A uns divulgatton orals, A un usage, k activittA inventive loronua Ie document eat associtAa un ou une eaposition ou tous sutree moyens piusteurs suites documents do memo nature, cats combi. aP a document pulil avant Ia date do d~o6t International, mats naion ktant 4VIdenta pour un. permonne au metier, Posthriourement A as date do prioriti revendiquiie sAadocument qul felt pate do as mime tamille do brevets IV, CERTIFICATION oata It laqualbe, Is rechterch~e International# a 6t4 etiectiviment Date d'expidition du Present rapport de recherche Internationale ach wie 16 septembre 1988 Administration chargile de I& recherche international. SiA', cin r utorisi OFFICE EUROPEEN DES BREVETS Formyulaire PCTIISA/210 Ideausime teulle) iJanvi., 1965) Damando internstionale N PCT/FR 88/00318 Ill2DOUMNTS CONS5IRds Commg PIRTININTs DUXIkM9 FPIULLEI) IDQ A EP, A, 0165138 (STEPAN EUROPE) 18 d6ceMbre 1 1985, voir exemples; reveridications A EP, A, 0059502 (PROCTER GAMBLE) 1 8 septembre 1982, voir exemples; revendications Formulaire PCT/ISA2IO (touliI. addltlonnolI.) (Janw ANNEXE AU RAPPORT DE RECHJERCHIE INTERNATIONALE RELATIF A LA DEMANDE INTERNATIONALE NO. FR 8800318 SA 23011 L a pr~sento annexe Idqcles inembres; dc In famille do brevets rclatifs aux documents brevets cit~s dans le rapport do recherche intern ati onal vsi ci-dessus. Lesdits members sont contenus au flchler informatique de I'Ofice europ~en des brevets ~i la date du 29/09/88 Les rcnsclgncments fournis sont donn~s A titro indicatif et n'engagent pas la rtsponsaiilite' dc I'Ornice europ~en des brevets. Document brevet cit6 Date do MIombrc(s) de la Date do au rapport do recherche publication ranille do brevet(s) -T publication FR-A- 2523606 23-09-83 SE-A- 8301476 23-09-83 AGB-A, B 2118221 26-10-83 NL-A- 8301026 17-10-83 AU-A- 1267683 29-09-83 j E-A- 3309569 27-10-83 US-A- 4442013 10-04-84 1200658 1-02-86 IGB-A,B 2167092 21-05-86 CH-B- 663962 29-01-88 EP-A- 0060003 15-09-82 JP-A- 57205581 16-12-82 US-A- 4422949 27-12-83 ICA-A- 1192005 20-08-85 IEP-A- 0199382 29-10-86 AU-A- 5535486 02-10-86 GB-A- 2174423 05-11-86 JP-A- 61275475 05-12-86 US-A- 4661269 28-04-87 AU-B- 577009 08-09-88 FR-A- 2295122 16-07-76 NL-A- 7514462 18-06-76 BE-A- 836689 16-06-76 DE-A,C 2459354 24-06-76 LU-A- 74010 11-11-76 GB-A- 1538866 24-01-79 AT-B- 345948 10-10-78 CH-A- 617456 30-05-80 [1GB-A- 1165007 24-09-69 Aucun IIEP-A- 0165138 18-12-85 FR-A,B 2564495 22-11-85 FR-A,B 2578559 12-09-86 EP-A- 0059502 08-09-82 JP-A- 57205580 16-12-82 CA-A- 1206705 01-07-86 Pour tout renfseignoment concernant cette annexe voir Journal Oficiel do l'Office europeen des brevets, No.12/82