CA2094786C - Rinse conditioner - Google Patents

Rinse conditioner

Info

Publication number
CA2094786C
CA2094786C CA002094786A CA2094786A CA2094786C CA 2094786 C CA2094786 C CA 2094786C CA 002094786 A CA002094786 A CA 002094786A CA 2094786 A CA2094786 A CA 2094786A CA 2094786 C CA2094786 C CA 2094786C
Authority
CA
Canada
Prior art keywords
powder
quaternary ammonium
dispersion
softening compound
ammonium softening
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA002094786A
Other languages
French (fr)
Other versions
CA2094786A1 (en
Inventor
Graham Andrew Turner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Original Assignee
Unilever PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever PLC filed Critical Unilever PLC
Publication of CA2094786A1 publication Critical patent/CA2094786A1/en
Application granted granted Critical
Publication of CA2094786C publication Critical patent/CA2094786C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/835Mixtures of non-ionic with cationic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00Compositions of detergents, not provided for by one single preceding group
    • C11D10/04Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • C11D2111/12

Abstract

A powder progenitive of a rinse conditioner which is used to form an aqueous dispersion of a rinse conditioner. The conditioning dispersion is formed outside the washing machine shortly before it is to be added to the washing machine. It is preferred if the rinse conditioner contains a cationic active.

Description

' -209478~

RINSE CONDITIONER

This invention relates to Rinse Conditioners comprising a softening or anti-static component delivered to the wash from suspension in the wash liquor during a rinsing step.

In the past fabric conditioning has been carried out either during then rinsing step of a fabric washing and rinsing process or during tumble drying of the fabric. In almost all cases rinse conditioning is accomplished by adding a liquid dispersion of a rinse conditioning agent to the rinse water. The liquid dispersion was traditionally distributed and made available to consumers as a ready to use aqueous dispersion. More recently, concern for the environment and consumer convenience has led to the sale of concentrated aqueous dispersions which are either used in smaller amounts or are mixed with water to form a predilute before use.

In EP 234082 it has been proposed to supply rinse conditioner as a solid block. This approach requires the use of a special restraint for the block and may also require the modification of the washing machine to enable the block to be dissolved and dispensed by a spray system.

.

7 8 ~
Various proposals have been made to supply fabric softener in granular or powdered form. EP 111074 is typical and uses a silica to carry the softener. A disadvantage of using a carrier such as silica is that it bulks up the product and serves no function beyond making the powder compatible with other ingredients that may be contained in a washing powder.
3 describes a granular fabric softening composition comprising a nonionic fabric softener and a single long alkyl chain cationic material. The specification teaches that effective cationic softening compounds when used in granular form exhibit poor dispersion properties.
It has been suggested to add rinse conditioner in powdered form directly to the washing machine. If this is done via the normal dispensing compartment there is a considerable risk that the rinse conditioner will thicken or gel after contact with residual water from a previous wash. This would prevent or hinder dispensing of the proper dose of conditioner. A way round this problem is to add th~e powder directly to the wash at the appropriate time. This is extremely inconvenient and may entail stopping the washing machine at the end of the main wash cycle, opening it and trying to sprinkle powder over the washing before continuing with the rinse stage.

For these reasons, despite the obvious environmental and transport saving advantages of selling a water free powdered rinse conditioner, manufacturers have not done so .

According to the invention there is provided a rinse conditioner powdercomprising 40-95% of a quaternary ammonium softening compound of formula ~Rt)3N+~~ n--ICH 1l wherein each Rl is independently selected from Cl~ aLkyl, hydroxyalkyl or C2-C4, hydroxy alkenyl; and wherein each R2 is independently selected from C7 27 alkyl or alkenyl groups, and n is an integer from 0 to 5, together with about 2 to about 16% by weight of a nonionic dispersion aid compr~sing a linear long-chain alcohol ethoxylate having more than 5 moles of ethoxylation such that the powder forms a dispersion having 5-20% by weight of the quaternary ammonium softening compound when mixed with water outside the washing machine for use in a washing procedure during a time taken to complete the washing procedure.

According to another aspect of the invention there is provided a process to form an aqueous dispersion of a rinse conditioner consisting essentially of the steps of:

(a) preparing a rinse conditioner powder containing 40 to 95 wt. % of a quaternary ammonium softening compound having a formula o ~C~2 (R1)3N+~ ~ 8 C:H20CR2 ~. ...
4 ~ 7~ ~

wherein each Rl is independently s~lecte~ from Cl~ alkyl, hydroxyalkyl or C2-C4 hydroxy alkenyl; and wherein each R2 is independently selected from C7 27 alkyl or alkenyl groups, and n is an integer from 0 to 5, together with about 2 to about 16% by weight of a nonionic dispersion aid comprising a linear long-chain alcohol ethoxylate having more than 5 moles of ethoxylation; and (b) mixing the powder with water having a temperature of 7~ C. to 20~
C. and shaking for up to 5 seconds to form a dispersion having 5-20% of the quaternary ammonium softening compound, the dispersion formed outside the washing machine for use in a washing procedure during a time taken to complete the washing procedure.

1~ In the context of this invention forming the dispersion shortly before it is used means forming the dispersion for use in a particular washing procedure during the time taken to complete that washing procedure.

In the context of this invention a washing machine can be defined as a machine which works by a mechanical mechanism or a more simple device such as a bucket or bowl.

The powder may also contain a co-active. Preferably at levels of up to 20%.
The coactive is ~rereLably a fatty acid. The fatty acid coactive preferably comprises hardened tallow fatty acid.

The level of fatty acid should be kept as low as possible, pre~e~dbly less than 15%, to minimise the reduction of softening performance in the case that there is carry-over of anionic active from the earlier washing part of the fabric washing and rinsing process.

....
, ' -- 5 ~ 7 ~ ~

Advantageously the powder contains a nonionic dispersion aid, such dispersion aids have also been shown to add an additional softening benefit. Examples of nonionic dispersion aids include long chain alcohol ethoxylates, sugars and sugar alcohols.

The powder of this invention is prereldbly used with water to make a fabric conditioning dispersion by the consumer in the home. It is thus advantageous if the powder is dispersed by manual shaking. rre~eLably the powder is shaken with water for 5 seconds, more ~rerelably the powder is shaken with water for 2 seconds, most ~leferdbly the powder is dispersed by merely once inverting a sealed container comprising powder and water.

It is preferred if the dispersion is made using water at ambient temperature as this is more convenient for the consumer.
1~
The composition may also contain a flow aid and other ingredients commonly found in rinse conditioners such as perfume, antifoam, preservative and dye.

rrefelred quaternary ammonium softening compounds used in the powder of the invention and their method of preparation are, for example, described in US 4137180 (Lever Brothers). Preferably these materials comprise small amounts of the colre~onding monoester as described in US 4 137180 for example 1-tallowoyloxy, 2-hydroxytrimethyl ammonium 2~ propane chloride.

Plereldbly the level of cationic active:fatty acid is greater than 6:1. More preferably the ratio of cationic:fatty acid is 12:1.

-~ -6- ~ 7 ~ ~

The invention will now be described with refelel,ce to the following non-limiting examples:

Example 1 A powder having the composition as in Table 1 was prepared in three different ways first by dry mixing, secondly by a melt process, and finally by prilling:

B

Table 1 COMPONENT WEIGHT % IN SUPPLIER CHEMICAL NAME
PRODUCT
1. HT TMAPC 73.1 Hoescht l-trimethyl ammonium-2,3-dihardened tallowoyloxy propane chloride 2. Hardened tallow fatty acid 3.1 Hoescht Hardened tallow fatty acid 3. IPA 13.4 Hoescht (propanol-2) 4. Genapol C-100 3.0 Hoescht Coco alcohol ethoxylated with 10 mols ethylene oxide 5. Perfume 3.6 Quest 6. Microsil GP 3.8 Crosfield Aluminosilicate c~

209~786 Dry mixing - The solid HT TMAPC was placed in a high shear cutting vessel along with the nonionic surfactant and ground for 2-5 minutes. Perfume in an inorganic porous carrier was added to the mixture. This mixture was then - 5 sieved to the desired particle size or granulated.

In this example the HT TMAPC contained solvent (IPA) but the process works just as well in solvent-free systems.

Melt process - The above formulation was also prepared by a melt process. In this case the HT TMAPC, nonionic and perfume were melted to ensure intimate mixing of ingredients and allowed to cool and solidify. The solid premix and Microsil was then transferred to a high shear cutting vessel and ground to a powder as before.

It is also possible to add the perfume with the flow aid or other carrier instead of including it in the melt stage alternatively the perfume can be sprayed on.
Prilling - A molten mixture prepared as for the melt process was dropped 4cm at a rate of about 65g/min. onto a heated (150~C) rotating (-2,000 rpm) disc. As the molten material was spun off the disc it was air cooled (as it radiates outward) and near-spherical granule particles (50-500 ~m) were formed.

Powders made by all three methods exhibited good dispersion properties when used to prepare an aqueous dispersion. The aqueous dispersion dispersed well when further diluted in the rinse liquor of a front loading washing machine.

ExamPle 2 A powder having the composition as in table 2 was prepared by the melt process, followed by grinding to a particle size of less than 350 ~. The solvents are present simply because they were contained in the cationic as supplied.

a~e~ soul~nl~ plal~sol~ 5 9llsnl~ ~ L
~sano ~-~(d~8~ n~) a~n~lad 9 01 oll~ au~dold-~~Z~ saoH 9 6 ~lola~ S
louedold-Z ~saoH 9 6 ~louedoldOsI ~~
UOI ~,~l~coT~a S1~~ 0l ~lIM IO~O~Ie 0~0~ saoH 8 Z (%001) 001-~ l~deUa~ ~~
pl~e ~ Molle~ pauapleH ~saOH L- 6~pl~e ~e~ Moll~ paUaPl~H Z O
apllol~ auedold ~XOI~OMO
pauaple~lp-~'z-~nluow~e l~a~ll~ saOH ~ 85 ~d~L ~H 1 L~naO~d NI(paAIa~al se aAI~e %) ~N ~ H~ dans % ~H~I~M ~N~NOd~O~

Z alqe~L

_ ~ C3444 The Genapol C-100 nonionic is chosen for its biodegradability and for the viscosity control that it imparts to the predilute. The Alusil is included as a flow aid.

The powder was then used to make a 5% cationic predilute by shaking it for a few seconds with 1 litre of warm water at 40~C. A good bit-free dispersion was obtained which remained stable for over one month and gave good softening when used as a liquid rinse conditioner.

It will be understood that although these examples describe the formation of predilutes having a cationic concentration of 5% by weight, the invention also encompasses other softening agents and higher concentrations of actives. For example, the powder could be dispersed to form a so-called concentrate for addition to the washing machine. Typical active levels in such a liquid concentrate would be 7-20% by weight.
Example 3 -Example 3 was prepared using the melt process as described for Example 2 and used to prepare a 5% predilute in the same manner as demonstrated for Example 2.

The composition of Example 3 is shown in Table 3.

~Q9~8~1~
~.

Table 3 ComponentWeight Supplier Chemical Name (% active as % in received) product Tetranyl AHT-1 79.7 Kao N,N
di(aryloxyethyl) N-hydroxy ethyl, N-methyl ammonium methy S04 Genapol C-100 2.8 Hoescht 2-propanol Perfume 3.4 Quest MSI/IPA* 14.1 Crosfield Aluminosilicate * solvent supplied with Tetranyl AHT-1 Softening performance was evaluated by adding O.lg of softening active (2ml of a 5% a.d. dispersion) to 1 litre of tap water, 10~FH, at ambient temperature containing 0.001% (w/w) sodium alkyl benzene sulphonate (ABS) in a tergotometer. The ABS was added to simulate carryover of anionic detergent from the main wash. Four pieces of terry towelling (2Ocm x 2Ocm, 50g total weight) were added to the tergotometer pot. The cloths were treated for 5 minutes at 60 rpm, spin dried to remove excess liquor and line dried overnight.

Softening of the fabrics was assessed by an expert panel of 4 people using a round robin paired comparison test protocol. Each panel member assessed four sets of test cloths. Each set of test cloths contained one cloth of each test system under a evaluation. Panel members were asked to pick the softer cloth of each pair during evaluation. A "no difference~ vote was not permitted.
Softness scores were calculated using an "Analysis of - 2~7~6 Variance~ technique. Higher values are indicative of lower softening.

The results of Example 3 was compared with Example 2. The molar ratios of cationic active:nonionic are the same for the two formulations (95:5), the results are shown in table 4.

Table 4 Example Softening Score Total Votes 2 3.0 38 3 3.5 27 It can be seen that a composition containing Tetranyl AHT-l has a softening effect not as great as with the composition comprising HT TMAPC.

Example 4 The conditioner powder of Example 4 was prepared with a composition as in table 5 using the melt process.

Table 5 Component % Weight Adogen lOOP 86.1 Genapol C-100 - 4.2 Perfume 4.3 IPA* 5,4 * IPA was used to form the melt, however it is likely that the level of IPA present in the final powder 209~78~

composition is minimal due to evaporation during the melt stage.

The powder exhibited good softening of fabrics when used in the same manner as Example 1.

Examples 5-14 Compositions were prepared using the melt process. In all cases the ratio of HTTMAPC:fatty acid is kept constant at 6:1 IPA was present in all formulations at a level of 0.4%. The ratios of H TTMAPC:nonionic are listed in table 6.

Table 6 Molar Ratio of Weight Ratio of HTTMAPC:CocolOEO HTTMAPC:CocolOEO
Example 5 100:0 100.0 Example 6 99:1 99.2:0.8 Example 7 97.5:2.5 97.9:2.
Example 8 19:1 95.8:4.2 Example 9 22:3 89.9:10.1 Example 10 21:4 86.4:13.6 Example 1181.3:18.7 84:16 Example 1280.6:19.4 83.4:16.6 Example 13 4:1 82.9:17.1 Example 1478.8:21.2 81.8:18.2 Examples 12,13 and 14 could not be prepared as a powder as they were too sticky.

20947~6 It can be seen that a molar ratio of HT TMAPC:Nonionic less than 80.6:19.4 the powder cannot be prepared.

The softening performance as described in Example 2 and 3 was tested in two series of experiments the results of which are demonstrated in tables 7 and 8.

Table 7 10Example Softening Score 8 5.5 7 6.25 6 5.5 Table 8 Example Softening Score 7 5.25 8 5.75 9 3.5 3.0 11 3.25 It is demonstrated that the lower the cationic:nonionic surfactant molar ratio the more effective the softening properties of the composition.

:- 2~gg~

Example 15 Table 9 Component Weight % Supplier Chemical Name in product HT TMAPC* 72.7 Hoescht 1-trimethyl ammonium-2,3 dihardened tallowoyloxy propane chloride Fatty acid* 3.1 Hoescht Hardened tallow fatty acid IPA* 13.8 Hoescht propan-2-ol Genapol C100 3.0 Hoescht Coco alcohol ethoxylated with 10 mols ethylene oxide Perfume 3.6 Quest Microsil 3.8 Crosfields Aluminosilicate HT TMAPC*, fatty acid*, and IPA* were supplied as a continous solid by Hoescht.
The powder of Example 15 has the initial composition as shown in table 9. The powder was prepared using the dry mix process described in Example 1.

The powder was sieved to provide a particle between 150-250 ~m.

The dispersability of Example 15 was tested in water at 7~C and 20~C using the following method:
Example 15 was weighed into a container. Demineralised (water 95g at 20~C or at 7~C) is added to the powder and :- 209~78~

the container was sealed. The mixture was either shaken for 2 seconds or inverted once.

All of the resulting dispersions were filtered through the ~Polymon 43T" 150 ~m mesh (trademark ex George Hall Ltd).
The mesh was dried in a oven at 105~C for 2 hours, then weighed. The percentage of solid material retained by the mesh was calculated. The dispersion results of carrying out these tests are shown in table 10.
Table 10 % of powder retained on 150~m mesh water at 7~C water at 20~C
2 second 1 inversion 2 second 1 inversion shake shake 5g powder/95g 3.34 8.4 1.44 5 water 15g powder/85g 4.6 66 6.6 73 water Table 10 demonstrates that with 5g of powder the p~wder disperses rapidly with minimum agitation at 7~C and 20~C.
When 15g of powder is used it can be seen that greater agitation is needed.
The powder of Example 15 has been tested for softening using the procedure described for Example 3. The results are given in table 11.

n 1~ ~ A 1~ i~a L~

Table 11 water at 7~C water at 20~C
prediluted prediluted (lx) (lx) Softening Score 4.00 3.00 Water would be expected to give a softening score of 8.

Examples 16-20 Table 12 Weight % in Product Component SupplierExample 16 Example 17 Example 18 Example 19 Example 20 HT TMAPC Hoescht 73.2 71.2 73.6 73.5 72.7 Fatty acid Hoescht 3.0 3.0 3.0 3.0 3.0 IPA Hoescht 13.4 13.2 13.6 13.6 13.4 Perfume Quest 3.6 3.6 3.7 3.7 3.6 Microsil Crosfields 3.8 3.8 3.9 3.9 3.8 Genapol C1001 Hoescht 3.0 Genapol C2002 Hoescht - 5.2 Genapol T1503 Hoescht - - 2.2 - - r~
Dobanol 25-5 nonionic Shell - - - 2.3 -C12-C15 alcohol ethoxylated with 5 mols ethylene oxide ic~
Arosurf 66-10 Sherex - - - - 3.5 Isostearethalcohol 10 mols ethylene oxide HT TMAPC and IPA supplied as continuous solid.

20~47~6 = (coco alcohol ethoxylated with 10 mols ethylene oxide) 2 = ( COCO alcohol ethoxylated with 20 mols ethylene oxide) 5 3 = (COCO alcohol ethoxylated with 15 mols ethylene oxide) The powders of Examples 16-20 have the compositions as shown in Table 12. The powders were prepared using the 10 dry mix process described in Example 1.

The powders were tested for softening using the process described for Example 3. The results are given in table 13.
Table 13 Example Softening Score 16 3.50 17 3.25 18 3.75 19 4.50 4.75 25 It is thus demonstrated that softening occurs with a range of nonionic actives.

Claims (8)

1. A rinse conditioner powder comprising 40-95% of a quaternary ammonium softening compound of formula wherein each R1 is independently selected from C1-4 alkyl, hydroxyalkyl or C2-C4, hydroxy alkenyl; and wherein each R2 is independently selected from C7-27alkyl or alkenyl groups, and n is an integer from 0 to 5, together with about 2 to about 16% by weight of a nonionic dispersion aid comprising a linear long-chain alcohol ethoxylate having more than 5 moles of ethoxylation such that the powder forms a dispersion having 5-20% by weight of the quaternary ammonium softening compound when mixed with water outside the washing machine for use in a washing procedure during a time taken to complete the washing procedure.
2. A powder according to claim 1 having an average particle diameter of less than 1000 microns.
3. A powder according to claim 2 wherein the average particle diameter is 150-350 microns.
4. A process according to claim 3 wherein the molar ratio of the quaternary ammonium softening compound to the nonionic dispersion aid is about 97.5:2.5 to 81.
5. A process according to claim 3 wherein the quaternary ammonium softening compound is 1-trimethyl ammonium-2,3 dihardened tallowoyloxy propane chloride.
6. A process according to claim 3 wherein the powder further comprises up to 20% of a fatty acid.
7. A process according to claim 6 wherein the molar ratio of the quaternary ammonium softening compound to the fatty acid is greater than 6:1.
8. A process to form an aqueous dispersion of a rinse conditioner consisting essentially of the steps of:
(a) preparing a rinse conditioner powder containing 40 to 95 wt. % of a quaternary ammonium softening compound having a formula .

wherein each R1 is independently selected from C1-4 alkyl, hydroxyalkyl or C2-C4 hydroxy alkenyl; and wherein each R2 is independently selected from C7-27 alkyl or alkenyl groups, and n is an integer from 0 to 5, together with about 2 to about 16% by weight of a nonionic dispersion aid comprising a linear long-chain alcohol ethoxylate having more than 5 moles of ethoxylation; and (b) mixing the powder with water having a temperature of 7° C. to 20°
C. and shaking for up to 5 seconds to form a dispersion having 5-20% of the quaternary ammonium softening compound, the dispersion formed outside the washing machine for use in a washing procedure during a time taken to complete the washing procedure.
CA002094786A 1992-04-28 1993-04-23 Rinse conditioner Expired - Fee Related CA2094786C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9209170.1 1992-04-28
GB929209170A GB9209170D0 (en) 1992-04-28 1992-04-28 Rinse conditioner

Publications (2)

Publication Number Publication Date
CA2094786A1 CA2094786A1 (en) 1993-10-29
CA2094786C true CA2094786C (en) 1999-05-11

Family

ID=10714681

Family Applications (2)

Application Number Title Priority Date Filing Date
CA002094786A Expired - Fee Related CA2094786C (en) 1992-04-28 1993-04-23 Rinse conditioner
CA002094787A Expired - Fee Related CA2094787C (en) 1992-04-28 1993-04-23 Rinse conditioner

Family Applications After (1)

Application Number Title Priority Date Filing Date
CA002094787A Expired - Fee Related CA2094787C (en) 1992-04-28 1993-04-23 Rinse conditioner

Country Status (21)

Country Link
US (2) US5403500A (en)
EP (2) EP0568297B1 (en)
JP (2) JP2710743B2 (en)
KR (2) KR100186970B1 (en)
CN (2) CN1071375C (en)
AU (2) AU667213B2 (en)
BR (2) BR9301670A (en)
CA (2) CA2094786C (en)
CZ (2) CZ293520B6 (en)
DE (2) DE69320685T2 (en)
ES (2) ES2150434T3 (en)
GB (1) GB9209170D0 (en)
HU (2) HU218296B (en)
IN (1) IN178851B (en)
MY (2) MY107561A (en)
NZ (2) NZ247459A (en)
PH (1) PH30901A (en)
PL (2) PL298715A1 (en)
SK (2) SK282233B6 (en)
TW (1) TW248570B (en)
ZA (2) ZA932996B (en)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9209170D0 (en) * 1992-04-28 1992-06-10 Unilever Plc Rinse conditioner
HU215586B (en) * 1992-05-12 1999-01-28 The Procter & Gamble Co. Concentrated fabric softener compositions containing biodegradable fabric softeners, method for producing the same and method for softening fabric
WO1994007979A1 (en) * 1992-09-28 1994-04-14 The Procter & Gamble Company Method for using solid particulate fabric softener in automatic dosing dispenser
GB9319566D0 (en) * 1993-09-22 1993-11-10 Unilever Plc Rinse conditioner
GB9319567D0 (en) * 1993-09-22 1993-11-10 Unilever Plc Fabric conditioner
ES2119233T3 (en) * 1993-10-22 1998-10-01 Unilever Nv CONDITIONING COMPOSITION FOR TEXTILES.
EP0749473B1 (en) 1994-03-08 2005-10-12 Novozymes A/S Novel alkaline cellulases
GB9406824D0 (en) * 1994-04-07 1994-06-01 Unilever Plc Fabric softening composition
EP0754215B1 (en) * 1994-04-07 2001-05-23 Unilever Plc Fabric softening composition
US5429755A (en) * 1994-06-16 1995-07-04 Lever Brothers Company Fabric conditioning molecules derived from glycerol and betaine
NZ286025A (en) * 1995-03-01 1997-04-24 Colgate Palmolive Co Laundry detergent concentrates; contains nonionic surfactant and water insoluble oil with a hydrophilic polar group, converts to liquid crystal phase dispersion on dilution
US5674832A (en) * 1995-04-27 1997-10-07 Witco Corporation Cationic compositions containing diol and/or diol alkoxylate
EP0753571A1 (en) * 1995-07-10 1997-01-15 The Procter & Gamble Company Process for making granular detergent composition
ES2174913T3 (en) * 1995-09-18 2002-11-16 Procter & Gamble SOFTENING STABILIZED COMPOSITIONS OF FABRICS.
US5929025A (en) * 1995-09-18 1999-07-27 The Procter & Gamble Company Stabilized fabric softening compositions comprising a fabric softening compound, fatty acid, and perfume
GB9521667D0 (en) * 1995-10-23 1996-01-03 Unilever Plc Fabric softening composition
DE19640086C2 (en) * 1996-09-28 1998-09-17 Wella Ag Solid detergent mixture, its manufacture and use
US5874395A (en) * 1997-12-29 1999-02-23 Colgate-Palmolive Company Liquid rinse cycle fabric softening compositions containing diacid polymeric fatty ester quaternary ammonium compounds
DE10059340A1 (en) * 2000-11-29 2002-06-20 Henkel Kgaa Particulate textile aftertreatment agent
GB0118347D0 (en) 2001-07-27 2001-09-19 Unilever Plc Fabric conditioning compositions
GB0121805D0 (en) 2001-09-10 2001-10-31 Unilever Plc A method for preparing fabric conditioning compositions
GB0207481D0 (en) 2002-03-28 2002-05-08 Unilever Plc Solid fabric conditioning compositions
GB0207483D0 (en) 2002-03-28 2002-05-08 Unilever Plc Fabric conditioning compositions
GB0207484D0 (en) 2002-03-28 2002-05-08 Unilever Plc Solid fabric conditioning compositions
BRPI0509679A (en) 2004-04-09 2007-10-09 Unilever Nv granules for use in particulate cleaning product, manufacturing process and detergent composition
WO2023117331A1 (en) * 2021-12-21 2023-06-29 Unilever Ip Holdings B.V. Powdered cosmetic composition

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1567947A (en) * 1976-07-02 1980-05-21 Unilever Ltd Esters of quaternised amino-alcohols for treating fabrics
FR2482636A1 (en) * 1980-05-14 1981-11-20 Lesieur Cotelle Et Associes Sa CONCENTRATED SOFTENING COMPOSITION FOR TEXTILE FIBERS
US4395342A (en) * 1980-06-06 1983-07-26 The Procter & Gamble Company Granular fabric softening composition
US4427558A (en) * 1981-05-08 1984-01-24 Lever Brothers Company Fabric conditioning materials
JPS5851547A (en) * 1981-09-22 1983-03-26 Kansai Electric Power Co Inc:The Cooler for electric device
DE3243983C2 (en) * 1982-11-27 1984-11-22 Degussa Ag, 6000 Frankfurt Laundry softener concentrate
JPS6226078U (en) * 1985-07-31 1987-02-17
US4769159A (en) * 1986-02-18 1988-09-06 Ecolab Inc. Institutional softener containing cationic surfactant and organic acid
GB2188653A (en) * 1986-04-02 1987-10-07 Procter & Gamble Biodegradable fabric softeners
GB8614083D0 (en) * 1986-06-10 1986-07-16 Unilever Plc Dissolving & dispensing non-liquid chemicals
ATE82770T1 (en) * 1987-09-23 1992-12-15 Procter & Gamble LINEAR ALKOXYLATED ALCOHOL-CONTAINING STABLE, BIODEGRADABLE LAUNDRY SOFTENER COMPOSITIONS.
DE68919236T2 (en) * 1988-01-28 1995-04-06 Unilever Nv Textile treatment preparation and its manufacture.
GB8804818D0 (en) * 1988-03-01 1988-03-30 Unilever Plc Fabric softening composition
US5200097A (en) * 1988-05-31 1993-04-06 Sherex Chemical Company, Inc. Process for making a particulate water dispersible free flowing fabric softener composition
GB8823007D0 (en) * 1988-09-30 1988-11-09 Unilever Plc Conditioning of fabrics
US4970008A (en) * 1988-12-20 1990-11-13 Kandathil Thomas V Fabric conditioner comprising a mixture of quaternary ammonium compounds and select tertiary amines
JPH02182972A (en) * 1989-01-04 1990-07-17 Kao Corp Solid soft-finishing agent
US5002681A (en) * 1989-03-03 1991-03-26 The Procter & Gamble Company Jumbo particulate fabric softner composition
JPH0636302Y2 (en) * 1989-06-13 1994-09-21 三菱電機株式会社 Internal combustion engine ignition device
GB8916307D0 (en) * 1989-07-17 1989-08-31 Unilever Plc Fabric softening composition
GB8916306D0 (en) * 1989-07-17 1989-08-31 Unilever Plc Fabric softening composition
US5116520A (en) * 1989-09-06 1992-05-26 The Procter & Gamble Co. Fabric softening and anti-static compositions containing a quaternized di-substituted imidazoline ester fabric softening compound with a nonionic fabric softening compound
US5221794A (en) * 1990-01-31 1993-06-22 Sherex Chemical Company, Inc. Process and composition for multicomponent one hundred percent solid fabric softeners
US5223628A (en) * 1990-02-02 1993-06-29 Sherex Chemical Company, Inc. Process for making high solids fabric softeners using low amounts of solvents and no side reactions
EP0486113A3 (en) * 1990-11-16 1992-07-08 Akzo N.V. Biodegradable fabric softeners derived from aspartic acid or glutaminic acid
EP0557343A1 (en) * 1990-11-16 1993-09-01 Akzo Nobel N.V. Biodegradable fabric softeners
US5089148A (en) * 1990-11-27 1992-02-18 Lever Brothers Company, Division Of Conopco, Inc. Liquid fabric conditioner containing fabric softener and peach colorant
US5183580A (en) * 1990-11-27 1993-02-02 Lever Brothers Company, Division Of Conopco Inc. Liquid fabric conditioner containing fabric softener and green colorant
US5130035A (en) * 1990-11-27 1992-07-14 Lever Brothers Company, Division Of Conopco, Inc. Liquid fabric conditioner containing fabric softener and red dye
EP0730140A3 (en) * 1991-03-19 1998-08-05 Luc Riedo Load indicating device for vehicle
US5409621A (en) * 1991-03-25 1995-04-25 Lever Brothers Company, Division Of Conopco, Inc. Fabric softening composition
US5185088A (en) * 1991-04-22 1993-02-09 The Procter & Gamble Company Granular fabric softener compositions which form aqueous emulsion concentrates
US5259964A (en) * 1991-12-18 1993-11-09 Colgate-Palmolive Co. Free-flowing powder fabric softening composition and process for its manufacture
GB9301728D0 (en) * 1993-01-28 1993-03-17 Unilever Plc Fabric softening composition
GB9209170D0 (en) * 1992-04-28 1992-06-10 Unilever Plc Rinse conditioner

Also Published As

Publication number Publication date
MY107561A (en) 1996-04-08
EP0568297B1 (en) 1998-09-02
MY107560A (en) 1996-04-08
CA2094787A1 (en) 1993-10-29
PH30901A (en) 1997-12-23
ZA932996B (en) 1994-10-28
PL298716A1 (en) 1993-11-02
SK40393A3 (en) 1994-01-12
PL172250B1 (en) 1997-08-29
HUT64377A (en) 1993-12-28
HU9301215D0 (en) 1993-08-30
CA2094787C (en) 1999-05-11
CN1079774A (en) 1993-12-22
ZA932995B (en) 1994-10-28
AU3706893A (en) 1993-11-04
HU218296B (en) 2000-07-28
JP2710743B2 (en) 1998-02-10
KR930021772A (en) 1993-11-23
CZ285938B6 (en) 1999-12-15
NZ247459A (en) 1995-10-26
BR9301670A (en) 1993-11-03
CN1084881A (en) 1994-04-06
KR930021773A (en) 1993-11-23
CA2094786A1 (en) 1993-10-29
DE69320685T2 (en) 1999-02-04
GB9209170D0 (en) 1992-06-10
DE69329165D1 (en) 2000-09-14
AU664435B2 (en) 1995-11-16
IN178851B (en) 1997-07-05
CZ74693A3 (en) 1994-01-19
AU667213B2 (en) 1996-03-14
DE69329165T2 (en) 2001-04-05
SK40293A3 (en) 1994-01-12
EP0568297A1 (en) 1993-11-03
KR0169748B1 (en) 1999-01-15
KR100186970B1 (en) 1999-04-15
CZ293520B6 (en) 2004-05-12
BR9301671A (en) 1993-11-03
EP0569184A1 (en) 1993-11-10
US5403500A (en) 1995-04-04
JPH0610266A (en) 1994-01-18
JPH0610265A (en) 1994-01-18
US5525244A (en) 1996-06-11
TW248570B (en) 1995-06-01
ES2121946T3 (en) 1998-12-16
AU3706293A (en) 1993-11-04
SK282233B6 (en) 2001-12-03
CN1045116C (en) 1999-09-15
CN1071375C (en) 2001-09-19
CZ74793A3 (en) 1994-02-16
JP2803964B2 (en) 1998-09-24
DE69320685D1 (en) 1998-10-08
HU218162B (en) 2000-06-28
HUT64376A (en) 1993-12-28
SK280869B6 (en) 2000-08-14
ES2150434T3 (en) 2000-12-01
NZ247460A (en) 1994-10-26
PL298715A1 (en) 1993-11-02
HU9301214D0 (en) 1993-08-30
EP0569184B1 (en) 2000-08-09

Similar Documents

Publication Publication Date Title
CA2094786C (en) Rinse conditioner
US4203851A (en) Fabric softening compositions and methods for manufacture thereof
JP2611035B2 (en) Composition for softening textile products
AU666894B2 (en) Free-flowing powder fabric softening composition and process for its manufacture
GB2123848A (en) Soil release promoting nonionic detergent composition
JPH0665365B2 (en) Defoamer granules for laundry detergent, method for producing the same, and detergent composition containing the same
ZA200400892B (en) Perfumed coloured speckle composition and particulate laundry detergent compositions containing it.
MXPA02006276A (en) A method for preparing fabric softening compositions.
US20040102345A1 (en) Solid wrinkle reduction laundry product compositions containing hydrophilic oil derivatives
EP0720645B1 (en) Rinse conditioner
CZ367592A3 (en) Process for preparing a freely flowing particulate composition for softening textile materials
WO2007004094A1 (en) Granulated fragranced foam control agents
MXPA04009462A (en) Solid fabric conditioning compositions.
MXPA04009347A (en) Solid fabric conditioning compositions.
WO1995008617A1 (en) Fabric conditioner
GB2260771A (en) Fabric softener concentrate

Legal Events

Date Code Title Description
EEER Examination request
MKLA Lapsed