WO1993017085A1 - Biodegradable fabric softeners - Google Patents
Biodegradable fabric softeners Download PDFInfo
- Publication number
- WO1993017085A1 WO1993017085A1 PCT/EP1993/000173 EP9300173W WO9317085A1 WO 1993017085 A1 WO1993017085 A1 WO 1993017085A1 EP 9300173 W EP9300173 W EP 9300173W WO 9317085 A1 WO9317085 A1 WO 9317085A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- oxy
- oxo
- fabric softener
- alk
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Definitions
- the invention relates to fabric softeners of improved hydrolytic stability upon storage which contain as essential constituent a biodegradable quaternary ammonium compound.
- Fabric softeners of the above-mentioned type have earlier been suggested in US-A-4767 547.
- Preferred among the plurality ' of compounds described therein are compounds of the formula N,N-di (alkanoyl-oxy-ethy1)-N,N-dimethyl ammonium chloride, their principal representative being
- N,N-di (tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride N,N-di (tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride.
- the invention now provides quaternary ammonium compound-containing fabric softeners of greatly improved hydrolytic stability without any attendant deterioration of the biodegradability.
- the invention consists in that the fabric softeners of the known type mentioned in the opening paragraph contain as essential constituent a quaternary ammonium compound of the formula:
- Ri represents an alk(en)yl group having 11-22 carbon atoms
- R-x represents an alk(en)yl group having 11-21 carbon atoms
- X represents an anion
- R* and R* may be the same or different and represent an alk(en)yl group having 15-18 ° carbon atoms.
- Ri represents a stearyl group and the same goes for when R 2 represents a pentadecyl group.
- Other groups considered suitable within the scope of the invention include lauryl, oleyl, and palmityl .
- X ⁇ represents a halide anion, more particularly a chloride, sulphate, methosulphate, carboxylate or sulphonate anion.
- the present quaternary ammonium compounds can be prepared in the manner known for the preparation of analogous compounds. In the example which will follow the preparation of a representative quaternary ammonium compound according to the present invention is described in detail, and the remaining biodegradable fabric softening agents according to the present invention are directly accessible to the skilled man through adaptation of the starting substances concerned.
- the manner in which the present biodegradable fabric softening agent is applied is the same as for the conventional, now commercially available fabric softeners, where the agent, together with the surfactant, can be contacted with the textile material to be softened in the form of a rinsing agent or else in the dryer.
- the fabric softening action envisaged and actualised here is the same as that of the conventional fabric softeners.
- a portion of the fabric softener will end up in the waste water, where, because of the present invention, there will be less harm to the environment as a result of accelerated biodegradability.
- the present biodegradable fabric softening agents were tested for their fabric softening action and found to be comparable with dimethyl distearyl ammonium chloride and l-methyl-2-tallow alkyl-3-tallow amidoethyl imidazolinium ethosulphate.
- This test towels treated with the fabric softeners in question were line dried for 24 hours and then cut up into strips of 10 x 20 cm* .
- a test panel tested the softening action as compared with that of the standard test surfactant (IEC), whereupon the observational data was statistically processed in accordance with DIN standard 10954.
- IEC standard test surfactant
- Measuring was as follows. First, a melt of the compound to be tested was charged, with proper stirring, to a flask filled with distilled water, after which hydrochloric acid or sodium hydroxyde was employed to set the pH at a predetermined value. Next, the degree of hydrolysis was determined with the aid of H-NMR analysis, NaOH titration, and/or HPLC analysis.
- the present quaternary ammonium compounds were tested for biodegradability in accordance with the EEC/OECD guidelines (4.1, 4.2) using the closed bottle test.
- a test compound is added to an aqueous solution of mineral salts and exposed for 28 days under aerobic conditions to a relatively small number of micro-organisms.
- the formal test regulations were departed from on the following minor issues:
- the inoculum was taken from an apparatus containing activated sludge preconditioned in accordance with proposed amendments to the EEC guidelines (4.6, 4.7); ammonium chloride was not included in the medium to avoid nitrification; the test was continued for more than 28 days; in the comparative experiment for dimethyl distearyl ammonium chloride a recalcitrant sulphonate (1 mg/ml) was added to the medium to reduce this quaternary ammonium compound's toxicity.
- the dissolved oxygen concentrations were determined electrochemical ly using an oxygen electrode (WTW Trioxmatic EO 200) and an oxygen gauge (WTW 0X1 530) and biodegradability was calculated as the ratio of biological oxygen dependence (BOD) to theoretical oxygen dependence (ThOD): BOD/ThOD.
- 3 1 three-necked flask 359,4 g (3,80 moles) of onochloroacetic acid were mixed with 1020 g (3,77 moles) of stearyl alcohol and the whole was esterified at a temperature in the range of 120° to 200°C, with continuous removal of the generated reaction water, to form stearyl-2-chloroacetate. After an approximately 10-hour long esterification reaction a product having a degree of esterification of about 99% was obtained.
- the product When analysed for quaternary ammonium, the product was found to be 97% pure. The water content was determined to be 2,8 wt.%; the melting point was 106°-108°C. The structure was confirmed with the aid of H-NMR analysis.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Proposed are biodegradable fabric softeners of increased hydrolytic stability upon storage having as essential constituent a biodegradable quaternary ammonium compound of formula (I), wherein R1 represents an alk(en)yl group having 11-22 carbon atoms, R2 represents an alk(en)yl group having 11-21 carbon atoms, and X- represents an anion. Examples of such quaternary ammonium compounds include: N,N-dimethyl-2-(octadecyl-oxy)-2-oxo-N-(2-[(1-oxohexadecyl)-oxy]ethyl chloride and N,N-dimethyl-2-(H-tallow alkyl-oxy)-2-oxo-N-(2-[1-oxo-H-tallow alkyl)oxy]ethyl chloride.
Description
BIODEGRADABLE FABRIC SOFTENERS
The invention relates to fabric softeners of improved hydrolytic stability upon storage which contain as essential constituent a biodegradable quaternary ammonium compound.
Fabric softeners of the above-mentioned type have earlier been suggested in US-A-4767 547. Preferred among the plurality' of compounds described therein are compounds of the formula N,N-di (alkanoyl-oxy-ethy1)-N,N-dimethyl ammonium chloride, their principal representative being
N,N-di (tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride. However, it has been found that the hydrolytic stability of said compound during storage of a 5% dispersion in water over 4 weeks at 50°C was capable of being improved further.
The invention now provides quaternary ammonium compound-containing fabric softeners of greatly improved hydrolytic stability without any attendant deterioration of the biodegradability.
The invention consists in that the fabric softeners of the known type mentioned in the opening paragraph contain as essential constituent a quaternary ammonium compound of the formula:
It should be noted that compounds of a similar structure have already been proposed in US-A-4370272. However, in the compounds described
in said publication the group R* in the aforesaid formula in each case is esterϊfied with the use of 1 to 3 al oxy groups containing 2 or 3 carbon atoms. However, these compounds are found to be less hydrolytically stable than the compounds put forward in the 5 aforementioned US-A-4767547.
It should therefore be considered extremely surprising quaternary ammonium compounds of a structure comparable with that in the last patent specification, but without the presence of additional alkoxy groups will give compounds of an unexpectedly high hydrolytic ° stability. Surprisingly, said hydrolytic stability turns out to be much higher even than that of the corresponding symmetrical diesters of the formulae (CH3)2N+(CH2CH20C0R)2 Cl" and
(CH3)2N+(CH2C0 R)2 cl", respectively, wherein R stands for a higher alkyl group, such as a tallow alkyl or hydrogenated tallow alkyl 5 group.
Within the scope of the invention preference is given to compounds corresponding to the first structural formula in which R* and R* may be the same or different and represent an alk(en)yl group having 15-18 ° carbon atoms. Preference is given in this case to the utilisation of compound in which R* and R* may the same or different and represent a tallow alkyl or coco alkyl group which may be hydrogenated or not. Also, favourable results can be attained when Ri represents a stearyl group and the same goes for when R2 represents a pentadecyl group. 5 Other groups considered suitable within the scope of the invention include lauryl, oleyl, and palmityl . Alternatively, for Ri and R* use may be made of mixtures of alk(en)yl groups of different chain 1engths. All that can be required of the anion X~ which is contained in the 0 present quaternary ammonium compounds as counterion is for it to be compatible with the cationic fabric softening action, to be itself non-toxic, and to generate a water-soluble or water-dispersible salt with the quaternary ammonium cation. Preferably, X~ represents a halide anion, more particularly a chloride, sulphate, methosulphate, carboxylate or sulphonate anion.
The present quaternary ammonium compounds can be prepared in the manner known for the preparation of analogous compounds. In the example which will follow the preparation of a representative quaternary ammonium compound according to the present invention is described in detail, and the remaining biodegradable fabric softening agents according to the present invention are directly accessible to the skilled man through adaptation of the starting substances concerned.
The manner in which the present biodegradable fabric softening agent is applied is the same as for the conventional, now commercially available fabric softeners, where the agent, together with the surfactant, can be contacted with the textile material to be softened in the form of a rinsing agent or else in the dryer. The fabric softening action envisaged and actualised here is the same as that of the conventional fabric softeners. Inevitably, via the rinsing solution a portion of the fabric softener will end up in the waste water, where, because of the present invention, there will be less harm to the environment as a result of accelerated biodegradability.
The present biodegradable fabric softening agents were tested for their fabric softening action and found to be comparable with dimethyl distearyl ammonium chloride and l-methyl-2-tallow alkyl-3-tallow amidoethyl imidazolinium ethosulphate. In this test towels treated with the fabric softeners in question were line dried for 24 hours and then cut up into strips of 10 x 20 cm* . A test panel tested the softening action as compared with that of the standard test surfactant (IEC), whereupon the observational data was statistically processed in accordance with DIN standard 10954.
No significant difference in fabric softening action was found between the known fabric softeners and the fabric softener prepared in' conformity with the preparative process disclosed in Example I.
The hydrolytic stabil ty of the present quaternary ammonium compounds according to the invention was tested at a temperature of 50°C and a pH in the range of 3,5 to 4. To this end a 5% dispersion in water was prepared, after which the pH was set at a value in the range of 3 to 4,5 by the addition of a Bronstedt acid.
Measuring was as follows. First, a melt of the compound to be tested was charged, with proper stirring, to a flask filled with distilled water, after which hydrochloric acid or sodium hydroxyde was employed to set the pH at a predetermined value. Next, the degree of hydrolysis was determined with the aid of H-NMR analysis, NaOH titration, and/or HPLC analysis.
In a comparison of the product (A) prepared in conformity with the description in Example I with the known symmetrical diesters of the formulae (CH3)2N+(CH2CH20C0R)2 Cl" (B) and (CH3)2N+(CH2C02R)2 Cl" (C), respectively, wherein R represents a hydrogenated tallow alkyl group, the following values (given in the table below) were measured for the degree of hydrolysis.
Tabl e
Compound pH wt . hydro l ysed
A 4 < 7
B 3 , 5 69
C 4 32
The present quaternary ammonium compounds were tested for biodegradability in accordance with the EEC/OECD guidelines (4.1, 4.2) using the closed bottle test. In this experiment a test compound is added to an aqueous solution of mineral salts and exposed for 28 days under aerobic conditions to a relatively small number of micro-organisms. The formal test regulations were departed from on the following minor issues:
the inoculum was taken from an apparatus containing activated sludge preconditioned in accordance with proposed amendments to the EEC guidelines (4.6, 4.7);
ammonium chloride was not included in the medium to avoid nitrification; the test was continued for more than 28 days; in the comparative experiment for dimethyl distearyl ammonium chloride a recalcitrant sulphonate (1 mg/ml) was added to the medium to reduce this quaternary ammonium compound's toxicity.
The dissolved oxygen concentrations were determined electrochemical ly using an oxygen electrode (WTW Trioxmatic EO 200) and an oxygen gauge (WTW 0X1 530) and biodegradability was calculated as the ratio of biological oxygen dependence (BOD) to theoretical oxygen dependence (ThOD): BOD/ThOD.
Compared with the aforementioned commercially available fabric softeners a significantly accelerated biodegradability was observed.
The invention will be further illustrated with reference to the following examples. The scope of the invention, however, is not restricted to the specific details of the example.
Example
In a 1 1 three-necked flask 435 g (1,68 moles) of palmitic acid were mixed with 227 g (2,52 moles) of N,N-dimethyl ethanolamine and the whole was heated for 10 hours at a temperature in the range of 150° to 200°C, with continuous removal from the reaction mixture of the water generated during the reaction. On conclusion of the reaction a product having a degree of esterification of about 97% was obtained.
In another, 3 1 three-necked flask 359,4 g (3,80 moles) of onochloroacetic acid were mixed with 1020 g (3,77 moles) of stearyl alcohol and the whole was esterified at a temperature in the range of 120° to 200°C, with continuous removal of the generated reaction water, to form stearyl-2-chloroacetate. After an approximately 10-hour long esterification reaction a product having a degree of esterification of about 99% was obtained.
In a 11 three-necked flask 313 g (0,9 moles) of stearyl-2-chloroacetate were mixed in the melt with 302 g (0,9 moles) of "palmitic-2-dimethyl aminoethyl ester and the whole was then kept for three hours at a temperature in the range of 90° to 100°C. After cooling the solidified reaction product was recrystallised from 2-propanol .
When analysed for quaternary ammonium, the product was found to be 97% pure. The water content was determined to be 2,8 wt.%; the melting point was 106°-108°C. The structure was confirmed with the aid of H-NMR analysis.
Claims
A fabric softener of increased hydrolytic stability upon storage having as essential constituent a biodegradable quaternary ammonium compound of the formula:
2. A fabric softener according to claim 1, characterised in that Ri and R2 may be the same or different and represent an alk(en)yl group having 15-18 carbon atoms.
3. A fabric softener according to claim 1, characterised in that Ri and R~ may be the same or different and represent an H- tallow alkyl or coco-alkyl group.
4. A fabric softener according to claim 1, characterised in that Ri represents a stearyl group.
5. A fabric softener according to claim 1, characterised in that • - represents a pentadecyl group.
6. A fabric softener according to one or more of the preceding claims, characterised in that X~ represents a halide anion, more particularly a chloride, sulphate, methosulphate, carboxylate or sulphonate ion.
7. N,N-dimethyl-2-(octadecyl-oxy)-2-oxo-N-(2-[(l-oxohexadecyl) -oxy]ethyl chloride.
8. N,N-dimethyl-2-(H-tallow alkyl -oxy) -2-oxo-N-(2-[l-oxo-H- tallow alkyl) oxy] ethyl chloride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL9200319 | 1992-02-20 | ||
| NL9200319 | 1992-02-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993017085A1 true WO1993017085A1 (en) | 1993-09-02 |
Family
ID=19860465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1993/000173 WO1993017085A1 (en) | 1992-02-20 | 1993-01-26 | Biodegradable fabric softeners |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO1993017085A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5474690A (en) * | 1994-11-14 | 1995-12-12 | The Procter & Gamble Company | Concentrated biodegradable quaternary ammonium fabric softener compositions containing intermediate iodine value fatty acid chains |
| US5545340A (en) * | 1993-03-01 | 1996-08-13 | The Procter & Gamble Company | Concentrated biodegradable quaternary ammonium fabric softener compositions and compounds containing intermediate iodine value unsaturated fatty acid chains |
| US8785355B2 (en) | 2001-02-13 | 2014-07-22 | Schlumberger Technology Corporation | Viscoelastic compositions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4370272A (en) * | 1980-01-14 | 1983-01-25 | Stepan Chemical Company | Alkoxylated quaternary ammonium surfactants |
| EP0239910A2 (en) * | 1986-04-02 | 1987-10-07 | The Procter & Gamble Company | Biodegradable fabric softeners |
| EP0409502A2 (en) * | 1989-07-17 | 1991-01-23 | Unilever Plc | Fabric softening composition |
-
1993
- 1993-01-26 WO PCT/EP1993/000173 patent/WO1993017085A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4370272A (en) * | 1980-01-14 | 1983-01-25 | Stepan Chemical Company | Alkoxylated quaternary ammonium surfactants |
| EP0239910A2 (en) * | 1986-04-02 | 1987-10-07 | The Procter & Gamble Company | Biodegradable fabric softeners |
| EP0409502A2 (en) * | 1989-07-17 | 1991-01-23 | Unilever Plc | Fabric softening composition |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 111, 1989, Columbus, Ohio, US; abstract no. 216317, * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5545340A (en) * | 1993-03-01 | 1996-08-13 | The Procter & Gamble Company | Concentrated biodegradable quaternary ammonium fabric softener compositions and compounds containing intermediate iodine value unsaturated fatty acid chains |
| US5562849A (en) * | 1993-03-01 | 1996-10-08 | The Procter & Gamble Company | Concentrated biodegradable quaternary ammonium fabric softener compositions and compounds containing intermediate iodine value unsaturated fatty acid chains |
| US5574179A (en) * | 1993-03-01 | 1996-11-12 | The Procter & Gamble Company | Concentrated biodegradable quaternary ammonium fabric softener compositions and compouds containing intermediate iodine value unsaturated fatty acid chains |
| US5474690A (en) * | 1994-11-14 | 1995-12-12 | The Procter & Gamble Company | Concentrated biodegradable quaternary ammonium fabric softener compositions containing intermediate iodine value fatty acid chains |
| US8785355B2 (en) | 2001-02-13 | 2014-07-22 | Schlumberger Technology Corporation | Viscoelastic compositions |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5637743A (en) | Quaternary ammonium surfactants derived from tertiary amines and fabric softeners containing quaternary ammonium surfactants | |
| EP0122141B1 (en) | Fabric softening compositions | |
| EP0013780B1 (en) | Concentrated fabric softening composition | |
| EP0721936B1 (en) | Liquid softener composition and quaternary ammonium salt | |
| GB1599171A (en) | Textile treatment composition | |
| EP0008839B1 (en) | Process for preparing compositions containing quaternary ammonium compounds | |
| US4131562A (en) | Stabilized particulate peroxygen compounds | |
| EP1639067A1 (en) | Mdea ester quats with high content of monoester in blends with tea ester quats. | |
| CA1232414A (en) | Aqueous fabric softening composition | |
| EP0038862A1 (en) | Compositions containing amido amine salts, and their use as fabric softeners | |
| EP0638639B1 (en) | Biodegradable fabric softening composition | |
| EP0086106A2 (en) | Fabric softening composition | |
| US4948520A (en) | Softener composition | |
| WO1993017085A1 (en) | Biodegradable fabric softeners | |
| CA1232415A (en) | Aqueous concentrated fabric softening composition | |
| CA1232709A (en) | Aqueous concentrated fabric softening composition | |
| WO1992008837A2 (en) | Biodegradable fabric softeners | |
| EP0086104B1 (en) | Method of softening fabrics | |
| EP0687722B1 (en) | Biodegradable fabric conditioning molecules based on glyceric acid | |
| US5543066A (en) | Biodegradable fabric softening composition | |
| JPH0819619B2 (en) | Softener composition for textile products and method for softening textile materials using the same | |
| CA1226407A (en) | Aqueous fabric softening composition | |
| GB2032479A (en) | Novel fabric softeners | |
| CA1137110A (en) | Diamidoamine containing fabric softeners | |
| EP0790295A2 (en) | Fabric softening composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA CZ JP US |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE |
|
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) |
Free format text: CZ |
|
| 122 | Ep: pct application non-entry in european phase | ||
| NENP | Non-entry into the national phase |
Ref country code: CA |