EP0924291B2 - Wässrige Weichspülmittel mit verbessertem Weichgriff - Google Patents
Wässrige Weichspülmittel mit verbessertem Weichgriff Download PDFInfo
- Publication number
- EP0924291B2 EP0924291B2 EP98119569A EP98119569A EP0924291B2 EP 0924291 B2 EP0924291 B2 EP 0924291B2 EP 98119569 A EP98119569 A EP 98119569A EP 98119569 A EP98119569 A EP 98119569A EP 0924291 B2 EP0924291 B2 EP 0924291B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- fatty acid
- test
- fabric
- water
- 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 - Lifetime
Links
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 32
- 239000000194 fatty acid Substances 0.000 claims description 32
- 229930195729 fatty acid Natural products 0.000 claims description 32
- 150000004665 fatty acids Chemical class 0.000 claims description 30
- 239000002979 fabric softener Substances 0.000 claims description 17
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052740 iodine Inorganic materials 0.000 claims description 12
- 239000011630 iodine Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000003760 tallow Substances 0.000 claims description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 16
- 239000004744 fabric Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 239000002304 perfume Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000013530 defoamer Substances 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- -1 ester compounds Chemical class 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 150000001767 cationic compounds Chemical class 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical group 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- 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
- C11D3/0015—Softening compositions liquid
Definitions
- the present invention relates to fabric softeners in the form of aqueous emulsions or dispersions.
- cationic compounds are used as fabric softeners, for example quaternary ammonium compounds which, in addition to long-chain alkyl radicals, may also contain ester or amide groups, for example as described in US Pat. Nos. 3,449,033, 3,644,203, 3,946,115, 3,997,453 and 4,073,735, 4119 545. These components are added to the rinse bath alone or in mixtures with other cationic or even neutral substances in the form of aqueous dispersions.
- ammonium compounds containing ester bonds as described, for example, in EP-A-0 239 910, US Pat. No. 3,915,867, US Pat. No. 4,137,180, US Pat. No. 4,830,771.
- WO-A-94/20597 relates to concentrated softeners containing quaternary ammonium compounds in which the long-chain fatty acid residues contain 11 to 21 carbon atoms and have iodine numbers in the range of 5 to 100.
- US-A-5,637,743 discloses the provision of a fabric softener containing quaternary ammonium salts wherein the fatty acid moieties contain 5 to 23 carbon atoms, the ratio of fatty acid: amine is 1.85 to 1.40 and iodine numbers are in the range of 10 to 33.
- ester compounds based on triethanolamine such as N-methyl-N, N-bis (beta-C 14-18 -acyloxyethyl), N-beta-hydroxyethyl ammonium methosulfate, which are sold under trade names such as TETRANYL® AT 75 (trademark of KAO Corp.), STEPANTEX® VRH 90 (trademark of Stepan Corp.) or REWOQUAT® WE 18 (trademark of Witco Surfactants GmbH).
- Reverse wetting is generally understood to mean the absorption of moisture by the fiber.
- a defective reverse wetting effect has a disadvantageous effect where larger amounts of moisture are to be absorbed by the skin surface.
- the object of the invention was to overcome the abovementioned disadvantages of conventional fabric softener formulations and to provide fabric softeners which, in addition to good biodegradability, have a substantially improved level of good soft feel while retaining a good repellency.
- the object has been achieved by using quaternary fatty acid aminal alcohol esters of triethanolamine with partially hydrogenated fatty acids in a ratio of 1: 1.6 to 1: 2 in alcohols or glycols.
- the quaternary compounds of the general formula I used in accordance with the invention are prepared by esterification of triethanolamine with fatty acid and subsequent quaternization by processes which are generally known in the art.
- the fat components used for the esterification or transesterification are the monobasic fatty acids known and customary in this field and based on natural vegetable and animal oils with in particular 14-18 carbon atoms, such as tallow fatty acids and palm oil fatty acids or their methyl or ethyl esters.
- the content of these fatty acids or fatty acid esters of unsaturated constituents is adjusted by the known catalytic hydrogenation to iodine numbers between 15-25, or by mixing fully hydrogenated with non-hydrogenated fat components.
- the iodine number is the amount of iodine absorbed by 100 g of the compound to saturate the double bonds.
- Partially hydrogenated tallow fatty acids and palm oil fatty acids with iodine numbers between 15-25 are preferred according to the invention. They are commercial products and are offered by various companies under their respective trade names.
- the esterification or transesterification is carried out by known methods.
- the triethanolamine with the desired degree of esterification corresponding amount of fatty acid or fatty acid ester optionally in the presence of a catalyst, for.
- methanesulfonic acid reacted under nitrogen at 160-240 ° C and distilling off the water of reaction or the alcohol forming continuously, to optionally complete the reaction, the pressure can be reduced.
- the subsequent quaternization is carried out by known methods.
- the procedure is preferably such that the ester, optionally with the concomitant use of a solvent, preferably with isopropanol, ethanol, 1,2-propylene glycol and / or dipropylene glycol, at 60-90 ° C with equimolar amounts of the quaternizing agent with stirring, optionally under pressure and the completion of the reaction is monitored by controlling the total amine number.
- Examples of the quaternizing agents used are short-chain dialkyl phosphates and sulfates, such as diethyl sulfate, dimethyl phosphate, diethyl phosphate, short-chain halogenated hydrocarbons; In particular, according to the invention dimethyl sulfate is used.
- TAA triethanolamine
- fatty acids were reacted and quaternized by the usual methods.
- Fatty acid I Tallow fatty acid having an acid number of 200-210, an iodine value of 15-25 and a C chain distribution of ⁇ C - 16 about 2% C - 16 about 26% C - 16 ' about 2% C - 17 about 3% C - 18 about 48% C - 18 ' about 15% C - 18 " ⁇ 1%
- Fatty acid III Tallow fatty acid having an acid number of 200-210, an iodine value of 45-55 and a C chain distribution of ⁇ C - 16 about 4% C - 16 about 26% C - 16 ' about 2%
- TEA fatty acid I 1: 2
- Component B TEA: fatty acid I 1: 1.6
- Component C TEA: fatty acid II 1: 2
- Component D TEA: fatty acid II 1: 1.6
- Component E TEA: fatty acid III 1: 2
- Component F TEA: fatty acid III 1: 1.6
- the fabric softeners are prepared by emulsifying or dispersing the respective individual components in water. In this case, the usual procedures in this field can be used.
- the usual procedure is to initially charge the water preheated to about 10 ° C. below the clear melting point of the plasticizer, then, with good stirring, first the dye solution, then the optionally required antifoam emulsion and finally the clear melt of the individual plasticizers. After adding a partial amount of an electrolyte solution, perfume oil is added, followed by the remaining amount of electrolyte solution, and then allowed to cool to room temperature while stirring.
- the fabric softeners according to the invention may contain the specified components within the usual limits in this field, such as 15-22 wt .-% of the compounds of general formula (I); 2-5 wt .-% of a solvent such as in particular isopropanol, ethanol, propylene glycol, dipropylene glycol; 0.5-1.5% by weight of an alkali and / or alkaline earth salt; 0.5-1.5% by weight of perfume oil and the remainder to 100% by weight (ad 100) of water.
- a solvent such as in particular isopropanol, ethanol, propylene glycol, dipropylene glycol
- 0.5-1.5% by weight of an alkali and / or alkaline earth salt 0.5-1.5% by weight of perfume oil and the remainder to 100% by weight (ad 100) of water.
- the fabric softeners according to the invention are added following the actual washing process in the last rinse.
- Application dilution after dilution with water ranges from 0.1 to 10 g of fabric softener per liter of treatment liquor, depending on the application.
- test fabric (about 3 kg cotton twill fabric, 100% cotton, supplier: WFK-Testgewebe GmbH, Krefeld) is washed twice with 100 g test detergent and then without detergent (each 95 ° C program with prewash) , The test fabric is hung for one day at room temperature to dry. After drying, test strips of about 25 cm in length and 1.5 cm in width are cut. It is important to ensure that all test strips of a test series have the same thread course.
- test strips are marked with a ballpoint pen. Holes are punched at both ends of the test strips; while a 5 cm thick fabric edge should be preserved.
- the corresponding amount of demineralized water is introduced and stirred in 0.025%, based on the solids content, of the product to be tested.
- a blank test is carried out by submitting demineralized water in the immersion bath.
- test strips are added, stirred for 5 minutes at about 50 rpm using a magnetic stirrer and then left for 5 minutes without stirring. Subsequently, the test strips are dried hanging at room temperature for 24 h. After this time, draw a line parallel to the long outer edges with a water-soluble felt pen on the smooth side of each strip.
- test strips blank + test product (s)
- the immersion device with the strips is placed in the tub filled with demineralized water (about 10 l) to a height of 8 cm and left there for 5 min. 10 min after removing the immersion device from the tub, the height of rise of the water, the It is important to make sure that the lower edge of the hole, with its upper side, rests directly against the (hanging) hook in order to avoid reading errors.
- the demineralized water must be renewed after each attempt.
- test fabric fabric "Duosoft", 100% cotton, supplier: Vossen
- test fabric 100% cotton, supplier: Vossen
- a fixed mesh size of 15 results in a liquor ratio of 1: 5. After washing, the test fabric is hung for one day at room temperature to dry and then stored until processing at room temperature.
- the calculated amounts of fabric softener are placed in the beakers at 15-20 ° C and filled with tap water of about 9 ° dH and 15-20 ° C to 2 l. The mixture is then stirred on the magnetic stirrer until homogeneous dispersions or solutions have been present.
- a blank test is carried out by pure tap water is presented in the dip. 1 piece of test fabric is dipped per rinse bath. After 10 minutes, the tissue is removed from the rinse bath, gently wrung out, gently shaken three times and dried for one hour at room temperature in a single-layered suspension.
- test fabric thus treated is cut into 10 equal pieces (about 16x25 cm). Each subject receives a new test piece for the assessment. It must be prevented that the test pieces are "softened” after some attempts to grip.
- test fabrics treated with different softeners are now compared in pairs.
- the contestants can distribute whole points between 0 and 5, where 0 point means bad (hard) and 5 points means good (soft).
- dispersions are prepared from the components mentioned:
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19756434 | 1997-12-18 | ||
| DE19756434A DE19756434A1 (de) | 1997-12-18 | 1997-12-18 | Wäßrige Weichspülmittel mit verbessertem Weichgriff |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0924291A1 EP0924291A1 (de) | 1999-06-23 |
| EP0924291B1 EP0924291B1 (de) | 2003-09-03 |
| EP0924291B2 true EP0924291B2 (de) | 2006-07-26 |
Family
ID=7852465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98119569A Expired - Lifetime EP0924291B2 (de) | 1997-12-18 | 1998-10-16 | Wässrige Weichspülmittel mit verbessertem Weichgriff |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US6110887A (pl) |
| EP (1) | EP0924291B2 (pl) |
| CA (1) | CA2254399C (pl) |
| DE (2) | DE19756434A1 (pl) |
| ES (1) | ES2206808T5 (pl) |
| PL (1) | PL195045B1 (pl) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19855366A1 (de) * | 1998-12-01 | 2000-06-08 | Witco Surfactants Gmbh | Niedrigkonzentrierte, hochviskose wäßrige Weichspülmittel |
| AU4856399A (en) * | 1999-07-01 | 2001-01-22 | Procter & Gamble Company, The | Quaternary nitrogen compound, fabric care composition containing same, and process for forming same |
| US7371718B2 (en) * | 2005-04-22 | 2008-05-13 | The Dial Corporation | Liquid fabric softener |
| WO2011149475A1 (en) | 2010-05-28 | 2011-12-01 | Colgate-Palmolive Company | Fatty acid chain saturation in alkanol amine based esterquat |
| EP2997958B1 (de) | 2014-09-22 | 2021-03-10 | Evonik Operations GmbH | Emulsion enthaltend flüssige esterquats und polymerverdicker |
| EP2997959B1 (de) | 2014-09-22 | 2019-12-25 | Evonik Operations GmbH | Formulierung enthaltend esterquats basierend auf isopropanolamin und tetrahydroxypropylethylenediamin |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2021900A6 (es) * | 1989-07-17 | 1991-11-16 | Pulcra Sa | Procedimiento de obtencion de tensioactivos cationicos derivados de amonio cuaternario con funcion amino-ester. |
| DE4101251A1 (de) * | 1991-01-17 | 1992-07-23 | Huels Chemische Werke Ag | Fettsaeureester des n-methyl-n,n,n-trihydroxyethyl-ammonium-methyl- sulfat enthaltende waessrige emulsionen |
| ES2094893T3 (es) * | 1991-12-31 | 1997-02-01 | Stepan Europe | Tensioactivos a base de compuestos de amonio cuaternario, procedimientos de preparacion, bases, y composiciones suavizantes derivadas. |
| PT687291E (pt) * | 1993-03-01 | 2000-09-29 | Procter & Gamble | Composicoes concentradas e biodegradaveis amaciadoras de texteis a base de amonio quaternario e compostos contendo cadeias de acido gordo insaturado possuindo um valor de iodo intermedio |
| JP3235915B2 (ja) * | 1993-07-13 | 2001-12-04 | ファナック株式会社 | ワイヤ結線状態表示装置 |
| DE4339643C1 (de) * | 1993-11-20 | 1995-06-08 | Henkel Kgaa | Verfahren zur Herstellung von festen Esterquats |
| DE4400927A1 (de) * | 1994-01-14 | 1995-07-20 | Henkel Kgaa | Wäßrige Lösungen von quaternierten Fettsäuretriethanolaminester-Salze |
| DE4405702A1 (de) * | 1994-02-23 | 1995-08-24 | Witco Surfactants Gmbh | Hochkonzentrierte wäßrige Weichspülmittel mit verbesserter Lagerstabilität |
| US5869716A (en) * | 1994-03-18 | 1999-02-09 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of esterquats |
| US5503756A (en) * | 1994-09-20 | 1996-04-02 | The Procter & Gamble Company | Dryer-activated fabric conditioning compositions containing unsaturated fatty acid |
| DE4446137A1 (de) * | 1994-12-23 | 1996-06-27 | Huels Chemische Werke Ag | Quaternierte Triethanolamindifettsäureester |
| EP0850291B1 (en) * | 1995-08-31 | 2002-01-30 | Colgate-Palmolive Company | Stable fabric softener compositions |
| EP0768369A1 (en) * | 1995-10-11 | 1997-04-16 | The Procter & Gamble Company | Fabric softener compositions |
| US5916863A (en) * | 1996-05-03 | 1999-06-29 | Akzo Nobel Nv | High di(alkyl fatty ester) quaternary ammonium compound from triethanol amine |
-
1997
- 1997-12-18 DE DE19756434A patent/DE19756434A1/de not_active Ceased
-
1998
- 1998-10-16 DE DE59809482T patent/DE59809482D1/de not_active Expired - Lifetime
- 1998-10-16 ES ES98119569T patent/ES2206808T5/es not_active Expired - Lifetime
- 1998-10-16 EP EP98119569A patent/EP0924291B2/de not_active Expired - Lifetime
- 1998-11-23 US US09/198,181 patent/US6110887A/en not_active Expired - Lifetime
- 1998-11-24 CA CA002254399A patent/CA2254399C/en not_active Expired - Lifetime
- 1998-12-17 PL PL330381A patent/PL195045B1/pl unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA2254399A1 (en) | 1999-06-18 |
| EP0924291A1 (de) | 1999-06-23 |
| US6110887A (en) | 2000-08-29 |
| DE59809482D1 (de) | 2003-10-09 |
| ES2206808T3 (es) | 2004-05-16 |
| PL330381A1 (en) | 1999-06-21 |
| DE19756434A1 (de) | 1999-06-24 |
| ES2206808T5 (es) | 2007-04-01 |
| PL195045B1 (pl) | 2007-08-31 |
| EP0924291B1 (de) | 2003-09-03 |
| CA2254399C (en) | 2007-07-10 |
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