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    • 专利摘要:
    ACTIVE FABRIC SOFTENER COMPOSITION AND METHOD FOR PREPARATION OF THE SAME. The present invention relates to an active fabric softener composition comprising at least 50% by weight of a fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate having a molar ratio of fatty acid fractions to amine fractions from 1.5 to 1.99, the average chain length of the fatty acid fractions being 16 to 18 carbon atoms and the iodine value of the fatty acid fractions, calculating for the free fatty acid is 0.5 to 50, and 0.5 to 5% by weight of fatty acid provides high softener performance and good stability during storage in the aqueous dispersion and can be handled and processed in a liquid state without the addition of a flammable solvent .
    公开号:BR112012024811B1
    申请号:R112012024811-1
    申请日:2011-03-18
    公开日:2021-08-31
    发明作者:Hans-Jurgen Kohle；Ulrike Kottke；Harald Jakob；Jens Hildebrand
    申请人:Evonik Operations Gmbh；
    IPC主号:
    专利说明:

    [001] The present invention relates to active fabric softener compositions having high softener performance and good stability during storage in aqueous formulations, which can be processed to aqueous formulations without the use of volatile solvents.
    [002] Quaternary ammonium salts carrying two hydrophobic long chain hydrocarbon fractions have found wide use as fabric softening actives. The esterified quaternary ammonium salts of alkanolamines with on average two fatty acid fractions per molecule, commonly referred to as ester quats, have previously largely substituted alkyl quaternary ammonium compounds because of their biodegradability.
    [003] For use in rinse cycle softener products, an active softener composition has to meet the various and sometimes conflicting requirements: - high softener performance in terms of soft touch and fabric rewetability, - good stability during storage in dispersion aqueous with little change in dispersion viscosity, and - convenient processing and control in a liquid state.
    [004] The quat esters that have found the widest technical use and that currently set the standard for softening performance are methyltriethanolammonium methylsulfate fatty acid diesters and dimethyldiethanolammonium chloride fatty acid diesters. However, aqueous dispersions of these fabric softener actives have limited stability and prolonged storage of such aqueous dispersions at temperatures in excess of 40°C will generally lead to an unacceptable increase in dispersion viscosity or sedimentation of the softener active. Furthermore, these fabric softener actives cannot be manipulated and processed to aqueous dispersions without the addition of a solvent because of their high melting points and melt viscosities and the limited hydrolytic and thermal stability of the fabric softener actives. tissue. Therefore, they are generally released and processed with a content of 5 to 15% by weight of ethanol or isopropanol, which requires additional precautions due to the volatility and flammability of the solvent.
    [005] EP 0 293 955 A2 and EP 0 302 567 A2 describe aqueous fabric softener dispersions having high storage stability and little change in viscosity during storage and a method for preparing such dispersions. These compositions contain a bis-(2-hydroxypropyl)-dialkylammonium salt fatty acid diester as the fabric softener active in the form of submicrometer particles. However, the preparation of these dispersions requires processing the fabric softener active mixed with from 5 to 50% by weight of a C1-C4 monohydric alcohol. In the examples, bis-(2-hydroxypropyl)-dimethylammonium chloride palmitic acid diester is used as the fabric softener active and isopropanol is used as the solvent.
    [006] DE 24 30 140 C3 describes fatty acid diesters of bis-(2-hydroxypropyl)-dialkylammonium salt to provide liquid fabric softening actives. Example 2 describes the preparation of a bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid diester by reacting a bis-(2-hydroxypropyl)-methylamine fatty acid diester of a fatty acid having a chain length average of 19 to 20 carbon atoms and comprising 90% by weight of unsaturated fatty acid fractions with dimethyl sulphate in a molar ratio of 1:1.
    [007] EP 1 018 541 A1 describes clear fabric softener compositions comprising a quat ester and an alkoxylated phenol or branched C3-C6 alcohol solvent. Example 6 describes a composition containing a fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate having a molar ratio of fatty acid fractions to amine fractions of 1.8 derived from a fatty acid having a length of chain average of 18 carbon atoms and an iodine number of about 150. The quate ester active is processed with the addition of 10% by weight of isopropanol in masking this composition, as described in paragraph [0026].
    [008] WO 00/06678 describes incompletely esterified quat esters of branched-chain alkanolamines, which are claimed to have low melting points and high hydrolytic stability, and proposes to leave on average a hydroxyl group of the non-esterified alkanolamine. Example 50 describes a bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester made by quaternizing a bis-(2-hydroxypropyl)-methylamine fatty acid ester having a molar ratio of acid fractions. fatty to amine fractions of 1.26 derived from a fatty acid having a chain length of 12 to 14 carbon atoms.
    [009] DE 36 08 093 A1 describes concentrated aqueous fabric softener compositions comprising a quat ester with two acyl groups, a fatty acid or an alkali salt thereof in an amount of 1/70 to 1/3 of the amount of the ester quat and a combination of water solvent, glycerol and an additional organic solvent in a total amount of 1/6 to twice the amount of the quat ester. Example 4 describes a composition containing 45% by weight of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate oleic acid diester, 1% by weight of tallow fatty acid sodium salt, 11.5% by weight of water, 11.5% by weight of glycerol, 17.5% by weight of 2-propanol, 6% by weight of propylene glycol and 3% by weight of dipropylene glycol.
    [010] The quat ester actives described in DE 24 30 140 C3, EP 1 018 541 A1 and WO 00/06678 have low melting points but provide insufficient softening performance due to the high degree of establishment of the fatty acid fractions or the high content of monoester quat component. On the other hand, similar ester quats derived from bis-(2-hydroxypropyl)-methylamine with a low monoester quat content, made from fatty acids with a low degree of unsaturation, such as that described in EP 302 567 A2, provide the performance softening required, but show high melting points and melt viscosities and therefore require addition of a solvent for handling and processing.
    [011] Therefore, there is still a need for fabric softener actives that can be handled and processed without a solvent without compromising stability during storage in the aqueous dispersion with little change in dispersion viscosity.
    [012] It has now been observed that active fabric softener compositions based on a fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate made from fatty acids with a specific chain length and a specific degree of instauration and having a particular molar ratio of fatty acid fractions to amine fractions, which comprise a specific amount of free fatty acid, provide high softener performance and good stability during storage in aqueous dispersion, and at the same time can be handled and processed in a liquid state without the addition of a flammable solvent.
    [013] The present invention is therefore directed to an active fabric softener composition comprising at least 50% by weight of a fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate having a molar ratio of fatty acid fractions to amine fractions from 1.5 to 1.99, an average chain length of the fatty acid fractions from 16 to 18 carbon atoms, and an iodine index of the fatty acid fractions, calculated for the fatty acid free, from 0.5 to 50, and from 0.5 to 5% by weight of fatty acid.
    [014] The invention is also directed to a method for the preparation of such compositions, comprising the steps of reacting bis-(2-hydroxypropyl)-methylamine with a fatty acid having an average chain length of 16 to 18 carbon atoms and an iodine number of 0.5 to 50 at a molar ratio of fatty acid to amine of 1.51 to 2.1 with water removal until the acid value of the reaction mixture is in the range of 1 to 10 mg of KOH/g and also react with dimethyl sulphate in a molar ratio of dimethyl sulphate to amine of 0.90 to 0.97 and preferably 0.92 to 0.95 until the total amine value of the reaction mixture is in the range from 1 to 8 mg KOH/g.
    [015] The active fabric softener composition of the invention comprises at least 50% by weight of a fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate. The composition preferably comprises from 85 to 99% by weight of said ester. The use of a methylsulfate salt surprisingly provides both a lower melting point of the composition and better stability for hydrolysis of an aqueous dispersion of the composition compared to a chloride salt as used in EP 0 293 955 A2 and EP 0 302 567 A2 .
    [016] The fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is a mixture of at least one diester of the formula (CH3)2N+(CH2CH(CH3)OC(=O)R)2 CH3OSO3- and at least one monoester of the formula (CH3)2N+(CH2CH(CH3)OH)(CH2CH(CH3)OC(=O)R) CH3OSO3-, where R is the hydrocarbon group of a fatty acid moiety RCOO. The fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate has a molar ratio of fatty acid fractions to amine fractions from 1.5 to 1.99 and preferably from 1.85 to 1.99. The specified molar ratio is essential to simultaneously obtain high softener performance and low melting point of the composition. A molar ratio in the range of 1.85 to 1.99 provides high softener performance in the absence of anionic surfactants or in low concentrations of such surfactants. Active fabric softener compositions having such a molar ratio are therefore useful for preparing wash cycle softeners intended for use in a laundry application where the laundry is rinsed several times after washing before the wash cycle softener. rinse be added. A molar ratio in the range of 1.5 to less than 1.85 provides good softening performance in the presence of anionic surfactants. Active fabric softener compositions having such a molar ratio are therefore useful for preparing rinse cycle softeners intended for use in a laundry wash application where the rinse cycle softener is added to the rinse immediately following the wash. .
    [017] The fatty acid fraction of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester is derived from a mixture of fatty acids of the formula RCOOH, where R is a hydrocarbon group. The hydrocarbon group can be branched or unbranched and is preferably unbranched.
    [018] The fatty acid fraction has an average chain length of 16 to 18 carbon atoms and an iodine index, calculated for the free fatty acid, of 0.5 to 50. The average chain length is preferably 16 .5 to 17.8 carbon atoms. Preferably, the fatty acid fraction has an iodine number from 1.0 to 50, more preferably from 2 to 50, even more preferably from 5 to 40 and most preferably from 15 to 35. The average chain length is calculated based on the weight fraction of individual fatty acids in the fatty acid mixture. For branched chain fatty acids the chain length refers to the longest consecutive chain of carbon atoms. The iodine index is the amount of iodine in g consumed by the reaction of the double bonds of 100 g fatty acid, determined by the method of ISO 3961. To give the required average chain length and iodine index, the acid fraction A fatty acid is derived from a mixture of fatty acids comprising both saturated and unsaturated fatty acids. Unsaturated fatty acids are preferably monounsaturated fatty acids. The fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate preferably comprises less than 6% by weight of multiplied unsaturated fatty acid fractions. Examples of suitable saturated fatty acids are palmitic acid and stearic acid. Examples of suitable monounsaturated fatty acids are oleic acid and elaidic acid. The cis-trans ratio of double bonds of unsaturated fatty acid fractions is preferably greater than 55:45 and more preferably greater than 65:35. The fraction of multiple unsaturated fatty acid fractions can be reduced by touch-touch hydrogenation, which is a hydrogenation that selectively hydrogenates a double bond to a -CH=CH-CH2-CH=CH- substructure but not to bonds pairs of monounsaturated hydrocarbon groups. The specified average chain length and iodine values are essential to obtain high softener performance and low melting point of the composition. If the average chain length is less than 16 carbon atoms or the iodine index is greater than 50, the softener performance will be unsatisfactory, whereas the melting point of the composition may become too high if the chain length medium is greater than 18 carbon atoms.
    [019] The fatty acid fraction can be derived from fatty acids of natural or synthetic origin and is preferably derived from fatty acids of natural origin, more preferably from fatty acids of plant origin. The required iodine index can be provided using a naturally sourced fatty acid mixture that already has such an iodine index, eg a fatty acid of tallow. Alternatively, the required iodine number can be provided by partial hydrogenation of a fatty acid mixture or a triglyceride mixture having a higher iodine number. In another and preferred embodiment, the required iodine number is provided by mixing a fatty acid mixture having a higher iodine number with a saturated fatty acid mixture. The saturated fatty acid mixture can be obtained either by hydrogenating a fatty acid mixture containing unsaturated fatty acids or a hydrogenated triglyceride mixture, such as a hydrogenated vegetable oil.
    [020] The active fabric softener composition of the present invention also comprises from 0.5 to 5% by weight of fatty acid in addition to the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate. The composition preferably comprises from 1 to 5% and more preferably from 2 to 5% by weight of fatty acid. The fatty acid can be present as the free fatty acid or in the form of a salt of the fatty acid with non-quaternized bis-(2-hydroxypropyl)-methylamine esters. The active fabric softener composition preferably comprises a mixture of fatty acid, which is preferably of natural origin and more preferably of plant origin. In the most preferred embodiment, the fatty acid fractions of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester are derived from the same fatty acid mixture when present in the composition in an amount of 0.5 to 5% in Weight. The specified amount of fatty acid is essential to obtain a low melting point of the composition without compromising stability during storage in an aqueous dispersion. If the composition comprises less than 0.5% by weight of fatty acid, the melting point of the composition may become too high, whereas a content of more than 5% by weight of fatty acid in the composition will have the effect that the prepared aqueous dispersions of the composition have inappropriately high viscosities and low dispersion stability. By adjusting the amount of fatty acid in the claimed range, compositions of the present invention can be made which have low melt viscosities without using any solvent or diluent. Such compositions allow for the manufacture of rinse cycle softener aqueous dispersions containing no solvent or a minimal amount of solvent.
    [021] The active fabric softener composition of the present invention preferably comprises less than 2% by weight and more preferably less than 0.5% by weight of water. Compositions having such a low water content show improved stability during storage in the molten state and, therefore, can be stored and released as liquids without compromising product quality. Compositions comprising more water show a much higher melt viscosity and are therefore difficult to process into an aqueous dispersion.
    [022] The active fabric softener composition of the present invention preferably comprises less than 10% by weight and more preferably less than 1% by weight of solvents having a flash point of less than 20 °C.
    [023] In a preferred embodiment, the fabric softener active composition of the present invention comprises up to 9.9% by weight and preferably up to 5% by weight of at least one solvent selected from glycerol, ethylene glycol, propylene glycol, dipropylene glycol and C1-C4 alkyl monoethers of ethylene glycol, propylene glycol and dipropylene glycol. Examples of suitable C1-C4 glycol monoethers alkylation are 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, dipropylene glycol monomethyl ether and dipropylene glycol monobutyl ether. Compositions according to this modality have the advantages of low melt viscosity and a near Newtonian melt rheology, i.e. the viscosity shows little change with shear force.
    [024] In another preferred embodiment, the fabric softener active composition of the present invention comprises from 2 to 8% by weight of a fatty acid triglyceride having an average chain length of the fatty acid fractions of 10 to 14 atoms of carbon and an iodine index, calculated for the free fatty acid, from 0 to 15. Compositions according to this modality also have the advantages of low melt viscosity and a near Newtonian melt rheology, ie the viscosity shows little change with shear force.
    [025] In an alternative preferred embodiment, the amount of solvents present in the active fabric softener composition is less than 5% by weight and more preferably less than 1% by weight. Compositions according to this modality can also be processed in a molten state to provide aqueous solvent-free dispersions.
    [026] In addition to a fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate, a fatty acid and optionally a solvent, the active fabric softener composition of the present invention may preferably also comprise from 1.5 to 9 % by weight of a bis-(2-hydroxypropyl)-methylamine fatty acid ester containing the same fatty acid fractions as the bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester. The bis-(2-hydroxypropyl)-methylamine fatty acid ester is preferably a mixture of at least one diester of the formula (CH3)N(CH2CH(CH3)OC(=O)R)2 and at least one monoester of the formula (CH3)N(CH2CH(CH3)OH)(CH2CH(CH3)OC(=O)R). At least part of the bis-(2-hydroxypropyl)-methylamine fatty acid ester will be present as a salt with the fatty acid of the active fabric softener composition. Such salts are of the structure HN+(CH3)(CH2CH(CH3)OC(=O)R)2 RCOO- or HN+(CH3)(CH2CH(CH3)OH)(CH2CH(CH3)OC(=O)R) RCOO- . The presence of the bis-(2-hydroxypropyl)-methylamine fatty acid ester in the specified amount also lowers the melting point of the composition, without compromising softener performance and storage stability in the aqueous dispersion.
    [027] The active fabric softener composition of the present invention may also additionally comprise minor amounts of fatty acid esters of (2-hydroxypropyl)-(1-methyl-2-hydroxyethyl)-dimethylammonium methyl sulfate, fatty acid esters of bis-(1-methyl-2-hydroxyethyl)-dimethylammonium methylsulfate, (2-hydroxypropyl)-(1-methyl-2-hydroxyethyl)-methylamine fatty acid esters and bis-(1-methyl) fatty acid esters -2-hydroxyethyl)-methylamine.
    [028] The active fabric softener composition of the present invention can be prepared by mixing the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate, the fatty acid and optional components such as solvent or ester of bis-(2-hydroxypropyl)-methylamine fatty acid.
    [029] Preferably, the active fabric softener composition of the present invention is prepared by the method of the invention, comprising the steps of reacting bis-(2-hydroxypropyl)-methylamine with a fatty acid having an average chain length of 16 to 18 atoms of carbon and an iodine number of 0.5 to 50 at a molar ratio of fatty acid to amine of 1.51 to 2.1 with water removal until the acid value of the reaction mixture is in the range of 1 to 10 mg of KOH/g and also reacting with dimethyl sulphate in a molar ratio of dimethyl sulphate to amine of 0.90 to 0.97 and preferably from 0.92 to 0.95 until the total amine value of the mixture is reaction is in the range of 1 to 8 mg KOH/g.
    [030] In the first step of the method of the invention, bis-(2-hydroxypropyl)-methylamine is reacted with the fatty acid in a molar ratio of fatty acid to amine from 1.51 to 2.1, preferably from 1.86 to 2.1, with water removal. The reaction is preferably carried out at a temperature of 160 to 220°C. Water is preferably removed by distillation from the reaction mixture. During the course of the reaction, the pressure is preferably reduced from ambient pressure to a pressure in the range of 100 to 5 mbar to increase water removal. The first step can be carried out in the presence of an acid catalyst, which is preferably used in an amount of 0.05 to 0.2% by weight. Suitable acid catalysts are methanesulfonic acid, p-toluenesulfonic acid, and hypophosphorous acid. The reaction is carried out until the acid value of the reaction mixture is in the range of 1 to 10 mg KOH/g. The acid value is determined by titration with a standard alkaline solution according to ISO 660 and is calculated as mg of KOH per g of sample. The reaction can then be stopped by cooling to a temperature below 80°C to avoid further fatty acid reaction and keep the fatty acid unreacted to achieve the required amount of fatty acid in the final product.
    [031] In the second step of the method of the invention, the reaction mixture obtained in the first step is reacted with dimethyl sulfate in a molar ratio of dimethyl sulfate to amine of 0.90 to 0.97 and preferably of 0.92 at 0.95. The reaction is preferably carried out at a temperature of 60 to 100°C. The reaction is carried out until the total amine value of the reaction mixture is in the range of 1 to 8 mg KOH/g. The total amine value is determined by non-aqueous titration with perchloric acid according to American Oil Chemists Society method Tf 2a-64 and is calculated as mg of KOH per g of sample.
    [032] The method of the invention has the advantage of providing an active fabric softener composition according to the invention without requiring any step beyond the steps necessary for the manufacture of the fatty acid ester of bis-(2-hydroxypropyl)-methylsulfate- dimethylammonium. This advantage is obtained by choosing the proper molar ratio of fatty acid to amine and carrying out the reaction of fatty acid and amine in the specified range of acid value while maintaining an unreacted fatty acid fraction.
    [033] The invention is illustrated by the following examples, which are, however, not intended to limit the scope of the invention in any way. Examples General:
    [034] Table 1 lists the sources, fatty acid chain length distributions and iodine values of fatty acids A to G that were used in the examples. Fatty acid chain length distributions were determined by GC after derivatization of the fatty acid as methyl ester.
    [035] Active fabric softener compositions were prepared by the following general procedure unless otherwise specified in the individual examples. The fatty acid was placed with 0.2% by weight of 50% by weight of hypophosphorous acid in an electrically heated reactor equipped with a thermometer, a mechanical stirrer and a rectification column and the bis-(2-hydroxypropyl)-methylamine was added with stirring. The resulting mixture was heated with stirring to 200°C and held at this temperature for 4 hours at ambient pressure, the water distilling off through the rectification column. The pressure was then reduced to 10 mbar and the mixture was also stirred at 200°C, the water being removed with a vacuum pump, for the time specified in the individual example until the desired acid value of the reaction mixture was reached. The resulting mixture was then cooled to 75°C, dimethyl sulfate was added and the resulting mixture was stirred for 2 hours at 70 to 90°C.
    [036] The contents of free amine, amine salt and fatty acid in the fabric softener active composition were determined by non-aqueous potentiometric titration with tetrabutylammonium hydroxide after adding an excess of a solution of HCl in 2-propanol. Table 1 Sources, fatty acid chain length distributions and fatty acid iodine values
    Table 1 - (continued)

    Cx(y) means a linear fatty acid with x carbon atoms and y double bonds.* 20% fatty acids cannot be saponified and analyzed. Table 1 - (continued)
    Table 1 - (continued)

    [037] The fractions of monoester and diester in the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate were determined by HPLC (Waters Spherisorb® SCX column, methanol eluent with a formic acid triethylamine buffer, detection of RI).
    [038] Melting points were determined by the capillary method as the maximum temperature of the melting range using a heating rate of 1°C/min. The samples were conditioned by melting the composition, homogenizing the melt, shock solidifying the melt by pouring it onto a cold metal plate and cooling the shock solidified melt to -16°C for at least 4 hours before transferring it. for a melting point capillary.
    [039] Melt viscosities were measured at 70°C with a StressTech rheometer of REOLOGICA® instruments using 40 mm of parallel plates, a plate distance of 0.5 mm and shear rates of 1, 10 and 100 s- 1.
    [040] Storage stability was determined for 10% by weight of aqueous dispersions of the active fabric softener compositions which were stored for 6 weeks at 50°C in closed glass bottles. Dispersions were prepared by first dispersing a melt of the active fabric softener composition heated to 5 to 10°C above the melting point in a pre-warmed 0.05% by weight aqueous HCl solution at 5°C below the melting point. melting point of the composition using an IKA Super-Dispax-Reactor® SD 41 operated at 8000 min-1. Therefore, an aqueous solution of 25% by weight of CaCl2 was added with stirring to provide a CaCl2 concentration of 0.025% by weight. The acid values of the dispersions were determined before and after storage by acid-base titration with KOH or NaOH and are determined as mg KOH/g of dispersion. The viscosity of the dispersions before and after storage was determined at 20°C with a Brookfield viscometer using spindle number 1 for viscosities up to 100 mPa*s and spindle number 2 for viscosities higher than 100 mPa*s.
    [041] The softener performance of an active fabric softener composition was determined in a tactile test performed by a team of test persons on cotton towel pieces treated with an aqueous dispersion of the composition. 80 cm by 50 cm pieces of terry cloth cotton towel were washed twice with a heavy-duty powder detergent, rinsed twice with mid- and final rotation, and air-dried on a string. Samples of the 10% by weight aqueous dispersions of the active fabric softener compositions prepared as described above were diluted with cold potable water to produce 2 L of a rinse solution containing 0.025% by weight of the active fabric softener composition. The washed cotton towel pieces were immersed in this rinsing solution for 10 minutes, rotated and air dried at room temperature hanging from a rope. Therefore, the treated cotton towel pieces were cut into 10 equal pieces of 16 cm by 25 cm, which were distributed to a team of 9 test people who rated the fabric softener on a scale ranging from 0 to hard and a bad feel to 5 for soft and a good feel. The softener rating determined in the examples is the sum of the nine individual ratings and can therefore range from 0 to 45. Differences in softness rating of more than 4 are statistically significant, when determined from comparative repetition experiments. Example 1 (comparative example, corresponds to component A5 of EP 1 018 541 A1)
    [042] 644 g (2.25 mol) of fatty acid A were esterified with 182.5 g (1.25 mol) of bis-(2-hydroxypropyl)-methylamine at 190°C with 8 hours of reaction under reduced pressure until the acid value of the reaction mixture was 0.6 mg KOH/g. The resulting mixture was reacted with 151 g (1.20 mol) of dimethyl sulfate at 60°C. The resulting active fabric softener composition was a brownish viscous liquid containing 0.015 mmol/g (0.5% by weight) fatty acid and 0.070 mmol/g non-quaternized amine (0.041 mmol/g free amine and 0.029 mmol/g of protonated amine). HPLC analysis showed the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate to be comprised of 8.2% monoester and 91.8% diester (rel. area percent).
    [043] The composition had a melt viscosity of 685 mPa*s at 1 s-1, 488 mPa*s at 10 s-1 and 431 mPa*s at 100 s-1 shear rate.
    [044] The 1% aqueous dispersion had an acid value of 0.6 mg KOH/g and a viscosity of 34 mPa*s before storage and an acid value of 1.2 mg KOH/g and a viscosity of 265 mPa*s after storage for 6 weeks at 50°C.
    [045] The composition obtained a softness rating of 12. Example 2
    [046] Example 1 was repeated using 954 g (3.49 mol) of fatty acid B, 283 g (1.94 mol) of bis-(2-hydroxypropyl)-methylamine and 235 g (1.86 mol) of sulfate of dimethyl. The resulting active fabric softener composition was a white solid with a melting point of 42°C, containing 0.025 mmol/g (0.7% by weight) of fatty acid and 0.059 mmol/g of non-quaternized amine (0.033 mmol/ g of free amine and 0.026 mmol/g of protonated amine). HPLC analysis showed that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 8.8% monoester and 91.2% diester (rel. area percent).
    [047] The composition had a melt viscosity of 47200 mPa*s at 1 s-1, 9880 mPa*s at 10 s-1 and 2960 mPa*s at 100 s-1 shear rate.
    [048] The 10% aqueous dispersion had an acid value of 0.5 mg KOH/g and a viscosity of 18 mPa*s before storage and an acid value of 1.1 mg KOH/g and a viscosity of 18 mPa*s after storage for 6 weeks at 50°C.
    [049] The composition obtained a softness rating of 32. Example 3 (comparative example, corresponds to example 2 of DE 24 30 140 C3)
    [050] 744.5 g (2.38 mol) of fatty acid C were esterified with 174.1 g (1.19 mol) of bis-(2-hydroxypropyl)-methylamine with 15 hours of reaction under reduced pressure until the acid value of the reaction mixture was 1.5 mg KOH/g. The resulting mixture was reacted with 142.5 g (1.13 mol) of dimethyl sulfate for 4 hours. The resulting active fabric softener composition had a yellowish gel, containing 0.032 mmol/g (1.0% by weight) fatty acid and 0.113 mmol/g non-quaternized amine (0.042 mmol/g free amine and 0.071 mmol/g of protonated amine). The amounts of monoester and diester in the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate could not be determined by HPLC analysis.
    [051] The composition had a melt viscosity of 561 mPa*s at 1 s-1, 535 mPa*s at 10 s-1 and 469 mPa*s at 100 s-1 shear rate.
    [052] A 10% by weight aqueous dispersion prepared with 0.025% by weight of CaCl2 became very viscous. Therefore, the dispersion for the stability test was prepared with a four-fold amount of CaCl2, i.e. 0.1% by weight of CaCl2. The dispersion had an acid value of 0.7 mg KOH/g and a viscosity of 160 mPa*s before storage and an acid value of 1.4 mg KOH/g and a viscosity of 270 mPa*s after storage for 6 weeks at 50°C.
    [053] The composition obtained a softness rating of 24. Example 4
    [054] Example 3 was repeated using 948 g (3.47 mol) of fatty acid B, 253.4 g (1.735 mol) of bis-(2-hydroxypropyl)-methylamine and 208 g (1.65 mol) of sulfate of dimethyl with 15 hours of reaction under reduced pressure until the acid value of the reaction mixture was 1.4 mg of KOH/g. The resulting active fabric softener composition was a white solid with a melting point of 43°C, containing 0.032 mmol/g (0.9% by weight) of fatty acid and 0.073 mmol/g of non-quaternized amine (0.043 mmol/ g free amine and 0.030 mmol/g protonated amine). HPLC analysis showed that bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester is comprised of 3.1% monoester and 96.9% diester (rel. area percent).
    [055] The composition had a melt viscosity of 36200 mPa*s at 1 s-1, 7440 mPa*s at 10 s-1 and 2160 mPa*s at 100 s-1 shear rate.
    [056] The 10% aqueous dispersion had an acid value of 0.6 mg KOH/g and a viscosity of 16 mPa*s before storage and an acid value of 1.3 mg KOH/g and a viscosity of 18 mPa*s after storage for 6 weeks at 50°C.
    [057] The composition obtained a softness rating of 31.
    [058] Examples 1 and 4 and comparative examples 2 and 3 clearly demonstrate that the active fabric softener compositions of the invention provide significantly better softener performance in terms of soft touch and better storage stability of an aqueous dispersion at 10°C. % compared to the active fabric softener compositions known from EP 1 018 541 A1 and DE 24 30 140 C3. Example 5
    [059] 2780 g (10.18 mol) of fatty acid B were esterified with 783 g (5.36 mol) of bis-(2-hydroxypropyl)-methylamine with 3 hours of reaction under reduced pressure until the acid value of the reaction mixture was 5.2 mg KOH/g. The resulting mixture was reacted with 642 g (5.10 mol) of dimethyl sulfate. The resulting active fabric softener composition was a white solid with a melting point of 41°C, containing 0.075 mmol/g (2.2% by weight) of fatty acid and 0.123 mmol/g of non-quaternized amine (0.068 mmol/ g free amine and 0.055 mmol/g protonated amine). HPLC analysis showed that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 5.5% monoester and 94.5% diester (rel. area percent).
    [060] The composition had a melt viscosity of 2360 mPa*s at 1 s-1, 1090 mPa*s at 10 s-1 and 619 mPa*s at 100 s-1 shear rate.
    [061] The 10% aqueous dispersion had an acid value of 0.8 mg KOH/g and a viscosity of 28 mPa*s before storage and an acid value of 2.8 mg KOH/g and a viscosity of 12 mPa*s after storage for 6 weeks at 50°C.
    [062] The composition obtained a softness rating of 35. Example 6
    [063] 1365 g (5.0 mol) of fatty acid B was esterified with 384.2 g (2.63 mol) of bis-(2-hydroxypropyl)-methylamine with 14 hours of reaction under reduced pressure until the value of acid of the reaction mixture was 1.3 mg KOH/g. The resulting mixture was reacted with 315 g (2.5 mol) of dimethyl sulfate. The resulting active fabric softener composition was a white solid with a melting point of 43°C, containing 0.025 mmol/g (0.7% by weight) of fatty acid and 0.113 mmol/g of non-quaternized amine (0.081 mmol/ g of free amine and 0.032 mmol/g of protonated amine). HPLC analysis showed that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 5.7% monoester and 94.3% diester (rel. area percent).
    [064] The composition had a melt viscosity of 16200 mPa*s at 1 s-1, 4970 mPa*s at 10 s-1 and 1530 mPa*s at 100 s-1 shear rate.
    [065] The 10% aqueous dispersion had an acid value of 0.5 mg KOH/g and a viscosity of 19 mPa*s before storage and an acid value of 1.9 mg KOH/g and a viscosity of 13 mPa*s after storage for 6 weeks at 50°C.
    [066] The composition obtained a softness rating of 32. Example 7
    [067] The esterification step of example 6 was repeated and 1021 g of the reaction mixture obtained were examined with 45 g of fatty acid B. The resulting mixture was reacted with 193 g (1.53 mol) of dimethyl sulphate . The resulting active fabric softener composition was a white solid with a melting point of 41°C, containing 0.151 mmol/g (4.15% by weight) of fatty acid and 0.162 mmol/g of non-quaternized amine (0.070 mmol/g free amine and 0.092 mmol/g protonated amine). HPLC analysis showed that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 5.7% monoester and 94.3% diester (rel. area percent).
    [068] The composition had a melt viscosity of 842 mPa*s at 1 s-1, 663 mPa*s at 10 s-1 and 619 mPa*s at 100 s-1 shear rate.
    [069] The 10% aqueous dispersion had an acid value of 1.3 mg KOH/g and a viscosity of 23 mPa*s before storage and an acid value of 3.9 mg KOH/g and a viscosity of 8 mPa*s after storage for 6 weeks at 50°C.
    [070] The composition obtained a softness rating of 31.
    [071] Examples 5 to 7 demonstrate that the presence of fatty acid in the active fabric softener compositions of the invention contributes to a low melt viscosity of the composition, provides a rheology closer to the Newtonian of melt does not adversely affect the melt viscosity. an aqueous dispersion of the composition during storage. Example 8 (comparative, higher iodine content)
    [072] 970 g (3.5 mol) of fatty acid D were esterified with 287 g (1.84 mol) of bis-(2-hydroxypropyl)-methylamine with 3 hours of reaction under reduced pressure until the acid value of the reaction mixture was 5.6 mg KOH/g. The resulting mixture was reacted with 221 g (1.75 mol) of dimethyl sulfate. The resulting active fabric softener composition was a viscous yellow liquid, containing 0.054 mmol/g (1.6% by weight) of fatty acid and 0.129 mmol/g of non-quaternized amine (0.068 mmol/g of free amine and 0.061 mmol/ g of protonated amine). HPLC analysis showed that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 6.6% monoester and 93.4% diester (rel. area percent).
    [073] The composition had a melt viscosity of 581 mPa*s at 1 s-1, 538 mPa*s at 10 s-1 and 480 mPa*s at 100 s-1 shear rate.
    [074] The 10% aqueous dispersion had an acid value of 0.9 mg KOH/g and a viscosity of 40 mPa*s before storage and an acid value of 2.6 mg KOH/g and a viscosity of 36 mPa*s after storage for 6 weeks at 50°C.
    [075] The composition obtained a softness rating of 23.
    [076] Example 8 demonstrates that the fabric softener active composition, which has fatty acid fractions of the quaternary ammonium salt with a higher iodine content than claimed, did not achieve a softener performance as high as that of the composition active fabric softener of the invention. Example 9 (comparative, shorter average chain length)
    [077] 1125 g (5.25 mol) of fatty acid E was esterified with 403 g (2.76 mol) of bis-(2-hydroxypropyl)-methylamine with 2 hours of reaction under reduced pressure until the acid value of the reaction mixture was 4.1 mg KOH/g. The resulting mixture was reacted with 330 g (2.62 mol) of dimethyl sulfate. The resulting active fabric softener composition was a white gel, containing 0.049 mmol/g (1.1% by weight) of fatty acid and 0.122 mmol/g of non-quaternized amine (0.079 mmol/g of free amine and 0.043 mmol/g) of protonated amine). HPLC analysis showed the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 3.2% monoester and 96.8% diester (rel. area percent).
    [078] The composition had a melt viscosity of 552 mPa*s at 1 s-1, 550 mPa*s at 10 s-1 and 497 mPa*s at 100 s-1 shear rate.
    [079] The 10% aqueous dispersion had an acid value of 0.8 mg KOH/g and a viscosity of 30 mPa*s before storage and an acid value of 2.5 mg KOH/g and a viscosity of 79 mPa*s after storage for 6 weeks at 50°C.
    [080] The composition obtained a softness rating of 16.
    [081] Example 9 demonstrates that an active fabric softener composition, which has fatty acid fractions of the quaternary ammonium salt with an average chain length shorter than claimed, did not achieve as high a softener performance as that of the active fabric softener composition of the invention. Example 10
    [082] 1032 g (3.78 mol) of fatty acid B was esterified with 313.3 g (2.16 mol) of bis-(2-hydroxypropyl)-methylamine with 2 hours of reaction under reduced pressure until the value of acid of the reaction mixture was 4.6 mg KOH/g. The resulting mixture was reacted with 258.8 g (2.05 mol) of dimethyl sulfate. The resulting active fabric softener composition was a white solid with a melting point of 41°C, containing 0.047 mmol/g (1.3% by weight) of fatty acid and 0.134 mmol/g of non-quaternized amine (0.076 mmol/g free amine and 0.058 mmol/g protonated amine). HPLC analysis showed that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 16.6% monoester and 83.4% diester (rel. area percent).
    [083] The composition had a melt viscosity of 27100 mPa*s at 1 s-1, 6040 mPa*s at 10 s-1 and 1870 mPa*s at 100 s-1 shear rate.
    [084] The 10% aqueous dispersion had an acid value of 0.9 mg KOH/g and a viscosity of 19 mPa*s before storage and an acid value of 2.5 mg KOH/g and a viscosity of 13 mPa*s after storage for 6 weeks at 50°C.
    [085] The composition obtained a softness rating of 27.
    [086] Example 10 demonstrates that the fabric softener active composition, which has a lower molar ratio of fatty acid fractions to amine fractions than claimed, does not achieve a softener performance as high as that of the fabric softener active composition of fabric of the invention. Example 11
    [087] 919 g (3.37 mol) of fatty acid B were esterified with 245.7 g (1.68 mol) of bis-(2-hydroxypropyl)-methylamine with 7 hours of reaction under reduced pressure until the value of acid of the reaction mixture was 5.5 mg KOH/g. The resulting mixture was reacted with 201.3 g (1.60 mol) of dimethyl sulfate. The resulting active fabric softener composition was a white solid with a melting point of 43°C, containing 0.076 mmol/g (2.2% by weight) of fatty acid and 0.141 mmol/g of non-quaternized amine (0.084 mmol/g free amine and 0.057 mmol/g protonated amine). HPLC analysis showed that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 0.9% monoester and 99.1% diester (rel. area percent).
    [088] The composition had a melt viscosity of 1510 mPa*s at 1 s-1, 687 mPa*s at 10 s-1 and 553 mPa*s at 100 s-1 shear rate.
    [089] The 10% aqueous dispersion had an acid value of 0.9 mg KOH/g and a viscosity of 31 mPa*s before storage and an acid value of 3.3 mg KOH/g and a viscosity of 12 mPa*s after storage for 6 weeks at 50°C.
    [090] The composition obtained a softness rating of 31. Example 12
    [091] 4823 g (17.68 mol) of fatty acid F were esterified with 1337.4 g (9.16 mol) of bis-(2-hydroxypropyl)-methylamine with 5 hours of reaction at ambient pressure and 5 hours of reaction under reduced pressure until the acid value of the reaction mixture was 4.6 mg KOH/g. The resulting mixture was reacted with 1096.5 g (8.70 mol) of dimethyl sulfate. The resulting active fabric softener composition was a white solid with a melting point of 38°C, containing 0.069 mmol/g (2.0% by weight) of fatty acid and 0.130 mmol/g of non-quaternized amine (0.071 mmol/ g free amine and 0.059 mmol/g protonated amine). HPLC analysis showed that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 5.9% monoester and 94.1% diester (rel. area percent).
    [092] The composition had a melt viscosity of 592 mPa*s at 1 s-1, 610 mPa*s at 10 s-1 and 552 mPa*s at 100 s-1 shear rate.
    [093] The composition obtained a softness rating of 38. Example 13
    [094] 4088 g (14.9 mol) of fatty acid G were esterified with 1129.5 g (7.74 mol) of bis-(2-hydroxypropyl)-methylamine with 4 hours of reaction under reduced pressure until the value of acid of the reaction mixture was 3.7 mg KOH/g. The resulting mixture was reacted with 926.5 g (7.4 mol) of dimethyl sulfate. The resulting active fabric softener composition was a white solid with a melting point of 52°C, containing 0.066 mmol/g (1.9% by weight) of fatty acid and 0.128 mmol/g of non-quaternized amine (0.073 mmol/ g free amine and 0.055 mmol/g protonated amine). HPLC analysis showed that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 6.8% monoester and 93.2% diester (rel. area percent).
    [095] The composition had a melt viscosity of 34700 mPa*s at 1 s-1, 8100 mPa*s at 10 s-1 and 2630 mPa*s at 100 s-1 shear rate.
    [096] The composition obtained a softness rating of 38. Example 14
    [097] 2520.4 g (9.23 mol) of fatty acid B were esterified with 692.5 g (4.75 mol) of bis-(2-hydroxypropyl)-methylamine with 5 hours of reaction under reduced pressure until the acid value of the reaction mixture was 6.1 mg KOH/g. The resulting mixture was reacted with 568.6 g (4.51 mol) of dimethyl sulfate for 1 hour. Then 180.8 g of dipropylene glycol was added and the mixture was homogenized by stirring. The resulting active fabric softener composition was a white solid with a melting point of 40°C, containing 0.083 mmol/g (2.4% by weight) of fatty acid and 0.119 mmol/g of non-quaternized amine (0.048 mmol/ g of free amine and 0.071 mmol/g of protonated amine). HPLC analysis showed that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 6.8% monoester and 93.2% diester (rel. area percent).
    [098] The composition had a melt viscosity of 368 mPa*s at 1 s-1, 340 mPa*s at 10 s-1 and 318 mPa*s at 100 s-1 shear rate. Example 15
    [099] 3214 g (11.77 mol) of fatty acid B were esterified with 883.5 g (6.05 mol) of bis-(2-hydroxypropyl)-methylamine with 4 hours of reaction under reduced pressure until the value of acid of the reaction mixture was 3.3 mg KOH/g. Then, 157 g of refined coconut oil was added and the resulting mixture was reacted with 724.2 g (5.75 mol) of dimethyl sulfate for 1 hour. Therefore, 472 g of 2-propanol was added and the mixture was homogenized by stirring. The resulting active fabric softener composition was a white solid with a melting point of 36°C, containing 0.049 mmol/g (1.4% by weight) of fatty acid and 0.125 mmol/g of non-quaternized amine (0.067 mmol/ g free amine and 0.058 mmol/g protonated amine). HPLC analysis showed that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 6.3% monoester and 93.7% diester (rel. area percent).
    [0100] The composition had a melt viscosity of 144 mPa*s at 1 s-1, 107 mPa*s at 10 s-1 and 94 mPa*s at 100 s-1 shear rate.
    [0101] The composition obtained a softness rating of 34. Example 16 (comparative example, corresponds to example 50 of WO 0/06678)
    [0102] 250 g (1.15 mol) of Radiacid® 600 fatty acid were esterified with 176.3 g (1.21 mol) of bis-(2-hydroxypropyl)-methylamine for 14 hours at ambient pressure until the acid value of the reaction mixture was 2.6 mg KOH/g. The resulting mixture was reacted with 137.0 g (1.09 mol) of dimethyl sulfate. The resulting active fabric softener composition was a yellow wax with a melting point of 35°C, containing 1.1 wt% fatty acid. HPLC analysis showed that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 84.7% monoester and 15.3% diester (rel. area percent).
    [0103] The composition obtained a softness rating of 13. Example 17 (comparative, smallest molar ratio of fatty acid fractions to amine fractions)
    [0104] 378.6 g (1.38 mol) of fatty acid B were esterified with 211.5 g (1.45 mol) of bis-(2-hydroxypropyl)-methylamine for 12 hours at ambient pressure until the value of acid of the reaction mixture was 3.8 mg KOH/g. The resulting mixture was reacted with 164.5 g (1.60 mol) of dimethyl sulfate. The resulting active fabric softener composition was a yellow wax with a melting point of 40°C, containing 1.7% by weight of fatty acid. HPLC analysis showed that bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester is comprised of 80.7% monoester and 19.3% diester (rel. area percent).
    [0105] The composition obtained a softness rating of 13. Example 18
    [0106] 411.0 g (1.50 mol) of fatty acid B were esterified with 146.0 g (1.0 mol) of bis-(2-hydroxypropyl)-methylamine for 16 hours at ambient pressure until the value of acid of the reaction mixture was 5.0 mg KOH/g. The resulting mixture was reacted with 113.5 g (0.9 mol) of dimethyl sulfate. The resulting active fabric softener composition was a yellow wax with a melting point of 38°C, containing 2.2% by weight of fatty acid. HPLC analysis showed that bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid ester is comprised of 39.0% monoester and 61.0% diester (rel. area percent).
    [0107] The composition obtained a softness rating of 25.
    [0108] Comparative Examples 16 and 17 and example 18 demonstrate that a minimum molar ratio of fatty acid fractions to amine fractions of 1.5 is necessary to achieve useful softener performance. Example 19 (comparative, quaternary ammonium chloride salt)
    [0109] 2780 g (10.18 mol) of fatty acid B were esterified with 783 g (5.36 mol) of bis-(2-hydroxypropyl)-methylamine with 3 hours of reaction under reduced pressure until the acid value of the reaction mixture was 5.2 mg KOH/g. 469.2 g of the resulting mixture was charged to an agitated autoclave, 195 g of acetoniril was added and the autoclave was closed and heated to 75°C. 41.75 g (0.827 mol) of methyl chloride were fed into the autoclave while stirring at 75°C at a rate to maintain the pressure in the reactor below 4 bar and the mixture was stirred for a total of 90 hours from 75 to 80°C. Therefore, pressure was released and unreacted acetonitrile solvent and methyl chloride were distilled. The resulting active fabric softener composition was a white solid with a melting point of 69°C, containing 0.085 mmol/g (2.3% by weight) of fatty acid and 0.152 mmol/g of non-quaternized amine (0.103 mmol/ g of free amine and 0.049 mmol/g of protonated amine). HPLC analysis showed that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate is comprised of 1.0% monoester and 99.0% diester (rel. area percent).
    [0110] The 10% aqueous dispersion had an acid value of 1.2 mg KOH/g and a viscosity of 66 mPa*s before storage, however, it splits into two phases during storage for 6 weeks at 50° Ç.
    [0111] Comparative Example 19 demonstrates that the composition must comprise a quaternary ammonium methylsulfate salt to have a low melting point and provide stable aqueous dispersions, whereas a quaternary ammonium chloride salt leads to a high melting point and insufficient stability of aqueous dispersions.
    [0112] Table 2 summarizes the properties of the active fabric softener compositions prepared in examples 1 to 15. The molar ratio of fatty acid to amine in table 2 refers to the molar ratio in the bis-(2 methylsulfate fatty acid ester) -hydroxypropyl)-dimethylammonium when calculated from HPLC Analysis. The acid value increase and viscosity change data during storage refer to 10% by weight of aqueous dispersions of the active fabric softener compositions which were stored for 6 weeks at 50°C. Table 2: Properties of active fabric softener compositions
    * not according to the invention; ** gel; na = not determined.
    权利要求:
    Claims (16)
    [0001]
    1. Active fabric softener composition, characterized in that it comprises: (a) at least 50% by weight of a fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate having a molar ratio of acid fractions for amine fractions of 1.5 to 1.99, an average chain length of the fatty acid fractions of 16 to 18 carbon atoms, and an iodine index of the fatty acid fractions, calculated for the free fatty acid, of 0.5 to 50, and (b) from 0.5 to 5% by weight of fatty acid.
    [0002]
    2. Active fabric softener composition, according to claim 1, characterized in that the molar ratio of fatty acid fractions to amine fractions is from 1.85 to 1.99.
    [0003]
    3. Active fabric softener composition, according to claim 1 or 2, characterized in that the iodine index of the fatty acid fractions, calculated for the free fatty acid, is from 5 to 40.
    [0004]
    4. Active fabric softener composition, according to any one of claims 1 to 3, characterized in that it comprises from 1 to 5% by weight of fatty acid.
    [0005]
    5. Active fabric softener composition according to any one of claims 1 to 4, characterized in that it comprises from 85 to 99% by weight of bis-(2-hydroxypropyl)-methylsulfate fatty acid ester. dimethylammonium.
    [0006]
    6. Active fabric softener composition according to any one of claims 1 to 5, characterized in that the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate comprises less than 6% by weight of multiple fractions of unsaturated fatty acid.
    [0007]
    7. Active fabric softener composition according to any one of claims 1 to 6, characterized in that the cis-trans ratio of double bonds of unsaturated fatty acid fractions of the fatty acid ester of bis-(methylsulfate) 2-hydroxypropyl)-dimethylammonium is higher than 55:45.
    [0008]
    8. Active fabric softener composition according to any one of claims 1 to 7, characterized in that the fatty acid fractions of the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate are derived from the acid component grease (b).
    [0009]
    9. Active fabric softener composition, according to any one of claims 1 to 8, characterized in that it comprises less than 2% by weight of water.
    [0010]
    10. Active fabric softener composition, according to any one of claims 1 to 9, characterized in that it comprises less than 10% by weight of solvents having a flash point of less than 20°C.
    [0011]
    11. Active fabric softener composition, according to any one of claims 1 to 10, characterized in that it further comprises up to 9.9% by weight of at least one solvent selected from glycerol, ethylene glycol, propylene glycol, dipropylene glycol and C1-C4 alkyl monoethers of ethylene glycol, propylene glycol and di-propylene glycol.
    [0012]
    12. Active fabric softener composition according to any one of claims 1 to 4 or 6 to 11, characterized in that it further comprises from 2 to 8% by weight of a fatty acid triglyceride having an average chain length of fatty acid fractions of 10 to 14 carbon atoms and an iodine index, calculated for the free fatty acid, of 0 to 15.
    [0013]
    13. Active fabric softener composition according to any one of claims 1 to 4 or 6 to 12, characterized in that it further comprises from 1.5 to 9% by weight of a bis-(2 fatty acid ester) -hydroxypropyl)-methylamine containing the same fatty acid fractions as the fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate.
    [0014]
    14. Method for preparing a fabric softener composition as defined in claim 1, characterized in that comprising the steps of (c) reacting bis-(2-hydroxypropyl)-methylamine with a fatty acid having an average chain length of 16 to 18 carbon atoms and an iodine number of 0.5 to 50 at a molar ratio of fatty acid to amine of 1.51 to 2.1 with water removal until the acid value of the reaction mixture is in the range of 1 to 10 mg KOH/g; and (d) reacting the product of step (a) with dimethyl sulfate in a molar ratio of dimethyl sulfate to amine of 0.90 to 0.97 until the total amine value of the reaction mixture is in the range of 1 to 8 mg KOH/g.
    [0015]
    15. Method according to claim 14, characterized in that the molar ratio of fatty acid to amine is 1.86 to 2.1.
    [0016]
    16. Method according to claim 14 or 15, characterized in that the molar ratio of dimethyl sulfate to amine is from 0.92 to 0.95.
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    同族专利:
    公开号 | 公开日
    KR20130027478A|2013-03-15|
    US20110245138A1|2011-10-06|
    CO6571880A2|2012-11-30|
    AP3143A|2015-02-28|
    EG26891A|2014-11-25|
    WO2011120822A8|2012-10-11|
    AP2012006527A0|2012-10-31|
    ES2484719T3|2014-08-12|
    ZA201207286B|2013-06-26|
    RU2012146402A|2014-05-10|
    WO2011120822A1|2011-10-06|
    MX2012011011A|2012-11-06|
    CN102834496B|2014-01-15|
    EP2553066A1|2013-02-06|
    HK1179645A1|2013-10-04|
    SG184398A1|2012-11-29|
    KR101426635B1|2014-08-05|
    CA2795464A1|2011-10-06|
    JP2013525614A|2013-06-20|
    JP5570651B2|2014-08-13|
    RU2524954C2|2014-08-10|
    MA34102B1|2013-03-05|
    BR112012024811A2|2021-04-27|
    CN102834496A|2012-12-19|
    EP2553066B1|2014-04-30|
    MY160707A|2017-03-15|
    CA2795464C|2014-07-15|
    US8569224B2|2013-10-29|
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    法律状态:
    2021-05-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2021-05-11| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-06-29| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |
    2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-31| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/03/2011, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF, QUE DETERMINA A ALTERACAO DO PRAZO DE CONCESSAO. |
    优先权:
    申请号 | 申请日 | 专利标题
    US31995010P| true| 2010-04-01|2010-04-01|
    US61/319,950|2010-04-01|
    PCT/EP2011/054107|WO2011120822A1|2010-04-01|2011-03-18|Fabric softener active composition|
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