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
  • 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 invention relates to fabric softeners that can be used for the treatment of textiles after washing.
• Fabric softener is usually understood to mean ready-to-use or ready-to-use agents containing one or more active ingredients, which are used in the detergent and detergent sector and are used to give textiles a soft feel. Such agents usually contain one or more cationic surfactants which are able to make textiles treated with them soft and easy to grip.
• water-insoluble quaternary ammonium compounds have been proposed as cationic surfactants, in which the ammonium nitrogen atom, in order to ensure sufficient softener qualities of the fabric softener, has at least two long-chain aliphatic radicals with 16 to 18 carbon atoms or at least one excessively long radical, for example with carbon atom numbers in the range from 32 to 36, the long or excessively long residues can be interrupted by ether, ester or amido groups.
• Quaternary ammonium compounds of this type were specially produced for the manufacture of fabric softeners in large quantities and mostly in a complex manner.
• the present invention has set itself the task of avoiding the disadvantages known from the prior art, in particular the use of fabric softener constituents produced by complex synthesis, and of providing fabric softener, the active ingredients of which by simple chemical synthesis from inexpensive raw materials or from a large scale Synthesizable intermediates can be produced. It was surprisingly found that fabric softeners with a good softening effect (softening effect) can be obtained by simply mixing certain sulfonic acids and / or phosphonic acids and fatty amines or corresponding quaternary compounds of the fatty amines, which are inexpensively accessible on a large scale by simple oleochemical syntheses from natural raw materials .
• the fabric softeners according to the invention can therefore contain a large number of compounds of the general formulas (I) and (II) as amine components.
• one or more ammonium compounds are also suitable as "amine component", which are quaternized from amines of the general formulas (I) and / or (II) are derived.
• straight-chain alkyl radicals come independently from the group as meaning for R 1 and R 2 Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl as well as the branched homologs of the aforementioned which can be used with the same advantage in principle Alkyl residues in question.
• alkyl groups mentioned are interrupted by ether groups. This means nothing other than that oxygen atoms, which originate from alkoxylation reactions of corresponding alkyl radicals or their derivatives, can be inserted into - in particular longer - alkyl radicals.
• R 1 in the above general formula (II) is a radical of the formula CH3- (CH2) n -CO-NH- (CH2) 3- in which the index can take n values in the range from 8 to 18.
• Such fatty acid amidoalkyl radicals are then bound directly to the amino nitrogen atom or - in the case of the ammonium compounds derived from such amines by quaternization - to the ammonium nitrogen atom.
• R2 can also have further meanings.
• the amines which can be used in fabric softeners can also represent a hydroxyl group or a group of the formula (III) in the R5 is hydrogen or an alkyl radical from the group methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, the pentyl radicals which are homologous to n-pentyl and n-hexyl and the branched-chain hexyl radicals isomeric to n-hexyl.
• R3 and R4 in the amines which can be used in the fabric softeners according to the invention, in addition to hydrogen, can also be straight-chain or branched alkyl radicals having 1 to 6 carbon atoms.
• R3 and R4 in the amines which can be used in the fabric softeners according to the invention, in addition to hydrogen can also be straight-chain or branched alkyl radicals having 1 to 6 carbon atoms.
• residues methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl and the branched pentyl and isomers which are isomeric to the straight-chain pentyl and hexyl radicals Hexyl residues in question.
• R3 and R4 in the general formulas (I) and (II) also represent hydroxyalkyl radicals in which the alkyl groups are always straight-chain and come from the group of the radicals methyl, ethyl, propyl, butyl, pentyl and hexyl.
• the indices p and q can stand for numbers in the range from 0 to 22, the sum (p + q) always being in the range from 0 to 22. It is possible for p and q to assume any possible number in the range mentioned. This can also include fractional numbers, since - as will be explained later - compound mixtures are used in which there are different numbers of -CH2 groups in the molecule and the indices p and q only indicate the average numerical values; Due to the occurrence of compound mixtures of different proportions in a mixture, even fractional numbers as indices for p and q are possible.
• the usable amines of the general formula (I) can be divided into several groups.
• one or more compounds of the general formula (I) are preferably used as the amine component, in which R1 and R2 are hydrogen, R3 and R4 independently of one another for straight-chain or branched alkyl radicals with 1 to 6 carbon atoms or hydroxyalkyl radicals with 1 to 6 carbon atoms in the alkyl radical.
• the fabric softeners contain one or more amines of the general formula (I) in which R1 is hydrogen or straight-chain or branched alkyl radicals having 1 to 20 C atoms and R2 is a hydroxyl group or a group of the formula (III) in which R5 is hydrogen or a straight-chain or branched C1-C6 alkyl radical.
• amines are formed in accordance with the reaction equation (2) below from epoxidized fatty acids, fatty acid esters or fatty alcohols, which are cheaply accessible in large quantities from animal or vegetable fats or oils, i.e. from natural sources, and not only as individual substances, but also as natural ones Sources resulting mixtures can be used.
• Such mixtures include not only mixtures of compounds of different chain lengths as they occur in natural fats and oils - as homologues of otherwise identical structure - but also mixtures of compounds which carry epoxy groups at different positions in the molecular chain and thus also in lead in different ways through the reaction with the corresponding amines to give mixtures of ring-opening products of the general formula (I).
• the product mixtures of the general formula (I) resulting from reaction equation (2) are suitable as amine component of the fabric softener according to the invention.
• the fabric softeners contain one or more amines of the general formula (I) in which R1 is a straight-chain or branched alkyl radical having 1 to 20 C atoms and R2 is a hydroxyl group or a group of the formula (III) in which R5 has the meanings given above, and R3 and R4 independently of one another represent straight-chain or branched alkyl radicals having 1 to 6 C atoms or hydroxyalkyl radicals having 1 to 6 C atoms in the straight-chain alkyl radical.
• R1 is a straight-chain or branched alkyl radical having 1 to 20 C atoms
• R2 is a hydroxyl group or a group of the formula (III) in which R5 has the meanings given above
• R3 and R4 independently of one another represent straight-chain or branched alkyl radicals having 1 to 6 C atoms or hydroxyalkyl radicals having 1 to 6 C atoms in the straight-chain alkyl radical.
• R3 and R4 in the general formula (I) of the amine or amines used from the group of straight-chain alkyl radicals with 1 to select 3 carbon atoms and the hydroxyalkyl radicals with 1 to 3 carbon atoms in the straight-chain alkyl radical, in which case p 8 to 18 and q is 0.
• R1R3R4N R1 can be hydrogen, straight-chain or branched alkyl radicals having 1 to 20 C atoms, as already mentioned above, and R3 and R4, which can be the same or different, can independently of one another be hydrogen, straight-chain or branched Alkyl residues with 1 to 6 carbon atoms or hydroxyalkyl radicals with 1 to 6 carbon atoms in the straight-chain alkyl radical.
• the radical R 1 in the general formula (II) usually has a number of carbon atoms in the range from 12 to 20, preferably from 14 to 18.
• Amines with chain lengths in this preferred range can be conveniently synthesized from natural fats and oils by methods known per se. Because of the synthesis methods usually used, mixtures of amines of different chain lengths are usually obtained on an industrial scale and can be readily contained in the fabric softening agents according to the invention as an amine component. However, it is also possible to synthesize individual compounds and to provide them as an amine component of the fabric softener. From the group of the amines of the general formula (II) mentioned, laurylamine, cetylamine, lauryldimethylamine and cetyldimethylamine have proven particularly useful in practice.
• amine component together with or instead of the abovementioned amines of the general formulas (I) and (II), one or more, by quaternization from amines of the general formulas (I ) and (II) to use derived ammonium compounds.
• ammonium compounds can be used both as individual components and as mixtures of several ammonium compounds. It is irrelevant in which molar ratio they are mixed with the amines of the general formulas (I) and (II) mentioned above or in which molar ratios they are contained among one another in the fabric softeners according to the invention.
• ammonium compounds are advantageously used in addition to or instead of the amines of the general formulas (I) and / or (II) are derived by quaternization of the abovementioned amines of the general formulas (I) and (II) with a compound of the general formula (IV) (R8) m X (IV) in the stands.
• the alkyl radicals R8 in the quaternizing reagent are the groups methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl from the group of the alkyl radicals or the benzyl or phenethyl radicals from the group of the phenalkyl radicals Question.
• X can represent the acid residue of a large number of organic and / or inorganic acids; Usually, the residues chloride, bromide, methosulfate, ethosulfate, toluenesulfonate are to be considered as acid residue X.
• ammonium compounds those which are derived from the compounds of the general formulas (I) and / or (II) by quaternization with a quaternizing reagent from the group consisting of methyl chloride, ethyl chloride, benzyl chloride and dimethyl sulfate are used with particular advantage.
• reaction of the quaternization of the amines of the general formulas (I) and / or (II) with the quaternization reagents mentioned is generally known as such. It is also used to produce the ammonium compounds which can also be used according to the invention in the manner known from the prior art and way performed. This consists in reacting the respective amines in the presence or in the absence of a solvent at elevated temperature with the desired quaternizing reagent.
• the quaternization in a manner which is likewise known from the prior art by reacting the respective amine with an alkylene oxide, preferably with ethylene oxide, in the presence of an acid and thereby obtaining quaternization products which carry a hydroxyalkyl group instead of the hydrogen atom in the amine, the number of carbon atoms in the alkyl chain corresponding to the number of carbon atoms in the alkylene oxide used for the reaction and the statistical number of alkoxy groups by the molar ratio of alkylene oxide: amine set during the reaction is determined.
• the quaternary ammonium compounds formed in this way contain as anion X the acid residue of the acid used in the reaction.
• the radical X stands for example for a chloride, sulfate, acetate, lactate, phosphate or benzoate radical.
• the fabric softeners according to the invention which contain one or more amines of the general formula (I) or (II) and / or quaternary ammonium compounds derived therefrom as the amine component, have, as a further essential component, one or more sulfonic acids of the general formulas (V), (VI) , (VII) and (VIII) on, and / or one or more phosphonic acids of the general formulas (IX), (X), (XI) and (XII) in which R6 for straight-chain or branched alkyl or alkenyl radicals with 1 to 18 carbon atoms and R7 stand for straight-chain or branched alkyl radicals with 1 to 6 carbon atoms.
• Suitable sulfonic acids are therefore individual compounds or mixtures of those compounds of the general formula (V) which arise from fatty acid alkyl esters of the general formula (XIII) and SO3 according to the following reaction equation (3) by processes known per se from the prior art:
• fatty acids esters (XIII) or mixtures of such esters derived from natural fats and / or oils and converted into compounds of the formula (XIII) by transesterification in a manner known from the prior art are used in practice as starting materials for this reaction.
• fatty acids or mixtures of fatty acids derived from fats or oils of natural origin and with an alcohol of the general formula can also be used R7OH were converted into a fatty acid ester (XIII) or a mixture of several such esters.
• the radicals R6 in such sulfonic acids can mean straight-chain alkyl radicals from the group methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and Have octadecyl.
• straight-chain alkyl radicals it is also conceivable to use those which have a corresponding number of carbon atoms and are branched at any one or more positions in the molecule.
• straight-chain alkyl radicals R6 are preferred.
• R7 radicals represent alkyl radicals having 1 to 6 carbon atoms. These can therefore be radicals from the group consisting of methyl, ethyl, propyl, butyl, pentyl and hexyl, with straight-chain and branched radicals from this group also being conceivable here.
• the compounds of the above general formula (V) are usually obtained in practice by the carboxylic acid esters of the general formula (XIII), which can originate directly from natural sources or by transesterification, hydrogenation hardening or the like known from the prior art Reactions were made from such, implemented with SO3. This also takes place according to methods known from the prior art. For example, such reactions take place at temperatures in the range of 60 to 90 ° C and SO3 partial pressures in the range of 0.03 to 0.1 bar in the presence of a suitable organic solvent or in the absence of solvents. Reactions of mixtures (XIII) accordingly also lead to mixtures of the compounds of the general formula (V), which can be separated if desired, but can usually be used as such as an acid component for the fabric softener according to the invention.
• the fabric softeners according to the invention contain one or more sulfonic acids of the general formula (VI) instead of or in addition to the compounds of the general formula (V).
• the radical R6 has the meaning already given for the sulfonic acids of the general formula (V).
• the alkyl radicals or alkenyl radicals R6 can be at any point on the aromatic ring.
• particularly preferred embodiments of the invention contain one or more compounds in the fabric softening agents in which R6 for straight-chain alkyl radicals having 12 to 16 carbon atoms and / or R7 represent methyl or ethyl.
• Sulfonic acids or sulfonic acid mixtures of compounds from the group of hydropalm nucleic fatty acid methyl ester sulfonic acid, hydrotalg fatty acid methyl ester sulfonic acid, dodecylbenzenesulfonic acid and p-toluenesulfonic acid have proven particularly useful.
• “Hydropalm kernel fatty acid methyl ester sulfonic acid” is understood to mean those compounds which can be obtained from palm kernel oils by transesterification with methanol and hydrogenation of the unsaturated alkyl radicals and subsequent reaction with SO 3 in accordance with the above reaction equation.
• “Hydrotalg fatty acid methyl ester sulfonic acid” is understood to mean those compounds which are obtained from tallow by transesterification and hydrogenation of the unsaturated constituents and subsequent reaction with SO3.
• the fabric softeners contain one or more acids of the general formulas (VII) and (VIII) instead of or in addition to the compounds of the general formulas (V) and / or (VI).
• radicals R6 and R7 can have the meanings already defined above in connection with the sulfonic acids (V) and (VI). In this context, preference is also given to those alkyl radicals R6 which have 12 to 16 C atoms and / or R7 which are methyl or ethyl.
• one or more phosphonic acids of the general formula can preferably be present in the fabric softeners according to the invention.
• R6 has the meanings which have already been mentioned above in connection with the general formulas (V) and (VI).
• Compounds (IX) in which R6 represents straight-chain alkyl radicals having 12 to 16 carbon atoms are particularly preferred.
• Tetradecyl-1-phosphonic acid has proven particularly useful as a phosphonic acid component in the fabric softeners according to the invention.
• the fabric softeners according to the invention can also contain other phosphonic acids of the general formulas (X), (XI) and (XII) contain.
• the R6 radicals also represent straight-chain or branched alkyl radicals or alkenyl radicals having 1 to 18 C atoms
• the R7 radicals represent straight-chain or branched alkyl radicals having 1 to 6 C atoms, whereby - as already mentioned for the above Sulfonic acids defined - straight-chain alkyl radicals having 12 to 16 carbon atoms are preferred for the radicals R6, while methyl radicals or ethyl radicals are preferred for the radicals R7.
• the fabric softeners according to the invention usually contain the components mentioned, i.e. Amines of the general formulas (I) and / or (II) and / or quaternary ammonium compounds derived therefrom by quaternization on the one hand and sulfonic acids of the general formulas (V) to (VIII) and / or phosphonic acids of the general formulas (IX) to (XII) on the other hand in certain quantities.
• the amount of amine component is usually in the range from 10 to 90 mol%, while the amount of sulfonic acids and / or phosphonic acids is usually in the range from 90 to 10 mol%.
• the fabric softener according to the invention also contains water as a further component. This is present in the agents in an amount which adds up to 100% by weight with the amounts of the amine component and the sulfonic acid and / or phosphonic acid component and with the other constituents which may be present.
• the fabric softeners may also contain further substances conventionally used in such compositions. These can be, for example, fragrances, coloring substances, solvents, preservatives and viscosity regulators. Such substances are usually present in the fabric softener in amounts of 0 to 50% by weight, based on the total weight of the fabric softener. However, their presence or absence does not affect the fabric softening result.
• the amine component, sulfonic acid or phosphonic acid component and, if appropriate, further fabric softening agents according to the invention containing other constituents are packaged on an aqueous basis.
• the amounts of water are adjusted so that easy-to-handle, low-viscosity fabric softeners are produced, which in this form can be easily introduced into the post-wash liquor.
• the amounts of water in the ready-made fabric softeners according to the invention are usually in the range from about 98 to about 50% by weight.
• the fabric softeners according to the invention are produced by processes known per se from the prior art. This is essentially due to the fact that the individual components are mixed with one another in commercially available mixers. If desired, this is done using a solvent and / or at a slightly elevated temperature.
• the solvents that can be used for the production are expediently selected so that they can remain in the ready-made fabric softener. Examples of suitable solvents are ethanol, n-propanol, i-propanol, ethylene glycol, propylene glycol, diglycols and polyglycols. Suitable concentrations largely depend on the specific case, ie the miscibility of Amine component and carboxylic acid component dependent on water and can be selected within wide limits. An important criterion for the selection of the type and the amount of the solvent used in the production is the compatibility with water.
• the fabric softeners according to the invention obtained in this way are essentially soluble or finely dispersible in the aqueous phase and therefore have a particularly high storage stability.
• they When used in liquors, they are usually used in concentrations of 0.1 to 0.6 g / l, based on the amine and sulfonic acid or phosphonic acid components, and show the desired softening result in this concentration range. They give the textiles washed with them a good fluffiness and a soft feel, which test persons found to be extremely pleasant.
• the essential components used for the preparation of the agents according to the invention are easily accessible on an industrial scale from inexpensive, partly natural sources. Separating or cleaning operations of the individual components are not required for the production of the agents according to the invention.
• Fabric softeners according to the invention were produced using the components shown in Table 1 below.
• the acid component and the amine component were reacted with one another in a molar ratio of 1: 1 while heating on a steam bath to approx. 80 ° C. and stirring occasionally.
• Tetradecyl-1-phosphonic acid and dimethylhexadecylamine were reacted in a molar ratio of 1: 1 at about 80 ° C. in a manner corresponding to Examples 1 to 6 above.
• the mixtures obtained according to Examples 1 to 7 were dispersed in water.
• the active ingredient concentration of the fabric softener according to the invention was 0.3 g / l water.
• the terry samples were tested for their softness in comparison to the hard starting material by people who were skilled in the evaluation of the softness of textiles. The test was based on an evaluation scale in which the values can fluctuate between 0 (very hard grip) and 6 (very soft grip).
• the treated textiles have a very good fluffiness or great softness after drying.
• the absorbency of the treated textiles was not affected after drying compared to the untreated state.

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• 1987
  • 1987-11-19 DE DE19873739143 patent/DE3739143A1/de not_active Withdrawn
• 1988
  • 1988-11-11 EP EP88118812A patent/EP0316795A3/fr not_active Withdrawn
  • 1988-11-16 US US07/272,171 patent/US4913829A/en not_active Expired - Fee Related
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