DE19703362C1 - Use of anionic, cationic and/or nonionic chitosan and derivatives - Google Patents

Abstract

Use of 0.1-5 wt.% of anionic, cationic and/or nonionic chitosans and/or chitosan derivatives in the production of fabric conditioners is claimed.

Description

Field of the Invention

The invention relates to the use of chitosans and / or chitosan derivatives for the production of Finishing agents.

State of the art

A frequently undesirable effect both when washing textiles and during pretreatment of yarns, fabrics and the like, is that the fibers link and thereby the Give fabrics a certain hardness that is detrimental to comfort. Accordingly, the Consumers feel the need to remedy this disadvantage. This can be done mechanically, so For example, take place in a dryer, but with a not inconsiderable wear Textiles. Another possibility is during or preferably after Add washing agents to the wash liquor, which soak onto the fibers and, for example Prevent chaining via the path of electrostatic repulsion. With these avivants it is usually cationic surfactants, but again when used Disadvantages are associated: on the one hand, these cannot easily be combined with anionic surfactants use, as otherwise salt precipitation occurs, on the other hand they are very low but demonstrable potential for irritation, which is especially true for consumers with sensitive skin can lead to redness [cf. Lang et al. Soap-oil-fat waxes, 117, 690 (1991)]. Such problems can be avoided by focusing on certain anionic surfactants such as B. partial glyceride sulfates or nonionic surfactants such. B. polyol fatty acid esters, although also have advanced properties, but often improve in performance are worthy of mention. Another problem remains unsolved overall, namely to equip fibers in such a way that they are protected from splitting to reduce mechanical skin irritation and to further improve the wearing comfort.

Accordingly, the complex object of the present invention was to provide finishing agents To make available that are free from the disadvantages described and located next to one  excellent soft feel, improved dermatological compatibility at the same time still distinguished by the fact that they easily attach to the fibers and stick, the splitting of the Prevent fibers reliably and bind moisture in the fibers.

Description of the invention

The invention relates to the use of anionic, cationic and / or nonionic Chitosans and / or chitosan derivatives in amounts of 0.1 to 5 wt .-% - based on the agent - for Manufacture of anti-aging agents.

Surprisingly, it was found that chitosans or chitosan derivatives, their use up to now was only known for cosmetics, alone, but preferably in a mixture with other advanced ones cationic, anionic and / or nonionic surfactants, fibers not only a pleasant Give a soft feel, but also give rise to far less skin irritation. Another un The expected effect is that textile fibers treated with chitosans and / or chitosan derivatives According to scanning electron microscopic examinations, there are far fewer split ends than those that had been equipped with conventional anti-aging agents. In this way, the risk of - chemical and mechanical - skin irritation further reduced and the wearing comfort significantly improved.

Chitosans and chitosan derivatives

Chitosans are biopolymers and belong to the group of hydrocolloids. Chemically considered are partially deacetylated chitins of different molecular weights that contain the following - idealized - monomer module:

In contrast to most hydrocolloids, which are negatively charged in the range of biological pH values , chitosans are cationic biopolymers under these conditions. The positively charged Chitosans can and do interact with oppositely charged surfaces therefore in cosmetic hair and body care products as well as pharmaceutical preparations  used (cf.Ullmann’s Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, pp. 231-332). Overviews on this topic are also available from B. Gesslein et al. in HAPPI 27, 57 (1990), O.Skaugwd in Drug Cosm.Ind. 148: 24 (1991) and E. Onoyen et al. in Seifen-Öle-Fette-Wwachs 117, 633 (1991). To make the Chitosane is assumed to be from chitin, preferably the shell remains of crustaceans, which are considered cheap Raw materials are available in large quantities. The chitin is produced in a process that for the first time by Hackmann et al. has been described, usually first by adding bases deproteinized, demineralized by adding mineral acids and finally by adding strong bases deacetylated, the molecular weights being distributed over a broad spectrum can. Appropriate methods are, for example, made from Makromol. Chem. 177, 3589 (1976) or French patent application FR-A 2701266 known. Such types are preferred used, as disclosed in German patent application DE-A1 44 42 987 (Henkel). In addition to the chitosans as typical cationic biopolymers also come within the meaning of the invention anionically or nonionically derivatized chitosans, such as. B. carboxylation, succinylation or Alkoxylation products in question, such as those described in German Patent DE-C2 37 13 099 (L'Oreál) and the German patent application DE-A1 196 04 180 (Henkel) are described.

Esterquats

The surfactants that can be used together with the chitosans include in particular Esterquats. This term is generally used for quaternized fatty acid triethanolamine understood ester salts. These are known substances that are used according to the relevant Me can obtain methods of preparative organic chemistry. In this context, be on the international patent application WO 91/01295 (Henkel), according to which one triethanolamine in The presence of hypophosphorous acid is partially esterified with fatty acids, air is passed through and on finally quaternized with dimethyl sulfate or ethylene oxide. From the German patent specification DE-C1 43 08 794 (Henkel) is also known a process for the preparation of solid ester quats, in which one the quaternization of triethanolamine esters in the presence of suitable dispersants, preferably wise fatty alcohols. Overviews on this topic have been published, for example, by R.Puchta et al. in Tens.Surf.Det. 30,186 (1993), M.Brock in Tens.Surf.Det 30,394 (1993), R. Lagerman et al. in J.Am.Oil.Chem.Soc. 71, 97 (1994) and I.Shapiro in Cosm.Toil. 109, 77 (1994) appeared. The quaternized fatty acid triethanolamine ester salts follow the formula (I),

in the R¹CO for an acyl radical having 6 to 22 carbon atoms, R² and R³ independently of one another for hydrogen or R¹CO, R⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH₂CH₂O) _q H group, m, n and p in total for 0 or numbers from 1 to 12, q represents numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which can be used in the sense of the inven tion are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures how they occur, for example, in the pressure splitting of natural fats and oils. Technical C _12/18 coconut _fatty acids and in particular partially hardened C _16/18 tallow or palm fatty acids and elaidic acid-rich C _16/18 fatty acid cuts are preferably used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm fatty acid (iodine number 0 to 40 ). From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (I) have proven to be particularly advantageous in which R¹CO for an acyl radical having 16 to 18 carbon atoms, R² for R¹CO, R³ for hydrogen, R⁴ for a methyl group, m, n and p for 0 and X represents methyl sulfate.

In addition to the quaternized fatty acid triethanolamine ester salts also come as esterquats quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II),

in the R¹CO for an acyl radical having 6 to 22 carbon atoms, R² for hydrogen or R¹CO, R⁴ and R⁵ independently of one another for alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or Numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

Finally, the quaternized ester salts of fatty acids are a further group of suitable ester quats with 1,2-dihydroxypropyldialkylamines of the formula (III),

in the R¹CO for an acyl radical having 6 to 22 carbon atoms, R² for hydrogen or R¹CO, R⁴, R⁶ and R⁷ independently of one another for alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the for examples mentioned for (I) also for the esterquats of the formulas (II) and (III). Other types of esterquat, which are suitable as surfactant components in the sense of the invention are those based on sugar or glycerin Derivatives known from the patents DE-C1 195 39 846 (Henkel) and EP-B1 0258923 (Akzo) are. The ester quats usually come in the form of 50 to 90% by weight alcoholic solutions the trade, which can be easily diluted with water if necessary.

Quaternary tetraalkyl ammonium salts

In addition to the ester quats, conventional quaternary ammonium are also suitable as cationic surfactants salts which follow the formula (IV),

in which R⁸ and R⁹ independently of one another for alkyl and / or alkenyl radicals with 12 to 22 carbons atoms, R¹⁰ for R⁸, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms or one Benzyl radical, R¹⁰ represents a methyl radical and X represents halide or methyl sulfate. Two of the residues R⁸ bis R¹¹ can form a ring with 5 to 6 chain links together with the nitrogen atom. Typical Examples are dimethyldilaurylammonium chloride, dimethyldicetylammonium bromide, dimethyldistearyl ammonium chloride, methyltristearylammonium chloride, hydoxyalkyltristearylammonium chloride and / or Methylbenzylstearylammonium chloride. Also come as quaternary ammonium compounds the cationic sugar surfactants of the German patent DE-C2 44 13 686 in question.  

Partial glyceride sulfates

Partial glyceride sulfates, i.e. mono- and diglyceride sulfates and their technical mixtures. These substances are known anio African surfactants, which are obtained according to the relevant methods of preparative organic chemistry can be. Usually, their production is based on triglycerides, the opposite after transesterification to the partial glycerides if necessary and then sulfated and new be realized. It is also possible to pre-partial glycerides with suitable sulfating agents preferably to implement gaseous sulfur trioxide or chlorosulfonic acid [cf. EP-B1 0561825, EP-B1 561999 (Henkel)]. If desired, the neutralized substances can be subjected to ultrafiltration fen to reduce the electrolyte content to a desired level [DE-A1 42 04 700 (Hen kel)]. Overviews on the chemistry of partial glyceride sulfates are, for example, by A.K.Biswas et al. in J.Am.Oil.Chem.Soc. 37: 171 (1960), F.U.Ahmed in J.Am.Oil.Chem.Soc. 67, 8 (1990) and A. Behler et al. in Lipid 98, 309 (1996). The use of partial glyceride sulfates as a finishing agent is Subject of the international patent application WO 94/13768 (Henkel). In the sense of the invention Partial glyceride sulfates to be used follow the formula (V),

in the R¹²CO for a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z in Sum for 0 or for numbers from 1 to 30, preferably 2 to 10, and Y for an alkali or alkaline earth limetall stands. Typical examples of partial glyceride sulfates suitable for the purposes of the invention are Reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid mono glyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their Ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Preferential partial glyceride sulfates of the formula (V) are used in which R 12 CO for a linear acyl radical with 8 to 18 carbon atoms.

Polyol fatty acid esters

The preferred nonionic surfactant component is polyol fatty acid ester, which differs from Polyols can derive 2 to 15 carbon atoms and at least two hydroxyl groups. Fabrics this type and its use are the subject of US Pat. No. 5,290,459 (Colgate). Typical examples of suitable polyol components are:

• - glycerin;
• Alkylene glycols such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, Hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;
• - Technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;
• Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, Pentaerythritol and dipentaerythritol;
• - Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical such as Methyl and butyl glucoside;
• - Sugar alcohols with 5 to 12 carbon atoms such as sorbitol or mannitol;
• - Sugar with 5 to 12 carbon atoms such as glucose or sucrose;
• - aminosugars such as glucamine.

The acid component of the esters can differ from fatty acids with 6 to 22 carbon atoms and 0 and / or derive 1, 2 or 3 double bonds. Typical examples are caproic acid, caprylic acid, 2-ethylhexanoic acid, Capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmolein acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, Elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical Mixtures, e.g. B. in the pressure splitting of natural fats and oils, in the reduction of Aldehydes from Roelen's oxosynthesis or the dimerization of unsaturated fatty acids attack. Technical fatty acids with 12 to 18 carbon atoms such as, for example, are preferred Coconut, palm, palm kernel or tallow fatty acid. In total, the use of mono / di / triesters is preferred based on trimethylolpropane and / or pentaerythritol with saturated fatty acids with 12 to 18 Carbon atoms.

Other non-ionic surfactants

In addition to the polyol fatty acid esters, addition products also come as nonionic surfactants an average of 5 to 25 moles of ethylene oxide to fatty acid amides, in which the acid derives components of fatty acids with 6 to 22 and preferably 12 to 18 carbon atoms. The The use of these substances is known from European patent EP-B1 0415279 (BASF). The use of alkoxylated, especially low-propoxylated tri is also possible glycerides, as proposed in EP-A1 0569847 (Huls).  

Finishing agent

It has proven advantageous to use the chitosans and / or chitosan derivatives in amounts of 0.1 to 5, preferably 0.5 to 3 and in particular 1 to 2% by weight, based on the composition, to be used. Of the The proportion of further surfactants can range from 1 to 30, preferably 5 to 25 and in particular 7 up to 15% by weight, based on the composition. It is also recommended that the chitosans and / or chitosan derivatives and the other surfactants in a weight ratio of 1:99 to 50:50, preferably 2: 98 to 20: 80 and in particular 5: 95 to 40: 60. Which receives in the sense of the invention Means can represent concentrates, which the consumer on site to the application concentration can be diluted, but directly diluted preparations can also be purchased to be brought. Accordingly, the agents may have a non-aqueous content of 5 to 50, preferably Have 10 to 35 and in particular 15 to 25 wt .-% and other conventional auxiliaries and additives contain. The funds are suitable for the finishing of textile fabrics as a whole, i. H. Fibers, Yarns, fabrics, textiles and end products and can therefore be used both in textile pretreatment and actual laundry as well as used in the aftertreatment. In particular, the Chitosan derivatives because of their high compatibility with anionic surfactants also for the production of full washing use agents with fabric softener effect.  

Examples

Various aqueous preparations were used at application concentrations of 1 or 5 wt .-% for their soft feel, the dermatological compatibility and the fiber split examined.

• - Soft grip. Terrycloth fabric was first washed with a standard detergent and then treated with the test solutions. Then the fabric of 6 trained people were assessed subjectively on a scale from 4 = hard to 1 = very soft enough. The average of three measurements is given.
• - Total stimulus score. The potential for irritation was determined according to the OECD method No. 404 and the EEC Directive 84/449 EEC, Pt.B.4. The specified stimulus sum scores were from the stimulus scores obtained after 24, 48 and 72 hours. The was in Ver same experiment V6 determined irritation sum score for a 5% by weight solution of dimethyldistearyl 100% ammonium chloride and the stimulus sums obtained in the remaining experiments scores related to this.
• - Fibersplit terry cloth was washed 20 times alternately with a detergent and then treated with the test solutions. Subsequently, scanning electron microscopy Comparing images of the tissue with images before the treatment and the split fiber sub determined jective. "Sg" = very low, "g" = low, "d" = clearly and "st" = strong.

Preparations 1 to 8 in Table 1 are according to the invention, mixtures V1 to V8 in Table 2 serve for comparison.  

Table 1

Execution of finishing agents (quantities as% by weight)

Table 2

Execution of finishing agents (quantities as% by weight)

Claims (8)

1. Use of anionic, cationic and / or nonionic chitosans and / or chito sand derivatives in amounts of 0.1 to 5 wt .-% - based on the agent - for the production of Aviva averaged. 2. Use according to claim 1, characterized in that the chitosans and / or Chitosan derivatives together with other cationic, anionic and / or nonionic ten siden uses. 3. Use according to claim 2, characterized in that as cationic surfactants Ester quats and / or quaternary tetraalkylammonium salts are used. 4. Use according to claim 2, characterized in that one as anionic surfactants Partial glyceride sulfates used. 5. Use according to claim 2, characterized in that one as nonionic surfactants Polyfatty acid esters, fatty acid amide ethoxylates or alkoxylated triglycerides. 6. Use according to claims 2 to 5, characterized in that the other Surfactants in amounts of 1 to 30 wt .-% - based on the agent - used. 7. Use according to claims 2 to 6, characterized in that the chitosans and / or chitosan derivatives and the other surfactants in a weight ratio of 1:99 to 50:50 starts. 8. Use according to claims 1 to 7, characterized in that means with one produces non-aqueous content of 5 to 50 wt .-%.