DE1278682B - Process for the production of glossy and dirt-repellent coatings on fur hair - Google Patents

Description

Process for producing gloss-increasing and dirt-repellent coatings on fur-fur hair It has been found that gloss-increasing and dirt-repellent coatings are obtained on fur-fur hair if the hair side of the fur-skins is obtained at temperatures between 10 and 100.degree. C. and at pH values of 6 to 10, preferably 7 up to 9, treated with aqueous solutions of products which have been obtained by mixing compounds which contain more than one epoxy and / or halohydrin group with polyamines containing water-soluble polyalkylene oxide residues which contain more than one hydrogen atom bonded to nitrogen in the molecule, reacted and has stabilized the reaction products, which are still readily water-soluble, optionally by acidification, and the treated pelts are then dried at normal or elevated temperature, with the coating formed condensing out on the hair at the same time.

The products used according to the invention, the production of which is not the subject of the present invention, can, for. B. be prepared by the process of the French Patent 1,247,042 and the associated additional patent 79266, by reacting compounds which contain more in the molecule than one epoxide group and / or halohydrin-containing containing water-soluble polyalkylene polyamines having in the molecule more than one contain reactive hydrogen atom bonded to nitrogen, reacts at temperatures between 50 and 1001 C. The reaction can preferably be carried out in the presence of water, but also in the presence of organic solvents with or without the addition of any acid-binding substances, such as caustic alkali, alkali metal carbonate, magnesium carbonate or triethanolamine. Instead of the polyamines containing polyalkylene oxide radicals mentioned, condensation products of mono- and / or polyvalent chlorohydrin ethers of polyalkylene oxides or compounds containing polyalkylene oxide groups and ammonia or mixtures of ammonia and polyvalent aliphatic amines can also be used with advantage. After reaching the desired degree of precondensation, at which the still water-soluble condensation products already have a higher molecular weight structure, which can be recognized by a considerable increase in the viscosity of the reaction mixture, the reaction is expediently terminated by acidification with any inorganic or organic acid, which at the same time Stabilization of the products in the water-soluble state is achieved.

As compounds that have more than one epoxy and / or halohydrin group in the molecule contain epichlorohydrin and dichlorohydrin can be used. Also can you can also use reaction products of this, which are still reactive epoxy or contain halohydrin groups, so for example reaction products of Epichlorohydrin or dichlorohydrin with glycols, diglycols, polyalkylene oxides, glycerine, Dicarboxylic acids, polycarboxylic acids or polyhydric phenols. Also known to other people Well-obtained compounds with more than one epoxy group in the molecule are suitable.

The polyamines containing water-soluble polyalkylene oxide radicals are obtained by reacting with polyamines mono- and / or polyfunctional derivatives of polyalkylene oxides which contain reactive groups which are able to react with amino groups by exchanging the hydrogen atoms. Monofunctional or polyfunctional derivatives of polyalkylene oxides are understood to be those which contain, as reactive groups, chlorohydrin residues, glycidyl residues, halogen or other residues capable of forming anions, such as sulfuric acid ester residues. The basic bodies of these derivatives are built up from a total of about 3 to 70 alkylene oxide residues. Suitable alkylene oxides are primarily ethylene oxide, but also other cyclic oxides, such as propylene oxide or cyclohexanone oxide. The following compounds, for example, can be used as derivatives of polyalkylene oxides: mono- and bis-chlorohydrin ethers of polyalkylene oxides, mono- and bis-glycid ethers of polyalkylene oxides, bis-sulfuric acid esters of polyalkylene oxides, dihalides of polyalkylene oxides, oxyalkylation products of ethylene chlorohydrin, mono-, di- and trihalides of oi # * ethylated glycerine, mono-, di-, tri- and tetrahalides of oxethylated pentaerythritol, monochlorohydrin ethers of oxalkylated alcohols, monoglycidyl ethers of oxyalkylated alcohols, reaction products of oxyethylated ethylene chlorohydrin and a diisocyanate or reaction products of an oxyethylated ethyric acid.

These polyalkylene oxide derivatives are condensed, for example, with polyamines which contain at least two nitrogen groups in the molecule, preferably with polyalkylene polyamines. Examples of suitable polyamines are ethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, 1,4-phenylenediamine or 1,4-diaminoeyelohexane. For the implementation of the aforementioned starting components for the formation of polyalkylene oxide-containing polyamines are the proportions, the chain lengths and reaction conditions to be chosen so that products are obtained which have good water solubility. It is also essential that the amount of polyamines used is measured in such a way that, after the reaction, there are still sufficient reactive amino groups which are capable of reacting with epoxy and / or halohydrin groups. In place of the above polyamines or in admixture with these one can for the implementation of ammonia in the presence of alkali use, with less than 1 mole of ammonia should be used per reactive group of the Polyalkylenoxidderivats.

In the event that polyalkylene glycol halohydrin ethers containing more than one halohydrin group in the molecule are used to produce the polyalkylene glycol polyamines used as starting materials and the polyalkylene glycol polyamines obtained are converted to the products used according to the invention with the same polyalkylene glycol halohydrin ethers as If they were used to prepare the polyalkylene glycol polyamines, the preparation can be carried out in one operation by reacting the corresponding polyalkylene glycol halohydrin ethers with polyamines in such a ratio that the number of halogen atoms present is equal to the number of reactive nitrogen atoms present bonded hydrogen atoms as 4: 5 to 7: 5 behaves. As starting materials for this version of the process, in addition to polyalkylene oxide halohydrin ethers, halohydrate ethers of polyglycols containing heteroatom groups, such as. B. of oxalkylated diols and polyols (for example butanediol, glycerin , trimethylolpropane, pentaerythritol), oxalkylated polycarboxylic acids (for example phthalic acid, adipic acid, tartaric acid, citric acid), oxalkylated di- and polycarbonamides (for example adipamide, phthalic acid diamide) of oxyalkylation products Mono- and polyamines can be used. In this case, too, the progress of the condensation is interrupted by acidification after the desired degree of precondensation has been reached.

The water-soluble, curable products obtained are applied to the fur side of fur skins in an aqueous solution by brushing or spraying them. The solution is expediently mixed with any acid-binding agent (alkali, alkaline salts or a buffer substance such as sodium acetate) so that the pH of the solution is between 7 and 10 . The amount of acid binder added is by no means critical. The possibility of also being able to use alkali hydrocarbonates or alkali acetates as acid binders is particularly important for finishing sensitive fur skins, since the pH value of the working solution then hardly exceeds 7.5. The finished fur skins are dried in the usual way. Post-heating after drying is generally not necessary.

A preferred form of application is to carry out the fur-pelt treatment in connection with the so-called lautering process, in which the coat of hair is finished prepared fur skins in a rotating drum with moist sawdust from adhering Grease and dirt is freed and loosened. The ones used according to the invention hardenable condensates are here in an aqueous solution the sawdust with the necessary Dampening water was added, and a little alkali was added at the same time for complete hardening is added in the above-mentioned small amount. The mounting and hardening takes place at normal or slightly elevated temperature. Further processing of the skins takes place as in the usual lautering process.

The treatment according to the invention makes the surface of the hair smoothed. This is particularly the case with bleached ones that have been attacked by the bleaching chemicals Fur skins with a straw-like and brittle hair structure catch the eye. The one on the specified Film-like coatings produced away give the hair glossy, dirt-repellent properties and at the same time permanent antistatic properties, which are particularly beneficial for those with awn-haired Furs, such as mink and muskrat, come into their own. Have fur skins treated in this way also a particularly nice hair grip and hair game. The procedure can be used with advantage can also be used on all other types of fur, such as B. Lambskins, Persians, Fox skins, marmot skins or rabbit skins.

It was already known to make textiles real antistatic water-soluble, polyalkylene oxide chains containing polyamines, the epoxy groups or halohydrin groups forming epoxy groups and more than one in an alkaline medium reactive hydrogen atom bonded to nitrogen in the molecule should be used. A good antistatic effect is achieved here, but there are none Gloss effects, which are also not desired in textile materials. Rather, it has been shown that with these products even on textile materials Matting effects can be obtained. It was therefore surprising that the same Products used in the treatment of fur skins after curing and ironing off the coat to increase the shine and repel dirt result.

The following application examples are intended to explain the process according to the invention in more detail, without the process being restricted to these examples. Example 1 Grannenhaarige furs, such as mink, muskrat and receive a Bürstauftrag with an aqueous solution of 8 to 10 g / 1 of the reaction product of 3 moles of bis-chlorhydrinäther the polyglycol 600 with 1 mole of dipropylenetriamine on the hair side. Immediately before use, 1011 / o calcined soda, based on the amount by weight used, is added to the reaction product. The fur skins are then dried in the usual way at 30 to 35 ° C and moving air.

The fur skins obtained are now dirt and dust repellent and are characterized by a significantly increased shine of the coat.

The reaction product used was prepared as follows: 2.7 kg of tin tetrachloride were slowly added to 180 kg of polyglycol 600 at about 301 ° C. with stirring. After heating to 68 to 701 ° C. , 56 kg of epichlorohydrin were added rapidly with constant stirring and possibly cooling, so that the temperature remained between 68 and 70 ° C. , and stirring was continued at 701 ° C. for 1 hour. 80 kg of the crude chlorohydrin ether obtained were admixed with 13.2 kg of dipropylenetriamine, 35 kg of 40% strength sodium hydroxide solution and 150 kg of water with stirring, and the mixture was refluxed for about 40 minutes. The remaining amount of crude chlorohydrin ether was then added with stirring and the mixture was kept boiling for a further 20 to 30 minutes. The pH of the viscous reaction product had dropped to 7.2 after this time. After cooling , the pH was adjusted to about 5.5 with about 66 kg of 101% hydrochloric acid, and a pale yellowish, slightly cloudy, highly viscous liquid was obtained.

EXAMPLE 2 Ready-made muskrat skins are sprayed onto the hair side with a clearly alkaline aqueous solution of 8 to 10 g / l of a product which, according to the information given in Example 1, consists of 180 kg of polyglycol 600, 2.7 kg of tin tetrachloride , 56 kg of epichlorohydrin, 13.2 kg of dipropylenetriamine, 80 kg of water and 28 kg of 4011 /% sodium hydroxide solution and adjusted to a pH of 5.5 to 6 with 38 kg of 10% hydrochloric acid.

After drying, the fur hair has an increased shine and are dust-repellent and permanently antistatic.

Example 3 Grannenhaarige furs, such as mink, muskrat and are in Walkfaß with the concomitant use of from 300 to 5OOg of product per 50 described below of the sawdust used ready kg purified. The product is added to the moistening water required for the lautering process. Furthermore, about 10% calcined soda, based on the weight of the product used, is added at the same time.

A significant increase in gloss, a dust-repellent and antistatic effect and a strikingly beautiful play of hair.

The product used has been obtained in the following way: To 34.44 kg to 30 to 40 'C heated polyglycol 600 were 0.415 kg of tin tetrachloride were stirred and the mixture heated to 701 C. 10.78 kg of epichlorohydrin were then added at the same temperature and the mixture was subsequently stirred at 70 to 72 ° C. for 30 minutes. Then 1.915 kg of coconut amine and 2.075 kg of 50% sodium hydroxide solution were added, the mixture was kept at 95 to 100 ° C. for 30 minutes with stirring and the mixture was cooled to 90 ° C. for a further 10 minutes. After adding 2.537 kg of dipropylenetriamine, 42 kg of water and 3.45 kg of 50% sodium hydroxide solution, the mixture was kept initially at 90 ° C. and later at about 82 ° C. with stirring until a sample of the product clearly pulled threads. The reaction was then interrupted by adding 1.4 kg of 8511% formic acid, 4 kg of water were added and the mixture was cooled. Example 4 Mink skins are refined in a fulling barrel, as described in Beispie13, using the product described below. To produce the product, 300 g of polyglycol 1000 were mixed with 6 g of boron trifluoride in the form of a 20% ethereal solution. After adding 55 g of epichlorohydrin, the mixture was kept at 68 to 751 ° C. for 30 minutes with stirring. Then 44 g of dipropylenetriamine were added to the crude polyglycol bis-chlorohydrin ether, the temperature was increased to 120 to 130 ° C. and held for 1 hour. After cooling to 90 to 951 ° C. , 135 g of water were added and stirring was continued at the same temperature until the pH of the mixture had dropped below 8.5. It was then cooled to 60 ° C. , 30 g of epichlorohydrin were added and the mixture was kept at this temperature for about 50 to 60 minutes until the pH had reached 7. Then water was added to make up to 600 g of the finished product.

The skins treated in this way show a significantly increased shine and a beautiful play of hair. In addition, they are dust-repellent and antistatic. Example 5 completely trimmed mink pelts are provided on the hair side by means of a weakly alkaline aqueous solution adjusted from 8 to 10 g / 1 of the product prepared as described below with a spray application. 300 g of polyglycol 1500 were stirred with 6 g of boron trifluoride and 25 g of epichlorohydrin at 68 to 75 ° C. for 1 hour. After 29 g of dipropylenetriamine have been added, the temperature is increased to 130 to 140 ° C. and held for 2 hours. The temperature was then lowered to 90 to 95 ° C. , 104 g of 10% strength sodium hydroxide solution and 60 g of water were added and the mixture was stirred for 1 hour until the pH of the mixture had fallen to 7.2. The pH was adjusted to 5 to 5.5 by adding a little concentrated hydrochloric acid and the product was made up to 600 g of finished product with water.

After drying, the treated pelts have a significantly increased color Gloss, dirt-repellent and antistatic properties and one particularly pleasant hair grip.

Example 6 Muskrats are refined in a fulling barrel as described in Example 3 using the product prepared as described below. The mixture was heated, with stirring, 290g of a reaction product from 1 mole of ethylene chlorohydrin and 20 moles of ethylene oxide with 31 g of diethylene triamine 4 hours at 120 'C. After cooling to 60 "C, adding 100 g of water and 55 g epichlorohydrin was added at 55 to 60' C for about Stirring was continued for 1½ to 2 hours until the pH of the mixture had dropped to 7. The viscous product obtained was adjusted to pH 6 with hydrochloric acid and made up to 510 g with water.

The skins cleaned in this way are dirt- and dust-repellent and are characterized by a significantly increased shine and beautiful play of hair. Example 7 A product obtained in the following way is used as an additive in the lautering process of mink skins. A mixture of 320 g of bisglycidyl ether of polyglycol 1500, 18 g of ethylenediamine and 50 g of water was stirred at 80 to 901 C for 60 minutes. After adding 68 g of the crude bis-chlorohydrin ether of triethylene glycol, which was obtained by reacting 1 mol of triethylene glycol with 2 mol of epichlorohydrin in the presence of boron trifluoride, the mixture was stirred for a further 11/2 hours and the product was then brought to pH 5 to 5 with hydrochloric acid. 5 set.

If the product obtained is used, as described in Beispie13, for the lautering of mink skins, a significant increase in gloss, a dirt-repellent effect and a pleasant hair feel are achieved. Example 8 Finished muskrats received, as described in Example 1 , a brush application with a slightly alkaline aqueous solution of 8 to 10 g / l of the reaction product described below. After drying, the treated skins show a significantly increased shine, a nice play of hair and dirt and dust-repellent properties. To produce the product used, 80 kg of bis-chlorohydrin ether of polyglycol 600 with 7 kg of 2511% ammonia solution and 50 kg of water at 25 to 301 C for 45 minutes. After addition of 14 kg 5011 / cent sodium hydroxide solution was heated within 1 hour to 90 to 95 'C and further stirred for 1 hour at this temperature. The mixture was then cooled to 651 ° C. , 5.7 kg of epichlorohydrin were added and stirring was continued until a sample pulled threads and the pH had dropped below 7.5. Finally, the pH was adjusted to 5 with a little formic acid.

EXAMPLE 9 Muskrats are refined in a fulling barrel using 300 to 500 g of the product described below per 50 kg of sawdust used. The product is added to the necessary moistening water after making it alkaline. The treated skins have a significant increase in shine, beautiful play of hair and dirt and dust-repellent properties.

To produce the product, 800 kg of bishlorohydrin ether of polyglycol 600 were stirred with 34 kg of 25% ammonia solution, 6.3 kg of ethylenediamine, 100 kg of 500% sodium hydroxide solution and 650 kg of water. The mixture was then heated to 90 ° C. for 3 hours until a sample clearly pulled threads and, when sodium hydroxide solution was added, immediately gelled at room temperature. 25 kg of 85% formic acid and 110 g of water were then added.

Claims (3)

Claims: 1. A method for producing gloss-increasing and dirt-repellent coatings on fur fur hair, characterized in that the hair side of the fur skins with neutral to slightly alkaline aqueous solutions of products which have been obtained by using compounds that contain more than one epoxy - and / or halohydrin groups, reacted with water-soluble polyalkylene oxide radicals containing polyamines which contain more than one hydrogen atom bonded to nitrogen in the molecule and which has stabilized the reaction products, which are still readily water-soluble, optionally by acidification, treated and then subjected to drying at normal or elevated temperature. 2. The method according to claim 1, characterized in that aqueous solutions of such products are used for the treatment, which have been obtained by reacting more than one halohydrin group in the molecule containing polyalkylene oxide compounds with ammonia and / or polyamines, the number of those present in the reaction mixture Halogen atoms related to the number of hydrogen atoms bonded to nitrogen such as 4: 5 to 7: 5 . 3. The method according to claim 1 and 2, characterized in that the treatment is carried out in connection with the refining process. Documents considered: Swiss Patent No. 371083; U.S. Patent No. 2,829,071; Japanese interpretative publication No. 3131/1962, reported in Chemisches Zentralblatt, 1965, 14-3107.