DE19942681B4 - Copolymer for the treatment of leather and fur skins - Google Patents

Abstract

A copolymer for treating leather and fur skins obtainable by polymerizing a mono- or dicarboxylic acid having a carbon-carbon double bond of 3 to 10 carbon atoms with a compound, the compound being preparable by:
a) a fatty alcohol and / or a wax alcohol optionally having from 4 to 20 units derived from ethylene oxide and / or propylene oxide reacted with a carbon-carbon double bond-containing dicarboxylic acid having 3 to 10 carbon atoms or an anhydride thereof,
b) the product from step a) reacts with an alkanolamine and
c) the product from step b) is reacted with a phosphating agent.

Description

The This invention relates to a copolymer for the treatment of leather and fur skins, a process for its preparation and its use for the softening, greasing and water repellency of leather and fur skins.

leather and fur skins are today on the one hand by chrome tanning and the others made by chrome-free tanning. For over 100 years Years proven Chrome tanning still has the largest share of tanning. The chrome-free tanning, mostly by using a combination of aldehyde modifiers, synthetic and vegetable tannins carried out is, however, decreases from ecological establish in their meaning constantly to.

decisive for the Leather character, in addition to the tannins, the fatliquoring and hydrophobing agents which have properties such as softness, Scar form, firmness and surface grip, crucial influence. They are used in natural and synthetic products and polymer products.

Especially for the Fatliquoring of leather and fur dominate the products on more natural Base. In the case of water repellents the synthetic products have The biggest part, however, the polymer products are becoming increasingly important.

Of the Advantage of polymer products over natural and synthetic products lies mainly in the elevated Washing and cleaning resistance, the disadvantage in the mediation of the required softness and Grip properties. The previously known polymer products give the Leather and fur skins a dull, rubbery handle. You can therefore only proportionally in combination with natural and / or synthetic Products are used.

The DE 42 23 111 A1 describes leather fatliquoring agents and their use of co-oligomers of fatty crotonates and free-radically copolymerizable hydrophilic desylenically unsaturated acids and / or their anhydrides as amphiphilic agents for greasing leather and fur skins.

From the DE 42 14 011 C1 For example, there is known a treatment agent for the retanning, filling, softening and hydrophobing of leather obtained by copolymerization of ethylenically unsaturated dicarboxylic acid anhydrides, ethylenically unsaturated dicarboxylic acid esters and ethylenically unsaturated dicarboxylic acid amides or mixtures thereof and a specific ω-ethylenically unsaturated compound.

The DE 42 05 839 A1 discloses the use of reaction products of homo- or copolymers based on monoethylenically unsaturated dicarboxylic anhydrides with amines or alcohols for the fat and filling of leather or fur skins.

From the DE 196 36 494 A1 Leather treatment agents are already known, these agents being obtainable by polymerization of acrylic acid and / or methacrylic acid and / or their acid chlorides or anhydrides and reaction of the polymer with fatty amines. These leather treatment agents are used for the production of low-fogging leather.

Furthermore, the describes DE 196 10 550 A1 Copolymers obtained by polymerization of building blocks, wherein the building blocks contain a) half esters of maleic acid with oleophilic alcohols and / or their lower Alyklenoxidaddukten and b) acrylic acid and / or methacrylic acid.

The US 5 558 675 describes complex polymers for the treatment of leather and a process for the post-treatment of tanned leather and furs.

The DE 44 05 205 A1 describes the use of water-dispersible and / or water-emulsifiable partial esters of cyclic polycarboxylic acids or their (partial) anhydrides and monofunctional alcohols having a fat character as an amphiphilic agent for greasing equipment and optionally retanning of leathers and furs.

From the DE 41 29 244 A1 is the use of aqueous dispersions of co-oligomers known that from the free-radically initiated aqueous emulsion copolymerization in weakly acidic to neutral have set the pH range of (a) half esters of maleic acid with oleophilic alcohols and / or their lower alkylene oxide adducts and (b) acrylic acid and / or methacrylic acid as main components, which also additionally (c) minor amounts of further hydrophilic and / or oleophilic comonomers in the oligomer -Molecule may be produced.

Of the The present invention is therefore based on the object compounds to provide for the treatment of leather and fur skins, these give a good grip.

• a) ein Fettalkohol und/oder ein Wachsalkohol, die gegebenenfalls 4 bis 20 von Ethylenoxid und/oder Propylenoxid abgeleitete Einheiten aufweisen, mit einer Kohlenstoff-Kohlenstoff-Doppelbindung aufweisenden Dicarbonsäure mit 3 bis 10 C-Atomen oder einem Anhydrid davon umgesetzt,
• b) das Produkt aus Schritt a) mit einem Alkanolamin reagiert und
• c) das Produkt aus Schritt b) mit einem Phosphatierungsmittel umgesetzt wird.

According to the invention this is obtainable by a copolymer for the treatment of leather and fur skins, which is obtainable by polymerization of a carbon-carbon double bond mono- or dicarboxylic acid having 3 to 10 carbon atoms with a compound, wherein the compound can be prepared by

• a) a fatty alcohol and / or a wax alcohol optionally having from 4 to 20 units derived from ethylene oxide and / or propylene oxide reacted with a carbon-carbon double bond-containing dicarboxylic acid having from 3 to 10 carbon atoms or an anhydride thereof,
• b) the product from step a) reacts with an alkanolamine and
• c) the product from step b) is reacted with a phosphating agent.

It was surprisingly found that this Copolymers are used to treat leather or fur skins can, these then have a round, warm, silky handle, d. H. not like the previously known polymer products to leather or Furskins with a dull, rubbery handle lead.

It was further surprisingly found that the Copolymers of the invention extremely resistant to washing and cleaning are.

One Another advantage of the copolymers of the invention is the high Badzezehrung, d. H. that usually used to treat leather and fur skins in a bath Copolymer becomes almost complete Applied to the leather or fur.

wobei R für den vom hydroxyfunktionellen Alkanolamid abgeleiteten Rest steht.It is believed, without, however, being bound by the foregoing reactions to provide a product based on a copolymer of phosphated long chain alkyl alkenyl ester mono / dialkanolamides of ethylenically unsaturated dicarboxylic acid with ethylenically unsaturated mono- / dicarboxylic acids. The reaction of the alcohol in step a) with the ethylenically unsaturated dicarboxylic acid or anhydride presumably forms the corresponding half-ester. In the subsequent step b), a hydroxy-functional alkanolamide is obtained by the reaction of this half ester with an alkanolamine. In the product obtained after step b) no base nitrogen is detectable, so that the assumption is justified that a hydroxy-functional alkanolamide is present, but it can not be excluded that an ester of the aforementioned half ester and the alkanolamine by reaction of the free carboxyl group of the half ester is formed with the OH group of alkanolamine. In step c), the reaction of the product from step b) with a phosphating agent, in particular phosphorus pentoxide, wherein the structure of the compound (s) thus obtained is no longer ensured, ie there are no longer clearly defined compounds. Presumably it is a mixture of

where R is the radical derived from the hydroxy-functional alkanolamide.

The copolymer according to the invention is available through that one Carbon-carbon double bond having mono- or dicarboxylic acid with the special compound obtainable by steps a) to c) is polymerized. The relationship the mono- or dicarboxylic acid to this compound may be 3: 1 to 1: 3, by weight, be.

The copolymer according to the invention can be made from the two aforementioned components or possibly also one or more further components, wherein the proportion of the further component 5 wt .-%, based on the Copolymer, do not exceed should.

The used for the preparation of the copolymer according to the invention Carbon-carbon double bond having mono- or dicarboxylic acid has 3 to 10 carbon atoms, wherein the monocarboxylic acid 3 bis 10 C atoms and the dicarboxylic acid 4 to 10 carbon atoms can have. Preferably, it is a monocarboxylic acid, the under methacrylic acid and acrylic acid selected can be.

to Preparation of the copolymer of the invention may be a mixture of two or more, different from each other, Carbon-carbon double bond containing mono- or dicarboxylic acids used become.

The second component of the copolymer of the invention is a special one Compound prepared by the aforementioned steps a) to c) is.

According to step a) becomes a fatty alcohol and / or a wax alcohol with a carbon-carbon double bond having dicarboxylic acid reacted with 3 to 10 carbon atoms or an anhydride thereof.

These dicarboxylic acid may have 4 to 10 carbon atoms. A representative of these is maleic acid; one Representative of the anhydride is maleic anhydride, due to its good reactivity is used particularly favored.

at a fatty alcohol is linear, saturated or unsaturated primary Alcohols with 6 to 22 carbon atoms. Be unsaturated fatty alcohols used, they usually have 1 carbon-carbon double bond on.

conveniently, are fatty alcohols having 16 to 22 carbon atoms, in particular those with 1 carbon-carbon double bond used. One Representative of this is the oleyl alcohol.

Of the The term "waxy alcohols" encompasses higher molecular weight water-insoluble, linear saturated or unsaturated primary Alcohols with 24 to 36 carbon atoms.

For the copolymer according to the invention Can be a fatty alcohol or a mixture of two or more, from each other different fatty alcohols are used. Used for the inventive copolymer Wax alcohol used, so either one or a mixture of two or more different waxy alcohols be used.

Further may be a mixture of one or more fatty alcohols with a or more wax alcohols are used.

Become of the aforementioned alcohols, those having a long carbon chain used, it has a positive effect on the hydrophobing properties the copolymer of the invention out. For alcohols with shorter Carbon chains will have the property of being a softener positively influenced by leather and fur skins. Another advantage of this Alcohol is that pleasant Gripping properties of the treated with the copolymers of the invention Leather and fur skins can be achieved.

In a preferred embodiment the copolymer of the invention the alcohol (fatty alcohol, wax alcohol) has at least 4, in particular 4 to 20, more particularly 4 to 8, of ethylene oxide (EO) and / or propylene oxide (PO) derived units.

there can these units be bound to the OH group of the alcohol. By ring opening of ethylene oxide or propylene oxide is formed from these one new terminal OH group, which reacts with other EO / PO units and with the dicarboxylic acid is capable.

Surprisingly was found that through the installation of the aforementioned units achieved a favorable electrolyte stability is so that copolymers of the invention can be used directly in the chrome tanning, d. H. Tanning, softening, Greasing and hydrophobing take place in the same working process. Thereby arise favorable Effects of splitting and folding the wetblue.

In Step b) in the preparation of the copolymer of the invention is the product from step a) reacted with an alkanolamine.

Under An "alkanolamine" becomes compounds understood of any kind, including both amino and hydroxy groups possess as functional groups. In this case, the amino and the hydroxy group be bound to different carbon atoms. The alkanolamine may have one or two hydroxy groups. Preferably the alkanolamine 2-aminoethanol.

to Preparation of the copolymer of the invention is in accordance with the above Step c) the product from step b) with a phosphating agent implemented.

Under the term "phosphating agent" becomes compounds understood of any kind, which when reacted with OH groups phosphoric acid ester form. Preferably, the phosphating agent is phosphorus pentoxide.

• a) der Fettalkohol und/oder der Wachsalkohol, die gegebenenfalls 4 bis 20 von Ethylenoxid und/oder Propylenoxid abgeleitete Einheiten aufweisen, mit der Kohlenstoff-Kohlenstoff-Doppelbindung aufweisenden Dicarbonsäure mit 3 bis 10 C-Atomen oder dem Anhydrid davon umgesetzt,
• b) das Produkt aus Schritt a) mit dem Alkanolamin reagiert,
• c) das Produkt aus Schritt b) mit dem Phosphatierungsmittel umgesetzt, und
• d) die Verbindung aus Schritt c) mit der eine Kohlenstoff-Kohlenstoff-Doppelbindung aufweisenden Mono- oder Dicarbonsäure mit 3 bis 10 C-Atomen copolymerisiert wird.

The present invention further provides a process for the preparation of a copolymer described in more detail above, wherein

• a) the fatty alcohol and / or the wax alcohol, which optionally have 4 to 20 units derived from ethylene oxide and / or propylene oxide, are reacted with the carbon-carbon double bond-containing dicarboxylic acid having 3 to 10 carbon atoms or the anhydride thereof,
• b) the product from step a) reacts with the alkanolamine,
• c) reacting the product from step b) with the phosphating agent, and
• d) the compound from step c) is copolymerized with the carbon-carbon double bond-containing mono- or dicarboxylic acid having 3 to 10 carbon atoms.

in the inventive method can while the carbon-carbon double bond mono- or dicarboxylic acid, the fatty alcohol, the wax alcohol, the alkanolamine and the phosphating agent can be used, which were explained above.

In Step a) of the method according to the invention the fatty alcohol and / or the wax alcohol with the aforementioned dicarboxylic acid or the anhydride thereof. Preferably, these are reacted to both components in equimolar amounts, as a result, optimum yields of the half-ester are obtained. It But also a surplus of one these two components are used, for. B. an excess of 30 Mol% of the alcohol, based on the acid.

to execution of step a) of the process according to the invention, the alcohol to the acid or be added to the anhydride. conveniently, the addition is at higher Temperatures, z. B. about 80 ° C, carried out.

The Reaction of the alcohol with the dicarboxylic acid can be done without using one Solvent be carried out. The alcohol and the dicarboxylic acid you can z. With stirring, until completion react to the reaction; For example, after about one Hour to be done. The reaction may be carried out at higher temperatures, e.g. B. 90 up to 125 ° C, carried out become.

In Step b) of the method according to the invention the reaction product from step a) is reacted with the alkanolamine. The alkanolamine can be added directly to the reaction mixture of the step a), d. H. without intermediate purification of the product from step a) become.

These Reaction can also be done without using a solvent. conveniently, she will be at higher Temperatures, z. B. 90 to 95 ° C, carried out. To avoid unwanted Side reactions, the reaction under inert gas, z. Nitrogen respectively. She can at higher Temperatures, z. B. about 110 ° C, with stirring carried out become.

In a preferred embodiment the method according to the invention in step b) the product from step a) with the alkanolamine in an approximately equimolar ratio implemented. It can also be a deficit of up to 30 mol% alkanolamine be used.

In Step c) of the method according to the invention the product from step b) is reacted with the phosphating agent, wherein, as already stated above, unspecified Connections are formed. There are several reaction possibilities are given, is probably a mixture of mono- and Diphosphorsäureestern.

This reaction can be carried out at a temperature of 50 to 80 ° C. It can at de Edukte until completion of the reaction, z. B. after about two hours, stirred.

The amount of phosphating agent is chosen so that conveniently substantially all OH groups of the product from step b) are reacted to form phosphoric acid esters. If P ₂ O _{5 is used} as the phosphating agent, it is preferably used in a ratio of 1 P ₂ O ₅ per 3 OH group of the product from step b).

To execution of step c) of the process according to the invention, the reaction mixture diluted with a glycol or a mixture of different glycols. For "glycol" in the sense of the present Invention is ethylene glycol or of this parent compound derived diols whose hydroxy groups are vicinal arranged or are located on non-adjacent OH groups, e.g. B. 1,3-butylene glycol, hexylene glycol, Diethylene and polyethylene glycols.

The Polyethylene glycol acts as a solvent, its quantity therefore chosen so will that the Compound from step c) is optimally solved therein.

If it wanted The solution can be of the product of step c) in glycol with a base, e.g. B. one Amine, such as triethanolamine, are neutralized.

The in this glycol solution contained connection is made according to step d) of the method according to the invention having a carbon-carbon double bond Mono- or dicarboxylic acid copolymerized. It is possible that only these two monomers, optionally copolymerized with conventional impurities or other polymerizable monomers are present, for. In an amount of up to 5 wt .-%, based on the copolymer.

Surprisingly was found that the Copolymerization using the unusual in this field solvent Glycol runs smoothly.

The Polymerization may be accomplished by a polymerization catalyst, e.g. B. Ammonium persulphate, at elevated temperature, z. B. 80 ° C, to be started. The polymerization can be carried out in customary manner the person skilled in this necessary equipment and materials are known. For example, the polymerization can be carried out at 80 ° C. for one hour. If necessary, the reaction mixture can then be diluted with water and optionally the polymerization is carried out further, z. During about an hour at elevated Temperature, z. B. 80 ° C.

By the inventive method Is it possible, for the Softening, oiling and waterproofing of leather and fur skins make suitable copolymers quickly, easily and inexpensively.

Further The present invention relates to the use of the copolymer of the invention for the softening, greasing and water repellency of leather and fur skins.

there Is it possible, the copolymers of the invention used alone, d. H. without the addition of further fatliquoring / hydrophobing agents on natural or synthetic basis. A combination with natural or synthetic fatliers and / or water repellents is also possible.

The Treatment of leather and fur skins for lubrication, softening and Hydrophobing takes place in accordance with the previously used Means, the skilled person are therefore necessary steps, Materials and devices known.

The The present invention will be further illustrated by the following examples, wherein "parts", parts by weight and "%" mean% by weight.

Example 1: Preparation a copolymer of the invention

11.3 Parts of oleyl alcohol were mixed with 4.1 parts of maleic anhydride at 80 ° C. The mixture was stirred for 1 hour at 90 to 95 ° C until the half ester was formed. For the half ester then 2.6 parts of monoethanolamine between 90 and 95 ° C added.

Then they left the Mix under nitrogen for four hours at 110 ° C with stirring.

The product obtained was then at 50 to 60 ° C with 2.6 parts Phosporpentoxid phosphated. The stirring time was two hours. The phosphoric acid ester was 10.0 parts Diluted hexylene glycol and neutralized with 14.9 parts of triethanolamine.

To To this mixture was added 5.0 parts of methacrylic acid. The copolymerization was introduced with 0.1 part of ammonium persulfate at 80 ° C. It was 1 hour at 80 ° C further polymerized. The polymer was mixed with 49.4 parts of water dilute and 1 more hour at 80 ° C held. The result was a clear, brown, clear water-soluble viscous product.

With the copolymer thus obtained was chromium retanned leather at 12%, based on shaved weight, greased and then dyed.

It became a soft, festrarbiges leather with round handle with a level and non-lightened coloring receive.

vegetable leathers was also greased at 12%, based on shaved weight, and then dyed. The Leather was also very soft and firm with a pleasant Handle. The color was very little and lightened.

Example 2: Preparation a copolymer of the invention

11.3 Parts of a saturated C18 fatty alcohol was added with 4.1 parts of maleic anhydride at 80 ° C. The mixture was stirred for 1 hour at 90 to 95 ° C until the half ester formed was. For half ester then 2.6 parts of monoethanolamine were between 90 and 95 ° C given. Subsequently was allowed to react under nitrogen for 4 hours at 110 ° C with stirring.

The product obtained was then at 50 to 60 ° C with 2.6 parts of phosphorus pentoxide phosphated. The stirring time was 2 hours. The phosphoric acid ester was diluted with 10.0 parts hexylene glycol and 14.9 parts triethanolamine neutralized.

To To this mixture was added 5.0 parts of methacrylic acid. The copolymerization was introduced with 0.1 part of ammonium persulfate at 80 ° C. It was 1 hour at 80 ° C further polymerized. The polymer was mixed with 49.4 parts of water dilute and 1 more hour at 80 ° C held. The result was a clear, brown, clear water-soluble viscous product.

With the product thus obtained, chromium retanned leather was greased at 8%, based on shaved weight, and fixed for hydrophobing with 3% chromium tanning agent (26% Cr ₂ O ₃ , 1/3 basic). It was obtained a soft leather with a round, warm handle. In the Ballypenetrometertest found for the water passage time a value of over 24 hours, the water absorption after 24 hours was on average between 10 and 50%.

One retanned with 5% synthetic tanning agent and 5% vegetable tanning agent and 8% above copolymer greased leather, also was fixed with 3% chrome tanning agent was also very soft and pleasant to handle. In Ballypenetrometertest resulted in the water passage time a value of over 24 hours, the water absorption after 24 hours was on average between 10 and 50%.

Example 3: Production a copolymer of the invention

22 Portions of a 6 EO C16-C18 fatty alcohol were 4.2 parts maleic anhydride mixed at 80 ° C. The mixture was stirred for 1 hour at 90 to 95 ° C until the half ester formed was. For half ester then 2.6 parts of monoethanolamine were between 90 and 95 ° C given. Subsequently was reacted under nitrogen for 4 hours at 110 ° C with stirring.

The product obtained was then at 50 to 60 ° C with 2.6 parts of phosphorus pentoxide phosphated. The stirring time was 3 hours.

Of the phosphoric esters was diluted with 10.0 parts of hexylene glycol and with 14, 9 parts of triethanolamine neutralized.

To this mixture was added 5.0 parts of methacrylic acid. The copolymerization was 0.1 Parts of ammonium persulfate introduced at 80 ° C. It was further polymerized at 80 ° C for 1 hour. The polymer was diluted with 38.6 parts of water and kept at 80 ° C for an additional 1 hour. The result was a clear, brown, clear water-soluble, viscous product.

The resulting copolymer was tested in chrome tanning. For this purpose, the pickle liquor was adjusted to a pH of 3.2 to 3.4 with sodium bicarbonate. Subsequently, 8% (based on pickle weight) of a commercial chrome tanning agent (26% Cr ₂ O ₃ , 1/3 basic) was added. After 30 minutes, 2% (based on pickle weight) of the copolymer of the invention was added and agitated for 6 hours. The tanning took place overnight.

It could a wetblue with even color by even chromium distribution, good inner softness and extremely good hemmability. The finished leather from this Wetblue were very soft high grain tightness and high tear strength.

Claims (12)

Copolymer for the treatment of leather and fur skins, by polymerization of a carbon-carbon double bond having mono- or dicarboxylic acid having 3 to 10 carbon atoms with a compound available is, wherein the compound can be produced by that a) a fatty alcohol and / or a wax alcohol, optionally 4 to 20 units derived from ethylene oxide and / or propylene oxide having a carbon-carbon double bond dicarboxylic acid having 3 to 10 carbon atoms or an anhydride thereof, b) the product from step a) reacts with an alkanolamine and c) the product from step b) reacted with a phosphating agent becomes. A copolymer according to claim 1 wherein the monocarboxylic acid is present under methacrylic acid and acrylic acid selected is. A copolymer according to any one of claims 1 or 2, wherein the dicarboxylic acid is maleic acid. A copolymer according to any one of claims 1 to 3, wherein the fatty alcohol Oleyl alcohol is. A copolymer according to any one of claims 1 to 4, wherein the alkanolamine 2-aminoethanol. A copolymer according to any one of claims 1 to 5, wherein the phosphating agent Phosphorus pentoxide is. Process for the preparation of a copolymer according to one the claims 1 to 6, wherein a) the fatty alcohol and / or the wax alcohol, optionally 4 to 20 of ethylene oxide and / or propylene oxide having derived units with the carbon-carbon double bond having dicarboxylic acid having 3 to 10 carbon atoms or the anhydride thereof reacted b) the product from step a) reacts with the alkanolamine, c) the product from step b) is reacted with the phosphating agent, and d) the compound of step c) having a carbon-carbon double bond Mono- or dicarboxylic acid is copolymerized with 3 to 10 carbon atoms. The method of claim 7, wherein the carbon-carbon double bond having mono- or dicarboxylic acid, the Fatty alcohol, the wax alcohol, the alkanolamine and the phosphating agent in the claims 2 to 6 are indicated. The method of claim 7 or 8, wherein in step a) the fatty alcohol and / or the wax alcohol with the dicarboxylic acid or the anhydride thereof is reacted in an equimolar ratio. Method according to one of claims 7 to 9, wherein in step b) the product from step a) with the alkanolamine in an approximately equimolar ratio is implemented. Method according to one of claims 7 to 10, wherein in step d) the product of step c) having one carbon-carbon double bond having mono- or dicarboxylic acid in glycol as a solvent is implemented. Use of the copolymer according to any one of claims 1 to 6 for softening, lipidation and Hy dribbling of leather and fur skins.