EP0255013A2 - Primer layer for surface finishing - Google Patents
Primer layer for surface finishing Download PDFInfo
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- EP0255013A2 EP0255013A2 EP87110470A EP87110470A EP0255013A2 EP 0255013 A2 EP0255013 A2 EP 0255013A2 EP 87110470 A EP87110470 A EP 87110470A EP 87110470 A EP87110470 A EP 87110470A EP 0255013 A2 EP0255013 A2 EP 0255013A2
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- greased
- ether phosphates
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- primer
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
Definitions
- the invention relates to a method for improving the adhesion of dressings to greased and / or hydrophobized leathers and to the use of aqueous dispersions as a primer for improving the adhesion of dressings to greased and / or hydrophobic leathers.
- Leather finishing is the protective layer that is applied to the leather that has been dried after tanning and greasing in order to protect it against moisture, dirt and damage.
- An optimal dressing is required, among other things, that it adheres well to the leather.
- most dressing systems do not meet this requirement satisfactorily: For example, very good fastness values and flexibility can be achieved with dressings based on polyurethane, so that breaking of the dressing film is almost impossible; liability problems often arise here (see "The Leather” 25 , 167-171 (1974)).
- Another problem with hydrophobized leathers is that in many cases an improvement in the adhesion is associated with a deterioration in the hydrophobization.
- the object of the invention was therefore to develop a primer for improving the adhesion of dressings.
- aqueous dispersions containing A) short- and / or medium-chain alkyl ether phosphates and B) finely divided, soft, urea group-terminated, aliphatic anionic polyurethane dispersions, on greased and / or hydrophobized leathers provide a very good primer for the form subsequent dressing processes. Furthermore, it was found that the improvement in the adhesion of the finish is not associated with a negative influence on the hydrophobization in the case of leathers which have been rendered hydrophobic.
- the alkyl ether phosphates contained in the aqueous dispersions preferably have 2 to 12 carbon atoms in the branched and / or unbranched alkyl chains and 2 to 6 alkylene oxide units in the ether chains. Alkyl ether phosphates with 2 to 6 ethylene oxide and / or propylene oxide units in the ether chains are particularly preferred.
- alkyl ether phosphates are prepared in a manner known per se by phosphating alkoxylated, in particular ethoxylated and / or propoxylated, primary, secondary and / or tertiary, straight-chain and / or branched-chain, aliphatic alcohols having 2 to 12 carbon atoms.
- alkyl ether phosphates means - depending on the production conditions - mono-, di- and / or trialkyl ether phosphates.
- mono-, di- and / or trialkyl ether phosphates preferably mono- and / or dialkyl ether phosphates, are used.
- the fine-particle, soft, urea group-terminated, aliphatic, anionic polyurethane dispersions suitable for the process according to the invention are prepared in a manner known per se (see, for example, D. Dieterich in Angew. Makrom. Chem. 98 , 133 (1981) and the literature cited therein), for example, by reacting aliphatic polyisocyanates with substoichiometric amounts of polyols in a melt reaction under an inert gas atmosphere to give the corresponding prepolymers.
- the prepolymers are then mixed with a deficit of mono- and / or polybasic polyhydroxycarboxylic acids in the form of their alkali, amine and / or ammonium salts, dissolved in an inert solvent. After the reaction solution has been refluxed for about 1 to 3 hours, the solvent is removed in vacuo and the polyurethane composition is first dispersed in water and then in aqueous solutions containing amines and / or ammonia.
- Suitable aliphatic polyisocyanates are, in particular, cyclic and / or non-cyclic diisocyanates, for example 1,6-hexamethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate and / or 2-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate).
- the second component required to prepare the prepolymers, the polyols are preferably polyester and / or polyether diols known per se from polyurethane chemistry with at least 2 alcoholic hydroxyl groups and a molecular weight between about 400 and 3,000, preferably between about 800 and 2,000.
- Difunctional polypropylene glycols are preferably used.
- Suitable mono- and / or polybasic polyhydroxycarboxylic acids are, for example, dihydroxypropionic acid, dimethylolpropionic acid, dihydroxysuccinic acid and / or dihydroxybenzoic acid. 2,2-Dimethylolpropionic acid is preferably used.
- Acetone and / or N-methylpyrrolidone are particularly suitable as solvents for the above-mentioned polyhydroxycarboxylic acids, which are used in the form of their alkali metal, amine and / or ammonium salts.
- the adhesive base liquors of the process according to the invention preferably contain 2 to 20 parts by weight of water, particularly preferably 4 to 15 parts by weight of water, 1 part by weight of the polyurethane dispersion characterized above. It has been shown that, in order to improve the adhesion of dressings, there are advantages in particular in aqueous dispersions in which the weight ratio of components A: B is between about 2: 1 and about 1:10. Mixtures in which the weight ratio of components A: B is between about 1: 1 and about 1: 5 are particularly preferred.
- the adhesive base liquors, containing components A and B, are greased using the process according to the invention and / or water-repellent leather injected or cast, preferably sprayed.
- the alkyl ether phosphates in the aqueous dispersions to be used according to the invention preferably contain 2 to 12 carbon atoms in the branched and / or unbranched alkyl chains and 2 to 6 alkylene oxide units in the ether chains.
- Alkyl ether phosphates which have 2 to 6 ethylene oxide and / or propylene oxide units in the ether chains are particularly preferred.
- alkyl ether phosphates means - depending on the production conditions - mono-, di- and / or trialkyl ether phosphates.
- the finely divided, soft, urea group-terminated, aliphatic, anionic polyurethane dispersions containing the aqueous dispersions to be used according to the invention are prepared in a manner known per se (see, for example, D. Dieterich in Angew. Makrom. Chem. 98 , 133 (1981) and the literature cited therein ) produced, for example by aliphatic polyisocyanates and substoichiometric amounts of polyols in a melt reaction under an inert gas atmosphere, the corresponding prepolymers are formed.
- prepolymers are then mixed with a deficit of mono- and / or polybasic polyhydroxycarboxylic acids in the form of their alkali, amine and / or ammonium salts, dissolved in an inert solvent. After refluxing for about 1 to 3 hours, the solvent is removed in vacuo and the polyurethane composition is first dispersed in water and then in an aqueous solution which contains amines and / or ammonia.
- Suitable aliphatic polyisocyanates are, in particular, cyclic and / or noncyclic diisocyanates, for example 1,6-hexamethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate and / or 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate).
- the preferred polyols required for the preparation of the prepolymers are polyester and / or polyether diols known per se from polyurethane chemistry with at least 2 alcoholic hydroxyl groups and a molecular weight between approximately 400 and 3000, preferably between approximately 800 and 2000. Difunctional polypropylene glycols are particularly preferably used.
- Suitable mono- and / or polybasic polyhydroxycarboxylic acids are, for example, dihydroxypropionic acid, dimethylolpropionic acid, dihydroxysuccinic acid and / or dihydroxybenzoic acid. 2,2-Dimethylolpropionic acid is preferably used.
- Acetone and / or N-methylpyrrolidone are particularly suitable as solvents for the above-mentioned polyhydroxycarboxylic acids, which are used in the form of their alkali metal, amine and / or ammonium salts.
- the aqueous dispersions used as a primer for dressings on greased and / or hydrophobized leathers preferably contain 1 part by weight of the polyurethane dispersion characterized above in 2 to 20 parts by weight of water, particularly preferably in 4 to 15 parts by weight of water, wherein the weight ratio of components A: B is preferably between about 2: 1 and about 1:10.
- Aqueous dispersions in which the weight ratio of components A: B is between about 1: 1 and about 1: 5 are particularly preferably used.
- the adhesive base liquors used are sprayed or poured, preferably sprayed, onto greased and / or hydrophobized leather.
- the proportion of the polyurethane dispersion in the base liquor is between 1 and 50 parts by weight, preferably between 2 and 30 parts by weight, per 100 parts by weight of binder in the base liquor.
- the weight ratio of components A: B is preferably between about 2: 1 and about 1:10, particularly preferably between about 1: 1 and about 1: 5.
- Binder includes, for example, acrylate, acrylonitrile, polybutadiene and / or Understand polyurethane dispersions.
- aqueous dispersions according to the invention containing A) short- and / or medium-chain alkyl ether phosphates and B) fine-particle, soft, urea-group-terminated, aliphatic, anionic polyurethane dispersions form a very good primer for greased and / or hydrophobized leathers the subsequent dressing processes.
- the mixtures penetrate very deeply into the leather so that there are no sticking problems when ironing and stacking during the finishing processes.
- the process according to the invention or the use according to the invention of the aqueous dispersions characterized above in the case of hydrophobized leathers creates a very good primer without negatively influencing the hydrophobization.
- the mixture is cooled to about 70 ° C. and the reaction mixture in 59.0 parts by weight of water with very strong Dispersed stirring. Then the dispersion is mixed with 1.73 parts by weight of 12.5% NH3 / H2O solution and stirred at 50 ° C for about 1 hour.
- the polyurethane dispersion obtained has the following characteristics: Solids content: 39% by weight pH: 7.0 Particle diameter: 58 to 80 nm Film: clear, soft, very sticky.
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- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Verfahren von Verbesserung der Haftung von Zurichtungen auf gefetteten und/oder hydrophobierten Ledern, welches dadurch gekennzeichnet ist, daß gefettete und/oder hydrophobierte Leder vor und/oder in der Grundierung mit wäßrigen Dispersionen, enthaltend A) kurz- und/oder mittelkettige Alkyletherphosphate und B) feinteilige, weiche, harnstoffgruppenterminierte, aliphatische, anionische Polyurethan-Dispersionen behandelt werden.Process for improving the adhesion of dressings on greased and / or hydrophobized leathers, which is characterized in that greased and / or hydrophobized leathers before and / or in the primer with aqueous dispersions containing A) short- and / or medium-chain alkyl ether phosphates and B ) finely divided, soft, urea group-terminated, aliphatic, anionic polyurethane dispersions are treated.
Description
Die Erfindung betrifft ein Verfahren zur Verbesserung der Haftung von Zurichtungen auf gefetteten und/oder hydrophobierten Ledern sowie die Verwendung wäßriger Dispersionen als Haftgrund zur Verbesserung der Haftung von Zurichtungen auf gefetteten und/oder hydrophobierten Ledern.The invention relates to a method for improving the adhesion of dressings to greased and / or hydrophobized leathers and to the use of aqueous dispersions as a primer for improving the adhesion of dressings to greased and / or hydrophobic leathers.
Als Lederzurichtung wird die Schutzschicht bezeichnet, die auf das nach der Gerbung und Fettung getrocknete Leder aufgetragen wird, um es gegen Feuchtigkeit, Verschmutzung und Beschädigungen zu schützen. Von einer optimalen Zurichtung wird u.a. verlangt, daß sie auf dem Leder gut haftet. Diese Forderung wird jedoch von den meisten Zurichtsystemen nicht in zufriedenstellender Weise erfüllt: So können beispielsweise mit Zurichtungen auf Polyurethanbasis sehr gute Echtheitswerte und Flexibilitäten erreicht werden, so daß ein Brechen des Zurichtfilms nahezu unmöglich ist; hierbei treten aber häufig Haftungsprobleme auf (s. "Das Leder" 25, 167 - 171 (1974)). Bei hydrophobierten Ledern kommt als weitere Schwierigkeit hinzu, daß in vielen Fällen eine Verbesserung der Haftung mit einer Verschlechterung der Hydrophobierung verbunden ist.Leather finishing is the protective layer that is applied to the leather that has been dried after tanning and greasing in order to protect it against moisture, dirt and damage. An optimal dressing is required, among other things, that it adheres well to the leather. However, most dressing systems do not meet this requirement satisfactorily: For example, very good fastness values and flexibility can be achieved with dressings based on polyurethane, so that breaking of the dressing film is almost impossible; liability problems often arise here (see "The Leather" 25 , 167-171 (1974)). Another problem with hydrophobized leathers is that in many cases an improvement in the adhesion is associated with a deterioration in the hydrophobization.
Die in "Das Leder" 25, 185 - 190 (1974) beschriebenen schwach vernetzenden wäßrigen Polyurethandispersionen, die als Haftgrund für Zurichtungen verwendet werden können, genügen ebenfalls nicht den an sie gestellten Anforderungen in zufriedenstellender Weise.The weakly crosslinking aqueous polyurethane dispersions described in "Das Leder" 25 , 185-190 (1974), which can be used as a primer for dressings, likewise do not satisfactorily meet the requirements placed on them.
Die Aufgabe der Erfindung bestand daher in der Entwicklung eines Haftgrundes zur Verbesserung der Haftung von Zurichtungen.The object of the invention was therefore to develop a primer for improving the adhesion of dressings.
Es wurde nun die überraschende Feststellung gemacht, daß wäßrige Dispersionen, enthaltend A) kurz- und/oder mittelkettige Alkyletherphosphate und B) feinteilige, weiche, harnstoffgruppenterminierte, aliphatische anionische Polyurethan-Dispersionen, auf gefetteten und/oder hydrophobierten Ledern einen sehr guten Haftgrund für die nachfolgenden Zurichtprozeße bilden. Des weiteren wurde gefunden, daß bei hydrophobierten Ledern die Haftungsverbesserung der Zurichtung nicht mit einer negativen Beeinflussung der Hydrophobierung verbunden ist.It has now been made the surprising finding that aqueous dispersions containing A) short- and / or medium-chain alkyl ether phosphates and B) finely divided, soft, urea group-terminated, aliphatic anionic polyurethane dispersions, on greased and / or hydrophobized leathers, provide a very good primer for the form subsequent dressing processes. Furthermore, it was found that the improvement in the adhesion of the finish is not associated with a negative influence on the hydrophobization in the case of leathers which have been rendered hydrophobic.
Gegenstand der Erfindung ist demzufolge mit Verfahren zur Verbesserung der Haftung von Zurichtungen auf gefetteten und/oder hydrophobierten Ledern, das dadurch gekennzeichnet ist, daß gefettete und/oder hydrophobierte Leder vor und/oder in der Grundierung mit wäßrigen Dispersionen, enthaltend
- A) kurz- und/oder mittelkettige Alkyletherphosphate und
- B) feinteilige, weiche, harnstoffgruppenterminierte, aliphatische, anionische Polyurethan-Dispersionen
- A) short and / or medium chain alkyl ether phosphates and
- B) fine-particle, soft, urea group-terminated, aliphatic, anionic polyurethane dispersions
Vorzugsweise besitzen die in den wäßrigen Dispersionen enthaltenen Alkyletherphosphate 2 bis 12 Kohlenstoffatome in den verzweigten und/oder unverzweigten Alkylketten und 2 bis 6 Alkylenoxideinheiten in den Etherketten. Besonders bevorzugt werden Alkyletherphosphate mit 2 bis 6 Ethylenoxid- und/oder Propylenoxideinheiten in den Etherketten.The alkyl ether phosphates contained in the aqueous dispersions preferably have 2 to 12 carbon atoms in the branched and / or unbranched alkyl chains and 2 to 6 alkylene oxide units in the ether chains. Alkyl ether phosphates with 2 to 6 ethylene oxide and / or propylene oxide units in the ether chains are particularly preferred.
Die Alkyletherphosphate werden in an sich bekannter Weise durch Phosphatierung alkoxylierter, insbesondere ethoxylierter und/oder propoxylierter, primärer, sekundärer und/oder tertiärer, gerad- und/oder verzweigtkettiger, aliphatischer Alkohole mit 2 bis 12 Kohlenstoffatomen hergestellt.The alkyl ether phosphates are prepared in a manner known per se by phosphating alkoxylated, in particular ethoxylated and / or propoxylated, primary, secondary and / or tertiary, straight-chain and / or branched-chain, aliphatic alcohols having 2 to 12 carbon atoms.
Unter dem Begriff "Alkyletherphosphate" werden - in Abhängigkeit von den Herstellungsbedingungen - Mono-, Di- und/oder Trialkyletherphosphate verstanden. Im Rahmen der Erfindung werden Mono-, Di- und/oder Trialkyletherphosphate, vorzugsweise Mono- und/oder Dialkyletherphosphate eingesetzt.The term “alkyl ether phosphates” means - depending on the production conditions - mono-, di- and / or trialkyl ether phosphates. In the context of the invention, mono-, di- and / or trialkyl ether phosphates, preferably mono- and / or dialkyl ether phosphates, are used.
Die für das erfindungsgemäße Verfahren geeigneten feinteiligen, weichen, harnstoffgruppenterminierten, aliphatischen, anionischen Polyurethan-Dispersionen werden in an sich bekannter Weise (siehe z.B. D. Dieterich in Angew. Makrom. Chem. 98, 133 (1981) und dort zitierte Literatur) hergestellt, beispielsweise indem aliphatische Polyisocyanate mit unterstöchiometrischen Mengen an Polyolen in einer Schmelzreaktion unter Inertgasatmosphäre zu den entsprechenden Prepolymeren umgesetzt werden. Anschließend werden die Prepolymeren mit einem Unterschuß an ein- und/oder mehrbasischen Polyhydroxycarbonsäuren in Form ihrer Alkali-, Amin- und/oder Ammoniumsalzen, gelöst in einem inerten Lösungsmittel, versetzt. Nachdem die Reaktionslösung etwa 1 bis 3 Stunden unter Rückfluß gekocht wurde, wird das Lösungsmittel im Vakuum entfernt und die Polyurethanmasse zuerst in Wasser und anschließend in wäßrigen Lösungen, enthaltend Amine und/oder Ammoniak, dispergiert.The fine-particle, soft, urea group-terminated, aliphatic, anionic polyurethane dispersions suitable for the process according to the invention are prepared in a manner known per se (see, for example, D. Dieterich in Angew. Makrom. Chem. 98 , 133 (1981) and the literature cited therein), for example, by reacting aliphatic polyisocyanates with substoichiometric amounts of polyols in a melt reaction under an inert gas atmosphere to give the corresponding prepolymers. The prepolymers are then mixed with a deficit of mono- and / or polybasic polyhydroxycarboxylic acids in the form of their alkali, amine and / or ammonium salts, dissolved in an inert solvent. After the reaction solution has been refluxed for about 1 to 3 hours, the solvent is removed in vacuo and the polyurethane composition is first dispersed in water and then in aqueous solutions containing amines and / or ammonia.
Als aliphatische Polyisocyanate eignen sich insbesondere cyclische und/oder nichtcyclische Diisocyanate, beispielsweise 1,6-Hexamethylendiisocyanat, Trimethyl-1,6-hexamethylendiisocyanat und/oder 2-Isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanat (Isophorondiisocyanat).Suitable aliphatic polyisocyanates are, in particular, cyclic and / or non-cyclic diisocyanates, for example 1,6-hexamethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate and / or 2-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate).
Die zur Herstellung der Prepolymeren benötigte zweite Komponente, die Polyole, sind vorzugsweise, aus der Polyurethan-Chemie an sich bekannte Polyester- und/oder Polyetherdiole mit mindestens 2 alkoholischen Hydroxylgruppen und einem Molekulargewicht zwischen etwa 400 und 3.000, vorzugsweise zwischen etwa 800 und 2.000. Vorzugsweise werden difunktionelle Polypropylenglycole eingesetzt.The second component required to prepare the prepolymers, the polyols, are preferably polyester and / or polyether diols known per se from polyurethane chemistry with at least 2 alcoholic hydroxyl groups and a molecular weight between about 400 and 3,000, preferably between about 800 and 2,000. Difunctional polypropylene glycols are preferably used.
Geeignete ein- und/oder mehrbasische Polyhydroxycarbonsäuren sind beispielsweise Dihydroxypropionsäure, Dimethylolpropionsäure, Dihydroxybernsteinsäure und/oder Dihydroxybenzoesäure. Vorzugsweise kommt 2,2-Dimethylolpropionsäure zum Einsatz.Suitable mono- and / or polybasic polyhydroxycarboxylic acids are, for example, dihydroxypropionic acid, dimethylolpropionic acid, dihydroxysuccinic acid and / or dihydroxybenzoic acid. 2,2-Dimethylolpropionic acid is preferably used.
Als Lösungsmittel für die oben erwähnten Polyhydroxycarbonsäuren, die in Form ihrer Alkali-, Amin- und/oder Ammoniumsalze eingesetzt werden, eignen sich insbesondere Aceton und/oder N-Methylpyrrolidon.Acetone and / or N-methylpyrrolidone are particularly suitable as solvents for the above-mentioned polyhydroxycarboxylic acids, which are used in the form of their alkali metal, amine and / or ammonium salts.
Die Haftgrundflotten des erfindungsgemäßen Verfahrens enthalten vorzugsweise auf 2 - 20 Gew.-Teile Wasser, besonders bevorzugt auf 4 - 15 Gew.-Teile Wasser 1 Gew.-Teil der oben charakterisierten Polyurethandispersion. Es hat sich gezeigt, daß zur Verbesserung der Haftung von Zurichtungen insbesondere solche wäßrigen Dispersionen Vorteile bringen, in denen das Gewichtsverhältnis der Komponenten A : B zwischen etwa 2 : 1 und etwa 1 : 10 liegt. Besonders bevorzugt werden Mischungen, in denen das Gewichtsverhältnis der Komponenten A : B zwischen etwa 1 : 1 und etwa 1 : 5 liegt.The adhesive base liquors of the process according to the invention preferably contain 2 to 20 parts by weight of water, particularly preferably 4 to 15 parts by weight of water, 1 part by weight of the polyurethane dispersion characterized above. It has been shown that, in order to improve the adhesion of dressings, there are advantages in particular in aqueous dispersions in which the weight ratio of components A: B is between about 2: 1 and about 1:10. Mixtures in which the weight ratio of components A: B is between about 1: 1 and about 1: 5 are particularly preferred.
Die Haftgrundflotten, enthaltend die Komponenten A und B, werden nach dem erfindungsgemäßen Verfahren auf gefettete und/oder hydrophobierte Leder gespritzt oder gegossen, vorzugsweise gespritzt.The adhesive base liquors, containing components A and B, are greased using the process according to the invention and / or water-repellent leather injected or cast, preferably sprayed.
Gegenstand der Erfindung ist ferner die Verwendung wäßriger Dispersionen, enthaltend
- A) kurz- und/oder mittelkettige Alkyletherphosphate und
- B) feinteilige, weiche, harnstoffgruppenterminierte, aliphatische, anionische Polyurethan-Dispersionen
- A) short and / or medium chain alkyl ether phosphates and
- B) fine-particle, soft, urea group-terminated, aliphatic, anionic polyurethane dispersions
Die Alkyletherphosphate in den erfindungsgemäß zu verwendenden wäßrigen Dispersionen enthalten vorzugsweise 2 bis 12 Kohlenstoffatome in den verzweigten und/oder unverzweigten Alkylketten und 2 bis 6 Alkylenoxideinheiten in den Etherketten. Besonders bevorzugt werden Alkyletherphosphate, die 2 bis 6 Ethylenoxid- und/oder Propylenoxideinheiten in den Etherketten besitzen.The alkyl ether phosphates in the aqueous dispersions to be used according to the invention preferably contain 2 to 12 carbon atoms in the branched and / or unbranched alkyl chains and 2 to 6 alkylene oxide units in the ether chains. Alkyl ether phosphates which have 2 to 6 ethylene oxide and / or propylene oxide units in the ether chains are particularly preferred.
Unter dem Begriff "Alkyletherphosphate" werden - in Abhängigkeit von den Herstellungsbedingungen - Mono-, Di- und/oder Trialkyletherphosphate verstanden. Im Rahmen der Erfindung werden Mono-, Di- und/oder Trialkyletherphosphate, vorzugsweise Mono- und/oder Dialkyletherphosphate verwendet.The term “alkyl ether phosphates” means - depending on the production conditions - mono-, di- and / or trialkyl ether phosphates. Mono-, di- and / or trialkyl ether phosphates, preferably mono- and / or dialkyl ether phosphates, are used in the context of the invention.
Die in den erfindungsgemäß zu verwendenden wäßrigen Dispersionen enthaltenden feinteiligen, weichen, harnstoffgruppenterminierten, aliphatischen, anionischen Polyurethan-Dispersionen werden in an sich bekannter Weise (siehe z.B. D. Dieterich in Angew. Makrom. Chem. 98, 133 (1981) und dort zitierte Literatur) hergestellt, beispielsweise indem aus aliphatischen Polyisocyanaten und unterstöchiometrischen Mengen an Polyolen in einer Schmelzreaktion unter Inertgasatmosphäre die entsprechenden Prepolymeren gebildet werden. Anschließend werden diese Prepolymeren mit einem Unterschuß an ein- und/oder mehrbasischen Polyhydroxycarbonsäuren in Form ihrer Alkali-, Amin- und/oder Ammoniumsalze, gelöst in einem inerten Lösungsmittel, versetzt. Nach etwa 1- bis 3-stündigem Rückflußkochen wird das Lösungsmittel im Vakuum entfernt und die Polyurethanmasse zuerst in Wasser und anschließend in einer wäßrigen Lösung, die Amine und/oder Ammoniak enthält, dispergiert.The finely divided, soft, urea group-terminated, aliphatic, anionic polyurethane dispersions containing the aqueous dispersions to be used according to the invention are prepared in a manner known per se (see, for example, D. Dieterich in Angew. Makrom. Chem. 98 , 133 (1981) and the literature cited therein ) produced, for example by aliphatic polyisocyanates and substoichiometric amounts of polyols in a melt reaction under an inert gas atmosphere, the corresponding prepolymers are formed. These prepolymers are then mixed with a deficit of mono- and / or polybasic polyhydroxycarboxylic acids in the form of their alkali, amine and / or ammonium salts, dissolved in an inert solvent. After refluxing for about 1 to 3 hours, the solvent is removed in vacuo and the polyurethane composition is first dispersed in water and then in an aqueous solution which contains amines and / or ammonia.
Als aliphatische Polyisocyanate eignen sich insbesondere cyclische und/oder nichtcyclische Diisocyanate, beispielsweise 1,6-Hexamethylendiisocyanat, Trimethyl-1,6-hexamethylendiisocyanat und/oder 3-Isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanat (Isophorondiisocyanat).Suitable aliphatic polyisocyanates are, in particular, cyclic and / or noncyclic diisocyanates, for example 1,6-hexamethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate and / or 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate).
Die zur Herstellung der Prepolymeren benötigten bevorzugten Polyole sind aus der Polyurethan-Chemie an sich bekannte Polyester-und/oder Polyetherdiole mit mindestens 2 alkoholischen Hydroxylgruppen und einem Molekulargewicht zwischen etwa 400 und 3.000, vorzugsweise zwischen etwa 800 und 2.000. Besonders bevorzugt werden difunktionelle Polypropylenglycole verwendet.The preferred polyols required for the preparation of the prepolymers are polyester and / or polyether diols known per se from polyurethane chemistry with at least 2 alcoholic hydroxyl groups and a molecular weight between approximately 400 and 3000, preferably between approximately 800 and 2000. Difunctional polypropylene glycols are particularly preferably used.
Geeignete ein- und/oder mehrbasische Polyhydroxycarbonsäuren sind beispielsweise Dihydroxypropionsäure, Dimethylolpropionsäure, Dihydroxybernsteinsäure und/oder Dihydroxybenzoesäure. Vorzugsweise kommt 2,2-Dimethylolpropionsäure zum Einsatz.Suitable mono- and / or polybasic polyhydroxycarboxylic acids are, for example, dihydroxypropionic acid, dimethylolpropionic acid, dihydroxysuccinic acid and / or dihydroxybenzoic acid. 2,2-Dimethylolpropionic acid is preferably used.
Als Lösungsmittel für die oben erwähnten Polyhydroxycarbonsäuren, die in Form ihrer Alkali-, Amin- und/oder Ammoniumsalze eingesetzt werden, eignen sich insbesondere Aceton und/oder N-Methylpyrrolidon.Acetone and / or N-methylpyrrolidone are particularly suitable as solvents for the above-mentioned polyhydroxycarboxylic acids, which are used in the form of their alkali metal, amine and / or ammonium salts.
Die als Haftgrund für Zurichtungen auf gefetteten und/oder hydrophobierten Ledern verwendeten wäßrigen Dispersionen enthalten vorzugsweise auf 2 - 20 Gew.-Teile Wasser, besonders bevorzugt auf 4 - 15 Gew.-Teile Wasser 1 Gew.-Teil der oben charakterisierten Polyurethan-Dispersion, wobei das Gewichtsverhältnis der Komponenten A : B vorzugsweise zwischen etwa 2 : 1 und etwa 1 : 10 liegt. Besonders bevorzugt werden wäßrige Dispersionen verwendet, in denen das Gewichtsverhältnis der Komponenten A : B zwischen etwa 1 : 1 und etwa 1 : 5 liegt.The aqueous dispersions used as a primer for dressings on greased and / or hydrophobized leathers preferably contain 1 part by weight of the polyurethane dispersion characterized above in 2 to 20 parts by weight of water, particularly preferably in 4 to 15 parts by weight of water, wherein the weight ratio of components A: B is preferably between about 2: 1 and about 1:10. Aqueous dispersions in which the weight ratio of components A: B is between about 1: 1 and about 1: 5 are particularly preferably used.
Die verwendeten Haftgrundflotten werden auf gefettete und/oder hydrophobierte Leder gespritzt oder gegossen, vorzugsweise gespritzt.The adhesive base liquors used are sprayed or poured, preferably sprayed, onto greased and / or hydrophobized leather.
Um eine Verbesserung der Haftung von Zurichtungen zu erzielen, ist es in manchen Fällen auch möglich, nur einen Teil der Haftgrundflotte auf das gefettete und/oder hydrophobierte Leder zu spritzen oder zu gießen, vorzugsweise zu spritzen und den anderen Teil in der Grundierflotte einzusetzen. In diesen Fällen liegt der Anteil der Polyurethan-Dispersion in der Grundierflotte zwischen 1 und 50 Gew.-Teilen, vorzugsweise zwischen 2 und 30 Gew.-Teilen auf 100 Gew.-Teile Binder der Grundierflotte. Das Gewichtsverhältnis der Komponenten A : B liegt vorzugsweise zwischen etwa 2 : 1 und etwa 1 : 10, besonders bevorzugt zwischen etwa 1 : 1 und etwa 1 : 5. Unter "Binder" sind beispielsweise Acrylat-, Acrylnitril-, Polybutadien- und/oder Polyurethan-Dispersionen zu verstehen.In order to improve the adhesion of dressings, it is in some cases also possible to spray or pour, preferably by spraying, only part of the base adhesive liquor onto the greased and / or hydrophobized leather and to use the other part in the base liquor. In these cases, the proportion of the polyurethane dispersion in the base liquor is between 1 and 50 parts by weight, preferably between 2 and 30 parts by weight, per 100 parts by weight of binder in the base liquor. The weight ratio of components A: B is preferably between about 2: 1 and about 1:10, particularly preferably between about 1: 1 and about 1: 5. "Binder" includes, for example, acrylate, acrylonitrile, polybutadiene and / or Understand polyurethane dispersions.
Die erfindungsgemäßen wäßrigen Dispersionen enthaltend A) kurz- und/oder mittelkettige Alkyletherphosphate und B) feinteilige, weiche, harnstoffgruppenterminierte, aliphatische, anionische Polyurethan-Dispersionen, bilden auf gefetteten und/oder hydrophobierten Ledern einen sehr guten Haftgrund für die anschließenden Zurichtprozesse. Die Mischungen dringen sehr tief in das Leder ein, so daß keine Klebeprobleme beim Bügeln und Stapeln während der Zurichtprozesse auftreten. Weiterhin wird durch das erfindungsgemäße Verfahren bzw. durch die erfindungsgemäße Verwendung der oben charakterisierten wäßrigen Dispersionen bei hydrophobierten Ledern ein sehr guter Haftgrund ohne negative Beeinflussung der Hydrophobierung geschaffen.The aqueous dispersions according to the invention containing A) short- and / or medium-chain alkyl ether phosphates and B) fine-particle, soft, urea-group-terminated, aliphatic, anionic polyurethane dispersions form a very good primer for greased and / or hydrophobized leathers the subsequent dressing processes. The mixtures penetrate very deeply into the leather so that there are no sticking problems when ironing and stacking during the finishing processes. Furthermore, the process according to the invention or the use according to the invention of the aqueous dispersions characterized above in the case of hydrophobized leathers creates a very good primer without negatively influencing the hydrophobization.
Bei Raumtemperatur werden 26,3 Gew.-Teile Polypropylenglycol mit einem Molekulargewicht von etwa 1000 und 8,95 Gew.-Teile 1,6-Hexamethylendiisocyanat in einer Rührapparatur gemischt und unter Stickstoff etwa 6 Stunden bei 100 °C gerührt. Das erhaltene lagerfähige Isocyanat-prepolymer wird auf etwa 50 °C abgekühlt und bei dieser Temperatur mit einer frisch hergestellten Lösung von 1,77 Gew.-Teilen 2,2-Dimethylolpropionsäure und 1,33 Gew.-Teilen Triethylamin in 9,42 Gew.-Teilen Aceton versetzt. Das Reaktionsgemisch wird bei etwa 100 °C 1,5 Stunden unter Rückfluß gekocht. Nachdem anschließend innerhalb von etwa 10 bis 15 Minuten im Vakuum bei 100 °C etwa 8,5 Gew.-Teile Aceton entfernt worden sind, wird auf etwa 70 °C abgekühlt und die Reaktionsmischung in 59,0 Gew.-Teilen Wasser unter sehr starkem Rühren dispergiert. Danach wird die Dispersion mit 1,73 Gew.-Teilen 12,5 %ige NH₃/H₂O-Lösung versetzt und etwa 1 Stunde bei 50 °C gerührt.At room temperature, 26.3 parts by weight of polypropylene glycol with a molecular weight of about 1000 and 8.95 parts by weight of 1,6-hexamethylene diisocyanate are mixed in a stirrer and stirred under nitrogen at 100 ° C. for about 6 hours. The storable isocyanate prepolymer obtained is cooled to about 50 ° C. and at this temperature with a freshly prepared solution of 1.77 parts by weight of 2,2-dimethylolpropionic acid and 1.33 parts by weight of triethylamine in 9.42 parts by weight. Parts of acetone are added. The reaction mixture is refluxed at about 100 ° C for 1.5 hours. After approximately 8.5 parts by weight of acetone have subsequently been removed in vacuo at 100 ° C. in the course of about 10 to 15 minutes, the mixture is cooled to about 70 ° C. and the reaction mixture in 59.0 parts by weight of water with very strong Dispersed stirring. Then the dispersion is mixed with 1.73 parts by weight of 12.5% NH₃ / H₂O solution and stirred at 50 ° C for about 1 hour.
Die erhaltene Polyurethan-Dispersion besitzt folgende Kenndaten:
Feststoffgehalt: 39 Gew.-%
pH-Wert: 7,0
Partikeldurchmesser: 58 bis 80 nm
Film: klar, weich, stark klebrig.The polyurethane dispersion obtained has the following characteristics:
Solids content: 39% by weight
pH: 7.0
Particle diameter: 58 to 80 nm
Film: clear, soft, very sticky.
Die Haftprüfungen wurden nach IUF 470 durchgeführt.
wie Beispiel 1,
jedoch ohne Haftgrund und ohne Polyurethan-Dispersion 1 in der Grundierung.like example 1,
however without primer and without polyurethane dispersion 1 in the primer.
Haftprüfung ergibt folgende Werte:
Beispiel 1: 2,4 N/cm
Beispiel 2: 1,3 N/cm
Example 1: 2.4 N / cm
Example 2: 1.3 N / cm
wie Beispiel 3,
jedoch ohne Haftgrund und ohne Polyurethan-Dispersion 1 in der Grundierung.like example 3,
however without primer and without polyurethane dispersion 1 in the primer.
Haftungsprüfung ergibt folgende Werte:
Beispiel 3: 4,0 N/cm
Beispiel 4: 1,8 N/cm
Example 3: 4.0 N / cm
Example 4: 1.8 N / cm
wie Beispiel 5,
jedoch ohne Haftgrund.like example 5,
but without a reason for detention.
Haftungsprüfung ergibt folgende Werte:
Beispiel 5: 3,4 N/cm
Beispiel 6: 2,1 N/cm Liability check gives the following values:
Example 5: 3.4 N / cm
Example 6: 2.1 N / cm
Claims (5)
A) kurz- und/oder mittelkettige Alkyletherphosphate und
B) feinteilige, weiche, harnstoffgruppenterminierte, aliphatische, anionische Polyurethan-Dispersionen
behandelt werden.1. A method for improving the adhesion of dressings on greased and / or hydrophobized leathers, characterized in that greased and / or hydrophobized leathers containing before and / or in the primer with aqueous dispersions
A) short and / or medium chain alkyl ether phosphates and
B) fine-particle, soft, urea group-terminated, aliphatic, anionic polyurethane dispersions
be treated.
A) kurz- und/oder mittelkettige Alkyletherphosphate und
B) feinteilige, weiche, harnstoffgruppenterminierte, aliphatische, anionische Polyurethan-Dispersionen
als Haftgrund für Zurichtungen von gefetteten und/oder hydrophobierten Ledern.5. Use of aqueous dispersions containing
A) short and / or medium chain alkyl ether phosphates and
B) fine-particle, soft, urea group-terminated, aliphatic, anionic polyurethane dispersions
as a primer for dressing greased and / or water-repellent leathers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3625442A DE3625442C1 (en) | 1986-07-28 | 1986-07-28 | Adhesion base for dressings |
| DE3625442 | 1986-07-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0255013A2 true EP0255013A2 (en) | 1988-02-03 |
| EP0255013A3 EP0255013A3 (en) | 1989-08-09 |
Family
ID=6306114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87110470A Withdrawn EP0255013A3 (en) | 1986-07-28 | 1987-07-20 | Primer layer for surface finishing |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4772289A (en) |
| EP (1) | EP0255013A3 (en) |
| BR (1) | BR8703866A (en) |
| DE (1) | DE3625442C1 (en) |
| IN (1) | IN169304B (en) |
| TR (1) | TR23351A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3922493A1 (en) * | 1989-07-08 | 1991-01-17 | Bayer Ag | PROCESS FOR PREPARING WAESSEN DISPERSIONS OF POLYURETHANES AND THEIR USE AS COATING AGENTS FOR ANY SUBSTRATE |
| DE4003422A1 (en) * | 1990-02-06 | 1991-08-08 | Basf Ag | WAITER POLYURETHANE PREPARATIONS |
| US5770264A (en) * | 1992-07-31 | 1998-06-23 | Bayer Aktiengesellschaft | Anionically modified polyurethane ureas having reduced tackiness for the coating of leather |
| US6875212B2 (en) | 2000-06-23 | 2005-04-05 | Vertelink Corporation | Curable media for implantable medical device |
| US6964667B2 (en) | 2000-06-23 | 2005-11-15 | Sdgi Holdings, Inc. | Formed in place fixation system with thermal acceleration |
| US6899713B2 (en) | 2000-06-23 | 2005-05-31 | Vertelink Corporation | Formable orthopedic fixation system |
| WO2002000126A1 (en) | 2000-06-23 | 2002-01-03 | University Of Southern California | Percutaneous vertebral fusion system |
| US7771476B2 (en) | 2006-12-21 | 2010-08-10 | Warsaw Orthopedic Inc. | Curable orthopedic implant devices configured to harden after placement in vivo by application of a cure-initiating energy before insertion |
| US8663328B2 (en) | 2006-12-21 | 2014-03-04 | Warsaw Orthopedic, Inc. | Methods for positioning a load-bearing component of an orthopedic implant device by inserting a malleable device that hardens in vivo |
| US8758407B2 (en) | 2006-12-21 | 2014-06-24 | Warsaw Orthopedic, Inc. | Methods for positioning a load-bearing orthopedic implant device in vivo |
| US8480718B2 (en) | 2006-12-21 | 2013-07-09 | Warsaw Orthopedic, Inc. | Curable orthopedic implant devices configured to be hardened after placement in vivo |
| CN110565389B (en) * | 2019-09-05 | 2022-02-22 | 兴业皮革科技股份有限公司 | Coating method for improving water washing resistance and cold bending resistance of leather coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2246928A1 (en) * | 1973-10-05 | 1975-05-02 | Basf Ag | |
| FR2247484A1 (en) * | 1973-10-12 | 1975-05-09 | Rhone Progil |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4018559A (en) * | 1974-06-14 | 1977-04-19 | Diamond Shamrock Corporation | Non-rewet leather and method of producing same |
| US3941733A (en) * | 1975-01-02 | 1976-03-02 | Minnesota Mining And Manufacturing Company | Silanol-containing urethane dispersions |
-
1986
- 1986-07-28 DE DE3625442A patent/DE3625442C1/en not_active Expired
-
1987
- 1987-03-17 IN IN185/MAS/87A patent/IN169304B/en unknown
- 1987-07-03 TR TR464/87A patent/TR23351A/en unknown
- 1987-07-20 EP EP87110470A patent/EP0255013A3/en not_active Withdrawn
- 1987-07-27 BR BR8703866A patent/BR8703866A/en unknown
- 1987-07-28 US US07/078,499 patent/US4772289A/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2246928A1 (en) * | 1973-10-05 | 1975-05-02 | Basf Ag | |
| FR2247484A1 (en) * | 1973-10-12 | 1975-05-09 | Rhone Progil |
Also Published As
| Publication number | Publication date |
|---|---|
| BR8703866A (en) | 1988-03-29 |
| US4772289A (en) | 1988-09-20 |
| DE3625442C1 (en) | 1987-11-05 |
| EP0255013A3 (en) | 1989-08-09 |
| IN169304B (en) | 1991-09-28 |
| TR23351A (en) | 1989-12-19 |
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