CA2101389A1 - Anionically modified polyurethane ureas having reduced tackiness for the coating of leather - Google Patents
Anionically modified polyurethane ureas having reduced tackiness for the coating of leatherInfo
- Publication number
- CA2101389A1 CA2101389A1 CA002101389A CA2101389A CA2101389A1 CA 2101389 A1 CA2101389 A1 CA 2101389A1 CA 002101389 A CA002101389 A CA 002101389A CA 2101389 A CA2101389 A CA 2101389A CA 2101389 A1 CA2101389 A1 CA 2101389A1
- Authority
- CA
- Canada
- Prior art keywords
- groups
- urea
- polyurethane urea
- isocyanate
- mmol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
ANIONICALLY MODIFIED POLYURETHANE UREAS HAVING
REDUCED TACKINESS FOR THE COATING OF LEATHER
ABSTRACT OF THE DISCLOSURE
This invention relates to anionically modified polyurethane ureas having a low urethane group content and a low urea group content that are prepared by the reaction of (A) aromatic diisocyanates, (B) polyether polyols having an average molecular weight greater than 1500, (C) at least one compound containing 1 to 2 isocyanate-reactive groups and at least one ionic group, (D) polyamines having an average molecular weight of at least 32, and (E) water, the average total functionality of the isocyanate-reactive compounds B to D being greater than 1.85, wherein the polyurethane ureas have from 800 to 1500 mmol urethane groups and from 800 to 1800 mmol urethane plus urea groups per kg of anionically modified polyurethane urea.
This invention further relates to the use of such anionically modified polyurethane ureas as adhesion promoters for leather.
REDUCED TACKINESS FOR THE COATING OF LEATHER
ABSTRACT OF THE DISCLOSURE
This invention relates to anionically modified polyurethane ureas having a low urethane group content and a low urea group content that are prepared by the reaction of (A) aromatic diisocyanates, (B) polyether polyols having an average molecular weight greater than 1500, (C) at least one compound containing 1 to 2 isocyanate-reactive groups and at least one ionic group, (D) polyamines having an average molecular weight of at least 32, and (E) water, the average total functionality of the isocyanate-reactive compounds B to D being greater than 1.85, wherein the polyurethane ureas have from 800 to 1500 mmol urethane groups and from 800 to 1800 mmol urethane plus urea groups per kg of anionically modified polyurethane urea.
This invention further relates to the use of such anionically modified polyurethane ureas as adhesion promoters for leather.
Description
2ln~3~9 Mo3921 LeA 29,228 ANIONlCALEY MODIFIED POLYURETHANE UREAS HAVING
REDUCED TACKINESS FOR THE COATING QF LEATHER
This invention relates to anionically modified poly-urethane ureas having low urethane and urea group content and to their use for the coating of leather.
For the practical application of f;nished leather, it is crucially important that the applied finishes adhere firmly to the substrate because otherwise the required physical fastness lo values cannot be achieved. Establishing the required adhesion level is particularly problematical for highly oiled and/or phobicized substrates because the oiling and phobicizing agents generally act as release agents for the finishes. Accordingly, it is standard practice to use a special adhesion promoter either as a special coating or in admixture with other base coat binders, particularly in the finishing of leathers of the type in question. Aqueous dispersions of polyether urethanes have been successfully used as adhesion promoters; German Offenlegungsschriften 2,551,094 and 2,730,514 and European Patent Applications 255,013 and 441,196.
Known polyether urethanes, particularly flexible types, have a certain tackiness. On the one hand, this tackiness is desirable because it improves adhesion but, on the other hand, tackiness is disadvantageous in terms of processing because it adversely affects the stackability of the leathers thus coated.
However, flexible formulations are absolutely essential for use as an adhesion promoter because rigid products ~n the adhes~on promoter adversely affect the phys~cal properties, appearance, and comfort of the finished leathers. The use of external plasticizers (European Patent Application 255,013, which is believed to correspond to German Offenlegungsschrift 3,625,442) is undesirable because migration effects cannot be ruled out.
German Offenlegungsschrift 4,003,442 (believed to correspond to European Patent Application 441,196) describes 2~01389 polyether urethane ureas in which the desired flexibility is achieved by using an NCO:(OH+NH) molar ratio of 0.9 to I in the production process. Not only the molecular weight and the hardness, but also the strength of these products are limited.
However, a decreased hardness by this method is disadvantageous, since the strength of the polymer is reduced and its tackiness is increased. However, its optimum fastness values can only be obtained with polymers of maximum strength (Das Leder. 25. 185-190 (1974)).
U.S. Patent No. 4,895,894 discloses aliphatic polyether urethane ureas with low contents of urethane and urea groups.
The products are branched or crosslinked and have high moduli, but excessively high Shore A hardness (in the Examples: Shore A
hardness of at least 58). Crosslinked polyurethanes cannot be transferred into the organic phase, and therefore when used as base coat binders for leather, their degree of penetration cannot be regulated in the customary manner by the addition of organic co-solvents.
Optimum polyurethane ureas for the required use have relatiYely high strength combined with a low degree of hardness and minimum tackiness and produce very good adhesion to oiled and/or phobicized leathers.
Polyurethane ureas which, despite good adhesion, are flexible and tack-free but still show high strength, are desirable for the application in question.
Although one skilled in the art might normally expect low urethane and/or urea group content to give flexible products, they also give rise to an increase in tackiness and to a reduction in strength at the same time. This applies particularly when using aromatic diisocyanates.
It has now been found that polyurethane ureas of high strength, low tackiness, and excellent adhesion to oiled and/or phobicized leathers can be obtained when polyurethane ureas prepared from aromatic diisocyanates and having a low content of urethane and urea groups are used.
Mo3921 r~
~".' ' : ' : '~ ' ' : ,, ', :' ', . ` . : :
~,' ~ , '' : :
.
REDUCED TACKINESS FOR THE COATING QF LEATHER
This invention relates to anionically modified poly-urethane ureas having low urethane and urea group content and to their use for the coating of leather.
For the practical application of f;nished leather, it is crucially important that the applied finishes adhere firmly to the substrate because otherwise the required physical fastness lo values cannot be achieved. Establishing the required adhesion level is particularly problematical for highly oiled and/or phobicized substrates because the oiling and phobicizing agents generally act as release agents for the finishes. Accordingly, it is standard practice to use a special adhesion promoter either as a special coating or in admixture with other base coat binders, particularly in the finishing of leathers of the type in question. Aqueous dispersions of polyether urethanes have been successfully used as adhesion promoters; German Offenlegungsschriften 2,551,094 and 2,730,514 and European Patent Applications 255,013 and 441,196.
Known polyether urethanes, particularly flexible types, have a certain tackiness. On the one hand, this tackiness is desirable because it improves adhesion but, on the other hand, tackiness is disadvantageous in terms of processing because it adversely affects the stackability of the leathers thus coated.
However, flexible formulations are absolutely essential for use as an adhesion promoter because rigid products ~n the adhes~on promoter adversely affect the phys~cal properties, appearance, and comfort of the finished leathers. The use of external plasticizers (European Patent Application 255,013, which is believed to correspond to German Offenlegungsschrift 3,625,442) is undesirable because migration effects cannot be ruled out.
German Offenlegungsschrift 4,003,442 (believed to correspond to European Patent Application 441,196) describes 2~01389 polyether urethane ureas in which the desired flexibility is achieved by using an NCO:(OH+NH) molar ratio of 0.9 to I in the production process. Not only the molecular weight and the hardness, but also the strength of these products are limited.
However, a decreased hardness by this method is disadvantageous, since the strength of the polymer is reduced and its tackiness is increased. However, its optimum fastness values can only be obtained with polymers of maximum strength (Das Leder. 25. 185-190 (1974)).
U.S. Patent No. 4,895,894 discloses aliphatic polyether urethane ureas with low contents of urethane and urea groups.
The products are branched or crosslinked and have high moduli, but excessively high Shore A hardness (in the Examples: Shore A
hardness of at least 58). Crosslinked polyurethanes cannot be transferred into the organic phase, and therefore when used as base coat binders for leather, their degree of penetration cannot be regulated in the customary manner by the addition of organic co-solvents.
Optimum polyurethane ureas for the required use have relatiYely high strength combined with a low degree of hardness and minimum tackiness and produce very good adhesion to oiled and/or phobicized leathers.
Polyurethane ureas which, despite good adhesion, are flexible and tack-free but still show high strength, are desirable for the application in question.
Although one skilled in the art might normally expect low urethane and/or urea group content to give flexible products, they also give rise to an increase in tackiness and to a reduction in strength at the same time. This applies particularly when using aromatic diisocyanates.
It has now been found that polyurethane ureas of high strength, low tackiness, and excellent adhesion to oiled and/or phobicized leathers can be obtained when polyurethane ureas prepared from aromatic diisocyanates and having a low content of urethane and urea groups are used.
Mo3921 r~
~".' ' : ' : '~ ' ' : ,, ', :' ', . ` . : :
~,' ~ , '' : :
.
3 8 ~
SUMMARY OF THE INVENTION
Accordingly, the present invention relates to anionically modif;ed polyurethane ureas prepared by the reaction of (A) diisocyanates, (B) polyether polyols having an average molecular weight greater than 1500 (preferably in the range of 1800 to 3000), (C) at least one compound containing 1 to 2 isocyanate-reactive groups and at least one ionic group, (D) polyamines having an average molecular weight o~ at least 32 (preferably in the range of 60 to 500), and (E) water, the average total functionality of the isocyanate-reactive compounds B to D being from 1.85 to 2.2, and preferably from 1.9 to 2.1, wherein the polyurethane ureas have from 800 to 1500, preferably less than 1400 mmol, urethane groups and from 800 to 1800, preferably from 1000 to 1700 mmol urethane plus urea groups per kg of anionically modified polyurethane urea.
Within these constraints, the preferred polyurethane ureas have a content of urea groups of more than 150 mmol (more preferably more than 200 mmol) per kilogram of polyurethane urea.
According to a preferred embodiment, the molar ratio between the isocyanate groups of component A and the isocyanate-reactive groups (i.e. in particular: OH~NH) of components B to D is greater than 1, and in particular greater than 1.05.
According to another preferred embodiment, the polyurethane ureas according to the invention have a Shore A .
hardness of at most 50.
The present invention also relates to the use of these anionically modified polyurethane ureas for the coating of leather.
The difference between the preferred subject matter of our invention and that of European Patent Application 441,190 is explained in more detail in the following: The ratio between Mo3921 . .. . - ..................... -, .
. ~, . . i . ~. .
:.::: . .: . - . . , NCO groups and NCO-reactive alcoholic and anionic groups in the Examples of European Patent Application 441,196 is 1Ø Since the water required for dispersion of the polymers must be added before all of the alcoholic hydroxyl groups have been completely reacted with isocyanate, water also takes part in the reaction as an isocyanate-reactive component. The actual ratio between isocyanate groups and isocyanate-reactive groups is thus always smaller than 1. Therefore, some of the alccholic hydroxylic groups remain unreacted. This means in other words that each molecule of water which takes part in the reaction indirectly causes chain termination. A relatively low molecular weight product with terminal hydroxyl groups is obtained.
This is not the case with the subject matter of our invention: The ratio between NCO groups and NCO-reactive alcoholic and amine groups is greater than 1. Since water is added at a stage at which all of the available alcoholic hydroxyl groups have already reacted with isocyanate, water does not compete in the reaction. The polyamines optionally added at the same time as the water react so quickly with isocyanate that water also does not compete in this reaction.
The water can therefore only react with excess isocyanate groups and thus plays an essential role in increasing the molecular weight of the product.
Our products have high flexibility and very low tackiness and in particular an extremely favorable combination of very high wet adhesion, high flexibility and low tackiness.
DETAILED DESCRIPTION OF THE INVENTION
The diisocyanate component (A) may be selected, for example, from aromatic diisocyanates of the type described, for example, by W. Siefken in Justus Liebiqs Annalen der Chemie.
562. pages 75 to 136. Aromatic diisocyanates or diisocyanate mixtures bearing lateral alkyl groups, for example, 2,4- and 2,6-toluene diisocyanate, are particularly preferred.
The polyether polyols (B) are preferably selected from the polyaddition products of ethylene oxide, propylene oxide, and Mo3921 ~.~ . . .
, , - . . , ,: ,. , : - , .
2 1 0 1~89 butylene oxide and copolyaddition and graft polyaddition products thereof, the polyethers obtained by condensation of polyhydric alcohols or mixtures thereof, and the polyethers obtained by alkoxylation of water, polyhydric alcohols, amines, or amino alcohols. Particularly preferred polyether polyols (B) are homo- and/or co-polyaddition compounds of ethylene oxide and/or propylene oxide having a molecular weight of greater than about 1500 (preferably in the range from 1800 to 3000) and an average functionality of greater than 1.85 (preferably from lo 2 to 3); difunctional polyethers are particularly preferred.
Other relatively high molecular weight polyhydroxyl components known from polyurethane chemistry belonging, to, for example, the classes of polyester, polylactone or, polycarbonate polyols may optionally be used in small lo quantities.
Suitable ionic compounds (C) containing 1 to 2 isocyanate-reactive groups and at least one ionic group include compounds such as, for example, hydroxycarboxylic and mercaptocarboxylic acids, aminocarboxylic acids, such as glycine, alanine, or 4-aminobutyric acid, di- and polyhydroxycarboxylic acids, such as dimethylolpropionic acid or dimethylol butyric acid, or aliphatic diols containing sulfonate groups according to German Offenlegungsschriften 2,446,440 and 2,437,218. Particularly -preferred ionic components (C) include sulfonate diols corresponding to the following formula H ~ CIH--CH2 ~ 0 --~X ~ C,H (Y ~ CH2 ICH--O ~ H
l CH3 ~ (C~H2)q+ L ~ m in which X and Y independently represent difunctional aliphatic hydrocarbon groups containing 1 to 6 carbon atoms, Mo3921 - .: - ,:
: :~:~ ., .- - : . . , 2 is an alkali metal ion or a proton, n and m independently represent O or numbers from 1 to 30, o and p have values of 0, 1, 2 or 3, and q has a value of 0, 1 or 2.
Dimethylolpropionic acid is also particularly preferred.
Other particularly preferred components (C) are diaminosulfonates of the type descr;bed in Canadian Patent 928,323, such as the sodium salt of N-(2-aminoethyl3-2-aminoethanesulfonic acid or the sodium salt of N-(2-Io aminoethyl)-2-aminopropanoic acid.
If ionic components (C) are used in the form of non-neutralized carboxylic and/or sulfonic acids, preferred neutralizing agents are tertiary amines, such as triethylamine, tripropylamine, tributylamine, triisopropanolamine, N,N- ~-dimethylethanolamine, or ammonia; alkali metal hydroxides, such as sodium or potassium hydroxide; or alkali metal carbonates or hydrogen carbonates.
Suitable polyamines (D) are compounds which have a molecular weight of greater than 32 (preferably in the range from 60 to 500) and which contain primary and/or secondary amino groups. Examples of suitable such polyamines include ethylene diamine, hexamethylene diamine, isophorone diamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, N,N'-dimethyl ethylene diamine, 4,4'-diamino-cyclohexylmethane, piperazine, 2,5-dimethyl-piperazine, 1,4-diaminocyclohexane, 1,2-diamino-propane, hydrazine or hydrazine hydrate diethylene triamine.
Monoamines such as, for example, dibutylamine, ethanol-amine, N-methylethanolamine, diethanolamine, or propanolamine may optionally be used in small quantities to modify 3o functionality The polyamines (D) may, of course, also be used in blocked form, that is, as the corresponding ketimines (German Offenlegungsschrift 2,725,589), ketazines (German Offenlegungsschrift 2,811,148 and U.S. Patent 4,269,748), or amine salts (U.S. Patent 4,292,226).
Mo3921 .... .
,: - , . .
:
.. ~: - ., -.,.. . , :.: ~ ~ , ; .
. ~ .: . .-.
2101~89 The polyurethane ureas according to the invention are particularly suitable when they have a content of urethane groups plus urea groups from 800 to 1800 mmol per kilogra~
(preferably from 10~0 to 1700 mmol per kilogram) of the polyurethane urea.
The polyurethane ureas are generally prepared by one of the follGwing known processes:
1. The so-called "acetone process" accord;ng to German Offenlegungsschrift 1,495,745 and U.S. Patent 3,479,310, in which an NCO-terminated prepolymer is prepared in the melt, dissolved in a suitable solvent, and allowed to react in solution with a chain-extending agent to form a polyurethane.
After the solution of the polyurethane has been mixed with water, the polyurethane dispersion is obtained by distilling off the solvent. Essentially linear polyurethanes can be synthesized by this process because crosslinked systems readily gel in the organic phase. ~-2. A process for the preparation of polyurethane-based dispersions using blocked amines or hydrazines as chain-extending agent is described in German Offenlegungsschrift 2,725,589 and U.S. Patents 4,269,748, 4,192,937 and 4,292,226. In this process, a hydrophilic j NCO-terminated prepolymer is mixed with at least partly blocked am;nes or hydrazines in the absence of water. Water is subsequently added to the resultant mixture so that the previously blocked amine or hydrazine is released and reacts as chain extender for the prepolymer. Although aromatic diiso-cyanates may also be used in this process to form the NCO-terminated prepolymers, prepolymers containing aliphatically ; 3a and/or cycloaliphatically bound NCO groups are preferred.
3. In another known process, the NCO-terminated prepolymers are chain-extended in aqueous medium by dispersion of the hydrophilic prepolymers in water and subsequently addition of the chain extending agent. The dispersion may be formed both by adding water to the prepolymer and by adding the Mo3921 . .
: :
21013~9 prepolymer to water. When chain extension is carried out in aqueous medium prepolymers terminated by aliphatic and/or cycloaliphatic NC0 groups are particularly preferred. When aromatically bound terminal NC0 groups are used these isocyanate groups are preferably capped before the addition of water, as described in U.S. Patent 4,387,181.
The acetone process 1) for the preparation of the dispersions is preferred. According to the invention, the polyurethanes may be dispersed by basically any process, o including, for example, dispersion without solvents, for example, by mixing the polyurethane melts with water in units capable of producing a high shear rate; the use of small quantities of solvent for plasticization during processing in such units; and the use of non-mechanical dispersion means, such as sound waves of extremely high frequency. However, -simple mixers, such as stirred tanks or so-called reflux mixers, may also be used when the polyurethanes are self-dispersible.
In general, the quantities of starting components (A) to (E) are selected in such a way that anionically modified polyurethane ureas containing 5 to 35 mmol (preferably 10 to 30 mmol) of anionic groups per 100 9 of polyurethane urea and dispersions having a solids content of 20 to 60% by weight are obtained.
The functionality of components (B) to (D) are selected in such a way that the average total functionality according to the claims is obtained.
Suitable organic solvents for the polyurethane ureas according to the invention are, for example, dimethyl 3o formamide, dimethyl acetamide, tetrahydrofuran or N-methyl pyrrolidine or solvent mixtures of ketones such as, for example, cyclohexanone, methyl ethyl ketone, methyl isobutyl -ketone or acetone, and alcohols such as, for example, isopropanol, n-butanol, tert.-butanol, methoxy propanol or butyl glycol Mo3921 .: ,~ . i - ' ' ' ' ~ , , : ."' " ' ~':`
2 1~1389 The an~onically modified polyurethane ureas of the present invention are imminently suitable for use as adheslon promoters in the finishing of leather.
The following examples further illustrate details for the preparation and use of the compounds of this invention. The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. --Those skilled in the art will readily understand that known variations of the conditions and processes of the following preparative procedures can be used to prepare these ~ompounds.
Unless otherwise noted, all temperatures are degrees Celsius and all parts and percentages are parts by weight and percentages by weight, respectively.
EXAMPLES
Determination of solubilitY and viscositv in THF
10 parts of an aqueous dispersion containing 90% of solid are diluted with 90 parts of THF (at 25~C with stirring for 60 minutes).
Evaluation: Complete solubility exists when a clear flowable solution without any gel content visible with the naked eye is obtained.
Viscosity: The indicated viscosities present outflow viscosities, determined according to DIN (German Industrial Standard) 53 211 from a DIN beaker (4 mm nozzle). The figures refer to the outflow time in seconds lsec] up to the point in time at which the thread of liquid breaks.
Hardness: Shore A hardness based on DIN 53 S05 10 ml of a 30% aqueous polyurethane urea dispersion are poured onto glass, left to dry overnight at room temperature and subsequently heated to 50-C for 1/2 hour. The film is peeled off and cut into strips. The strips are placed one above the other so that no air is enclosed and the stack is at least 6 mm high. This stack is then tested. The mean value of 3 measurements is indicated.
Mo3921 ~.,, ,. - .. .. .
-,; - - : .
~10138~
Example I
400 9 of a polypropylene ox;de diol (OH value 56) and 18.8 g of dimethylolpropionic acid were freed from water for 60 minutes at 110C and 15 mbar. 73.9 g of a 35:65 mixture of 2,6-and 2,4-toluene diisocyanate were added at 95'C. An isocyanate content of 1.34% was reached after 5 hours. The reaction mixture was diluted with 390 9 of acetone, and 10.6 9 of triethylamine were added over a period of 15 minutes at 50-C.
The solution was diluted with 1000 9 water and chain-extended lo with 2.7 9 of diethylene triamine in 100 g of water. After removal of the acetone by distillation, a fine-particle dispersion having the following data was obtained:
Solids content: 30.6 % by weight pH = 8.0 Urethane groups:1244 mmol/kg Urea groups:255 mmol/kg Sum: 1599 mmol/kg Shore A: 47 Solubility in THF:completely soluble (clear solution) Viscosity in THF:26 (sec) Example 2 The procedure is the same as in Example 1, except that 12.1 9 of isophorone diamine were used instead of 2.7 9 of diethylene triamine:
Solids content: 30.7% by weight pH = 8.2 Urethane groups:1319 mmol/kg Urea groups:303 mmol/kg Sum: 1622 mmol/kg Shore A: 44 Solubility in THF:completely soluble (clear solution) Viscosity in THF:13 (sec) Mo3921 ~r ~ .
~ . . . .
: . . - . . ..
21013~9 ExamQle 3 1380 9 of a polypropylene oxide diol (OH value 56) and 65 g of dimethylolpropionic acid were freed from water for 60 minutes at 110C and 15 mbar. 266 9 of a 35:65 mixture of 2,6-and 2,4-toluene diisocyanate were added at 90C. An isocyanate -content of 1.55% was reached after 5 hours. The reaction mixture was diluted with 3300 9 of acetone. 12.25 9 of ethylene diamine in 160 9 of water were added to the acetone solution at 55 to 65C. The solution was then neutralized with 35 9 lo triethylamine and dispersed with 4000 g of water. After removal of the acetone by distillation, a fine-particle d;spersion having the following data was obtained:
Solids content: 30.5% by weight pH = 7.7 Urethane groups: 1335 mmol/kg Urea groups: 332 mmol/kg Sum: 1667 mmol/kg Shore A: 49 Solubility in THF: completely solu ble (clear solution~
Viscosity in THF: 17 (sec) ExamDles 4 to 5 Preparation of the test specimens 11 x 20 cm samples were cut from a full grain leather phobicized with a commercially available fluorocarbon resin.
Aqueous preparations having a solids content of 6% and an isopropyl alcohol content of 10% were prepared from the products described in Examples 2 and 3. 5 9 of these preparations were sprayed onto the grain side of the leather samples. After drying (10 minutes at 50'C) and storing overnight at room temperature, the leathers thus treated were oversprayed twice with 5 9 of a mixture of 75 parts of EUDERM~
Gruiidschwarz C, 75 parts of EUDERM~ Filler VF, 50 parts of EUDERM~ Paste FO, 150 parts of EUDERM~ Dispersion 32 A, 150 parts of BAYDERM~ Grund 50 UD, and 500 parts water. The dried samples were tested for dry and wet adhesion in accordance with Mo3921 ~... . .
.. - . . ,, ~ ~ . . . . , . - , hl 1 0 1 3 8 9 JUF 470 (DESMOCOLL method), with results (in N-cm 1) given in the following Table.
Table:
Example Dispersion from Adhesion [N/cm]
Dry Wet .
4 Example 2 6.0/6.2* 2.8/2.8 S Example 3 7.5/7.0* 3.0/3.5 10 . - -* Grain tears Example 6 (comparison with U.S. 4,895,894) A mixture of 200 9 of a polypropylene oxide diol (OH
number = 56) and 13.6 9 of dimethyl propionic acid is dehydrated for 60 minutes at 110~C and IS mbar. 80 9 of 4.4'-methylene bis-(cyclohexyl isocyanate) are added at 100-C.
An isocyanate content of 2.72% is obtained after 4 hours. The melt is stirred with 9.8 9 of triethyl amine at 70-C for 15 minutes. Then the mixture is diluted with 700 9 of water. 5.41 9 of ethylene diamine in 100 9 of water are added to the solution. A finely divided dispersion which solidifies in a curd-like form after about 3 hours, is obtained.
Urethane groups: 1308 mmol/kg Urea groups: 625 mmol/kg Sum: 1933 mmol/kg Solubility in THF: insoluble Although the invention has been described in deSail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo3921 ~- -,, . , . ~ . .
r; '
SUMMARY OF THE INVENTION
Accordingly, the present invention relates to anionically modif;ed polyurethane ureas prepared by the reaction of (A) diisocyanates, (B) polyether polyols having an average molecular weight greater than 1500 (preferably in the range of 1800 to 3000), (C) at least one compound containing 1 to 2 isocyanate-reactive groups and at least one ionic group, (D) polyamines having an average molecular weight o~ at least 32 (preferably in the range of 60 to 500), and (E) water, the average total functionality of the isocyanate-reactive compounds B to D being from 1.85 to 2.2, and preferably from 1.9 to 2.1, wherein the polyurethane ureas have from 800 to 1500, preferably less than 1400 mmol, urethane groups and from 800 to 1800, preferably from 1000 to 1700 mmol urethane plus urea groups per kg of anionically modified polyurethane urea.
Within these constraints, the preferred polyurethane ureas have a content of urea groups of more than 150 mmol (more preferably more than 200 mmol) per kilogram of polyurethane urea.
According to a preferred embodiment, the molar ratio between the isocyanate groups of component A and the isocyanate-reactive groups (i.e. in particular: OH~NH) of components B to D is greater than 1, and in particular greater than 1.05.
According to another preferred embodiment, the polyurethane ureas according to the invention have a Shore A .
hardness of at most 50.
The present invention also relates to the use of these anionically modified polyurethane ureas for the coating of leather.
The difference between the preferred subject matter of our invention and that of European Patent Application 441,190 is explained in more detail in the following: The ratio between Mo3921 . .. . - ..................... -, .
. ~, . . i . ~. .
:.::: . .: . - . . , NCO groups and NCO-reactive alcoholic and anionic groups in the Examples of European Patent Application 441,196 is 1Ø Since the water required for dispersion of the polymers must be added before all of the alcoholic hydroxyl groups have been completely reacted with isocyanate, water also takes part in the reaction as an isocyanate-reactive component. The actual ratio between isocyanate groups and isocyanate-reactive groups is thus always smaller than 1. Therefore, some of the alccholic hydroxylic groups remain unreacted. This means in other words that each molecule of water which takes part in the reaction indirectly causes chain termination. A relatively low molecular weight product with terminal hydroxyl groups is obtained.
This is not the case with the subject matter of our invention: The ratio between NCO groups and NCO-reactive alcoholic and amine groups is greater than 1. Since water is added at a stage at which all of the available alcoholic hydroxyl groups have already reacted with isocyanate, water does not compete in the reaction. The polyamines optionally added at the same time as the water react so quickly with isocyanate that water also does not compete in this reaction.
The water can therefore only react with excess isocyanate groups and thus plays an essential role in increasing the molecular weight of the product.
Our products have high flexibility and very low tackiness and in particular an extremely favorable combination of very high wet adhesion, high flexibility and low tackiness.
DETAILED DESCRIPTION OF THE INVENTION
The diisocyanate component (A) may be selected, for example, from aromatic diisocyanates of the type described, for example, by W. Siefken in Justus Liebiqs Annalen der Chemie.
562. pages 75 to 136. Aromatic diisocyanates or diisocyanate mixtures bearing lateral alkyl groups, for example, 2,4- and 2,6-toluene diisocyanate, are particularly preferred.
The polyether polyols (B) are preferably selected from the polyaddition products of ethylene oxide, propylene oxide, and Mo3921 ~.~ . . .
, , - . . , ,: ,. , : - , .
2 1 0 1~89 butylene oxide and copolyaddition and graft polyaddition products thereof, the polyethers obtained by condensation of polyhydric alcohols or mixtures thereof, and the polyethers obtained by alkoxylation of water, polyhydric alcohols, amines, or amino alcohols. Particularly preferred polyether polyols (B) are homo- and/or co-polyaddition compounds of ethylene oxide and/or propylene oxide having a molecular weight of greater than about 1500 (preferably in the range from 1800 to 3000) and an average functionality of greater than 1.85 (preferably from lo 2 to 3); difunctional polyethers are particularly preferred.
Other relatively high molecular weight polyhydroxyl components known from polyurethane chemistry belonging, to, for example, the classes of polyester, polylactone or, polycarbonate polyols may optionally be used in small lo quantities.
Suitable ionic compounds (C) containing 1 to 2 isocyanate-reactive groups and at least one ionic group include compounds such as, for example, hydroxycarboxylic and mercaptocarboxylic acids, aminocarboxylic acids, such as glycine, alanine, or 4-aminobutyric acid, di- and polyhydroxycarboxylic acids, such as dimethylolpropionic acid or dimethylol butyric acid, or aliphatic diols containing sulfonate groups according to German Offenlegungsschriften 2,446,440 and 2,437,218. Particularly -preferred ionic components (C) include sulfonate diols corresponding to the following formula H ~ CIH--CH2 ~ 0 --~X ~ C,H (Y ~ CH2 ICH--O ~ H
l CH3 ~ (C~H2)q+ L ~ m in which X and Y independently represent difunctional aliphatic hydrocarbon groups containing 1 to 6 carbon atoms, Mo3921 - .: - ,:
: :~:~ ., .- - : . . , 2 is an alkali metal ion or a proton, n and m independently represent O or numbers from 1 to 30, o and p have values of 0, 1, 2 or 3, and q has a value of 0, 1 or 2.
Dimethylolpropionic acid is also particularly preferred.
Other particularly preferred components (C) are diaminosulfonates of the type descr;bed in Canadian Patent 928,323, such as the sodium salt of N-(2-aminoethyl3-2-aminoethanesulfonic acid or the sodium salt of N-(2-Io aminoethyl)-2-aminopropanoic acid.
If ionic components (C) are used in the form of non-neutralized carboxylic and/or sulfonic acids, preferred neutralizing agents are tertiary amines, such as triethylamine, tripropylamine, tributylamine, triisopropanolamine, N,N- ~-dimethylethanolamine, or ammonia; alkali metal hydroxides, such as sodium or potassium hydroxide; or alkali metal carbonates or hydrogen carbonates.
Suitable polyamines (D) are compounds which have a molecular weight of greater than 32 (preferably in the range from 60 to 500) and which contain primary and/or secondary amino groups. Examples of suitable such polyamines include ethylene diamine, hexamethylene diamine, isophorone diamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, N,N'-dimethyl ethylene diamine, 4,4'-diamino-cyclohexylmethane, piperazine, 2,5-dimethyl-piperazine, 1,4-diaminocyclohexane, 1,2-diamino-propane, hydrazine or hydrazine hydrate diethylene triamine.
Monoamines such as, for example, dibutylamine, ethanol-amine, N-methylethanolamine, diethanolamine, or propanolamine may optionally be used in small quantities to modify 3o functionality The polyamines (D) may, of course, also be used in blocked form, that is, as the corresponding ketimines (German Offenlegungsschrift 2,725,589), ketazines (German Offenlegungsschrift 2,811,148 and U.S. Patent 4,269,748), or amine salts (U.S. Patent 4,292,226).
Mo3921 .... .
,: - , . .
:
.. ~: - ., -.,.. . , :.: ~ ~ , ; .
. ~ .: . .-.
2101~89 The polyurethane ureas according to the invention are particularly suitable when they have a content of urethane groups plus urea groups from 800 to 1800 mmol per kilogra~
(preferably from 10~0 to 1700 mmol per kilogram) of the polyurethane urea.
The polyurethane ureas are generally prepared by one of the follGwing known processes:
1. The so-called "acetone process" accord;ng to German Offenlegungsschrift 1,495,745 and U.S. Patent 3,479,310, in which an NCO-terminated prepolymer is prepared in the melt, dissolved in a suitable solvent, and allowed to react in solution with a chain-extending agent to form a polyurethane.
After the solution of the polyurethane has been mixed with water, the polyurethane dispersion is obtained by distilling off the solvent. Essentially linear polyurethanes can be synthesized by this process because crosslinked systems readily gel in the organic phase. ~-2. A process for the preparation of polyurethane-based dispersions using blocked amines or hydrazines as chain-extending agent is described in German Offenlegungsschrift 2,725,589 and U.S. Patents 4,269,748, 4,192,937 and 4,292,226. In this process, a hydrophilic j NCO-terminated prepolymer is mixed with at least partly blocked am;nes or hydrazines in the absence of water. Water is subsequently added to the resultant mixture so that the previously blocked amine or hydrazine is released and reacts as chain extender for the prepolymer. Although aromatic diiso-cyanates may also be used in this process to form the NCO-terminated prepolymers, prepolymers containing aliphatically ; 3a and/or cycloaliphatically bound NCO groups are preferred.
3. In another known process, the NCO-terminated prepolymers are chain-extended in aqueous medium by dispersion of the hydrophilic prepolymers in water and subsequently addition of the chain extending agent. The dispersion may be formed both by adding water to the prepolymer and by adding the Mo3921 . .
: :
21013~9 prepolymer to water. When chain extension is carried out in aqueous medium prepolymers terminated by aliphatic and/or cycloaliphatic NC0 groups are particularly preferred. When aromatically bound terminal NC0 groups are used these isocyanate groups are preferably capped before the addition of water, as described in U.S. Patent 4,387,181.
The acetone process 1) for the preparation of the dispersions is preferred. According to the invention, the polyurethanes may be dispersed by basically any process, o including, for example, dispersion without solvents, for example, by mixing the polyurethane melts with water in units capable of producing a high shear rate; the use of small quantities of solvent for plasticization during processing in such units; and the use of non-mechanical dispersion means, such as sound waves of extremely high frequency. However, -simple mixers, such as stirred tanks or so-called reflux mixers, may also be used when the polyurethanes are self-dispersible.
In general, the quantities of starting components (A) to (E) are selected in such a way that anionically modified polyurethane ureas containing 5 to 35 mmol (preferably 10 to 30 mmol) of anionic groups per 100 9 of polyurethane urea and dispersions having a solids content of 20 to 60% by weight are obtained.
The functionality of components (B) to (D) are selected in such a way that the average total functionality according to the claims is obtained.
Suitable organic solvents for the polyurethane ureas according to the invention are, for example, dimethyl 3o formamide, dimethyl acetamide, tetrahydrofuran or N-methyl pyrrolidine or solvent mixtures of ketones such as, for example, cyclohexanone, methyl ethyl ketone, methyl isobutyl -ketone or acetone, and alcohols such as, for example, isopropanol, n-butanol, tert.-butanol, methoxy propanol or butyl glycol Mo3921 .: ,~ . i - ' ' ' ' ~ , , : ."' " ' ~':`
2 1~1389 The an~onically modified polyurethane ureas of the present invention are imminently suitable for use as adheslon promoters in the finishing of leather.
The following examples further illustrate details for the preparation and use of the compounds of this invention. The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. --Those skilled in the art will readily understand that known variations of the conditions and processes of the following preparative procedures can be used to prepare these ~ompounds.
Unless otherwise noted, all temperatures are degrees Celsius and all parts and percentages are parts by weight and percentages by weight, respectively.
EXAMPLES
Determination of solubilitY and viscositv in THF
10 parts of an aqueous dispersion containing 90% of solid are diluted with 90 parts of THF (at 25~C with stirring for 60 minutes).
Evaluation: Complete solubility exists when a clear flowable solution without any gel content visible with the naked eye is obtained.
Viscosity: The indicated viscosities present outflow viscosities, determined according to DIN (German Industrial Standard) 53 211 from a DIN beaker (4 mm nozzle). The figures refer to the outflow time in seconds lsec] up to the point in time at which the thread of liquid breaks.
Hardness: Shore A hardness based on DIN 53 S05 10 ml of a 30% aqueous polyurethane urea dispersion are poured onto glass, left to dry overnight at room temperature and subsequently heated to 50-C for 1/2 hour. The film is peeled off and cut into strips. The strips are placed one above the other so that no air is enclosed and the stack is at least 6 mm high. This stack is then tested. The mean value of 3 measurements is indicated.
Mo3921 ~.,, ,. - .. .. .
-,; - - : .
~10138~
Example I
400 9 of a polypropylene ox;de diol (OH value 56) and 18.8 g of dimethylolpropionic acid were freed from water for 60 minutes at 110C and 15 mbar. 73.9 g of a 35:65 mixture of 2,6-and 2,4-toluene diisocyanate were added at 95'C. An isocyanate content of 1.34% was reached after 5 hours. The reaction mixture was diluted with 390 9 of acetone, and 10.6 9 of triethylamine were added over a period of 15 minutes at 50-C.
The solution was diluted with 1000 9 water and chain-extended lo with 2.7 9 of diethylene triamine in 100 g of water. After removal of the acetone by distillation, a fine-particle dispersion having the following data was obtained:
Solids content: 30.6 % by weight pH = 8.0 Urethane groups:1244 mmol/kg Urea groups:255 mmol/kg Sum: 1599 mmol/kg Shore A: 47 Solubility in THF:completely soluble (clear solution) Viscosity in THF:26 (sec) Example 2 The procedure is the same as in Example 1, except that 12.1 9 of isophorone diamine were used instead of 2.7 9 of diethylene triamine:
Solids content: 30.7% by weight pH = 8.2 Urethane groups:1319 mmol/kg Urea groups:303 mmol/kg Sum: 1622 mmol/kg Shore A: 44 Solubility in THF:completely soluble (clear solution) Viscosity in THF:13 (sec) Mo3921 ~r ~ .
~ . . . .
: . . - . . ..
21013~9 ExamQle 3 1380 9 of a polypropylene oxide diol (OH value 56) and 65 g of dimethylolpropionic acid were freed from water for 60 minutes at 110C and 15 mbar. 266 9 of a 35:65 mixture of 2,6-and 2,4-toluene diisocyanate were added at 90C. An isocyanate -content of 1.55% was reached after 5 hours. The reaction mixture was diluted with 3300 9 of acetone. 12.25 9 of ethylene diamine in 160 9 of water were added to the acetone solution at 55 to 65C. The solution was then neutralized with 35 9 lo triethylamine and dispersed with 4000 g of water. After removal of the acetone by distillation, a fine-particle d;spersion having the following data was obtained:
Solids content: 30.5% by weight pH = 7.7 Urethane groups: 1335 mmol/kg Urea groups: 332 mmol/kg Sum: 1667 mmol/kg Shore A: 49 Solubility in THF: completely solu ble (clear solution~
Viscosity in THF: 17 (sec) ExamDles 4 to 5 Preparation of the test specimens 11 x 20 cm samples were cut from a full grain leather phobicized with a commercially available fluorocarbon resin.
Aqueous preparations having a solids content of 6% and an isopropyl alcohol content of 10% were prepared from the products described in Examples 2 and 3. 5 9 of these preparations were sprayed onto the grain side of the leather samples. After drying (10 minutes at 50'C) and storing overnight at room temperature, the leathers thus treated were oversprayed twice with 5 9 of a mixture of 75 parts of EUDERM~
Gruiidschwarz C, 75 parts of EUDERM~ Filler VF, 50 parts of EUDERM~ Paste FO, 150 parts of EUDERM~ Dispersion 32 A, 150 parts of BAYDERM~ Grund 50 UD, and 500 parts water. The dried samples were tested for dry and wet adhesion in accordance with Mo3921 ~... . .
.. - . . ,, ~ ~ . . . . , . - , hl 1 0 1 3 8 9 JUF 470 (DESMOCOLL method), with results (in N-cm 1) given in the following Table.
Table:
Example Dispersion from Adhesion [N/cm]
Dry Wet .
4 Example 2 6.0/6.2* 2.8/2.8 S Example 3 7.5/7.0* 3.0/3.5 10 . - -* Grain tears Example 6 (comparison with U.S. 4,895,894) A mixture of 200 9 of a polypropylene oxide diol (OH
number = 56) and 13.6 9 of dimethyl propionic acid is dehydrated for 60 minutes at 110~C and IS mbar. 80 9 of 4.4'-methylene bis-(cyclohexyl isocyanate) are added at 100-C.
An isocyanate content of 2.72% is obtained after 4 hours. The melt is stirred with 9.8 9 of triethyl amine at 70-C for 15 minutes. Then the mixture is diluted with 700 9 of water. 5.41 9 of ethylene diamine in 100 9 of water are added to the solution. A finely divided dispersion which solidifies in a curd-like form after about 3 hours, is obtained.
Urethane groups: 1308 mmol/kg Urea groups: 625 mmol/kg Sum: 1933 mmol/kg Solubility in THF: insoluble Although the invention has been described in deSail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo3921 ~- -,, . , . ~ . .
r; '
Claims (8)
1. An anionically modified polyurethane urea prepared by the reaction of (A) aromatic diisocyanates, (B) polyether polyols having an average molecular weight greater than 1500, (C) at least one compound containing 1 to 2 isocyanate-reactive groups and at least one ionic group, (D) polyamines having an average molecular weight of at least 32, and (E) water, the average total functionality of the isocyanate reactive compounds B to D being from 1.85 to 2.2, wherein the polyurethane ureas have from 800 to 1500 mmol urethane groups and from 800 to 1800 mmol urethane plus urea groups per kg of anionically modified polyurethane urea.
2. A polyurethane urea according to Claim 1 having a content of urethane groups plus urea groups of from 1000 to 1700 mmol per kilogram of polyurethane urea.
3. A polyurethane urea according to Claim 1 having a content of urea groups of more than 150 mmol per kilogram of polyurethane urea.
4. A polyurethane urea according to Claim 1 having a content of urea groups of more than 200 mmol per kilogram of polyurethane urea.
5. A polyurethane urea according to Claim 1 wherein the molar ratio between the isocyanate groups of component (A) and the total number of OH and NH groups of components (B), (C) and (D) is greater than l.
6. A polyurethane urea according to Claim 1 wherein the molar ratio between the isocyanate groups of component (A) and the total number of OH and NH groups of components (B), (C) and (D) is greater than 1.05.
7. A polyurethane urea according to Claim 1 having a Shore A hardness of at most 50.
8. In a method for finishing leather in the presence of an adhesion promoter, the improvement comprising treating leather with a polyurethane urea according to Claim I as the adhesion promoter.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4225290 | 1992-07-31 | ||
| DEP4225290.3-44 | 1992-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2101389A1 true CA2101389A1 (en) | 1994-02-01 |
Family
ID=6464523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002101389A Abandoned CA2101389A1 (en) | 1992-07-31 | 1993-07-27 | Anionically modified polyurethane ureas having reduced tackiness for the coating of leather |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0581159B1 (en) |
| JP (1) | JPH06220156A (en) |
| CA (1) | CA2101389A1 (en) |
| DE (1) | DE59306566D1 (en) |
| ES (1) | ES2102558T3 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2175403C (en) * | 1995-05-05 | 2008-09-02 | Stephen D. Seneker | Aqueous polyurethane dispersions based on polyether polyols of low monol content |
| DE102008014211A1 (en) | 2008-03-14 | 2009-09-17 | Bayer Materialscience Ag | Aqueous dispersion of anionically modified polyurethane ureas for coating a textile fabric |
| EP2319876A1 (en) | 2009-10-16 | 2011-05-11 | Bayer MaterialScience AG | Aromatic polyurethane urea dispersions |
| EP2395036A1 (en) | 2010-05-17 | 2011-12-14 | Bayer MaterialScience AG | Polyurethane dispersions with an acid-base mixture as an additive |
| KR20160088330A (en) * | 2013-11-21 | 2016-07-25 | 도레이 카부시키가이샤 | Sheet-like article |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1720617A1 (en) * | 1967-02-10 | 1971-07-01 | Bayer Ag | Process for the production of polyurethane polyureas |
| JPS5240676B2 (en) * | 1974-08-23 | 1977-10-13 | ||
| US4387181A (en) * | 1980-04-09 | 1983-06-07 | Textron, Inc. | Polymer compositions and manufacture |
| IT1222093B (en) * | 1987-07-22 | 1990-08-31 | Conceria Conti S P A | PROCEDURE FOR FINISHING LEATHER, LEATHER AND SIMILAR FIBROUS SUBSTRATES |
| DE4003422A1 (en) * | 1990-02-06 | 1991-08-08 | Basf Ag | WAITER POLYURETHANE PREPARATIONS |
-
1993
- 1993-07-19 ES ES93111542T patent/ES2102558T3/en not_active Expired - Lifetime
- 1993-07-19 EP EP93111542A patent/EP0581159B1/en not_active Expired - Lifetime
- 1993-07-19 DE DE59306566T patent/DE59306566D1/en not_active Expired - Lifetime
- 1993-07-26 JP JP5202522A patent/JPH06220156A/en active Pending
- 1993-07-27 CA CA002101389A patent/CA2101389A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0581159A1 (en) | 1994-02-02 |
| DE59306566D1 (en) | 1997-07-03 |
| EP0581159B1 (en) | 1997-05-28 |
| JPH06220156A (en) | 1994-08-09 |
| ES2102558T3 (en) | 1997-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1249391A (en) | Stable, aqueous dispersions of polyurethane-ureas and coatings and films prepared therefrom | |
| Wicks Jr et al. | Two package waterborne urethane systems | |
| CA1334231C (en) | Water soluble or dispersible polyurethanes, a process for their preparation and their use for coating substrates | |
| US4870129A (en) | Adhesive and use of the adhesive for the formation of bonds | |
| CA1163040A (en) | Aqueous polyurethane compositions | |
| CA1303769C (en) | Process for the production of aqueous dispersions of polyurethane polyureas, the dispersions obtainable by this process and their use as coating compositions | |
| US5306764A (en) | Water dispersible polyurethane and process for preparation thereof | |
| US4598121A (en) | Cold-crosslinking polyurethane dispersions, manufacture and use of the same | |
| CA2364603A1 (en) | Self-crosslinking polyurethane, polyurethane-polyurea or polyurea dispersions for sizing materials | |
| CA2487002C (en) | Polyurethane dispersions | |
| CA1102027A (en) | Process for the preparation of aqueous dispersions or solutions of polyurethanes and the use thereof | |
| JPH0535744B2 (en) | ||
| EP0847409A1 (en) | Improved water-based polyurethanes for footwear | |
| US4186118A (en) | Process for the preparation of modified aqueous synthetic resin dispersions | |
| EP1319032B1 (en) | Low-temperature, heat-activated adhesives with high heat resistance properties | |
| EP1153052B1 (en) | Process for the preparation of an aqueous dispersion of an anionic polyurethane free of volatile tertiary amines | |
| US5422186A (en) | Compositions containing mixtures of aqueous polymer dispersions and textile and leather substrates coated therewith | |
| JP2007525582A (en) | Improved polyurethane dispersion and coatings produced therefrom | |
| EP1233991B1 (en) | Process for the preparation of a coating, a coated substrate, an adhesive, a film or sheet, for the thus obtained products and the coating mixture to be used in the process | |
| CA2023840A1 (en) | Aqueous polyurethane dispersions and adhesives based thereon | |
| CA2101389A1 (en) | Anionically modified polyurethane ureas having reduced tackiness for the coating of leather | |
| US5770264A (en) | Anionically modified polyurethane ureas having reduced tackiness for the coating of leather | |
| EP0927211B1 (en) | Water-dispersible polyurethanes | |
| US20040260015A1 (en) | Aqueous preparations of hydrophilic polyurethane resins | |
| JP3391545B2 (en) | Method for producing aqueous polyurethane polyurea dispersion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |