US4408008A — Stable, colloidal, aqueous dispersions of cross-l…

Claim 1

Independent Claim 375 words

A process for the preparation of a stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which comprises (a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight of up to about 25,000 by reacting (i) an organic polyisocyanate which contains at least two aliphatically or cycloaliphatically bound isocyanate groups, (ii) an organic compound which has at least two isocyanate-reactive groups, (iii) an organic compound which comprises a member selected from the group consisting of diisocyanates which contain lateral, hydrophilic ethylene oxide units; compounds which are difunctional in the isocyanate-polyaddition reaction and contain lateral, hydrophilic ethylene oxide units; monoisocyanates which contain terminal, hydrophilic ethylene oxide units; compounds which are monofunctional in the isocyanate-polyaddition reaction and contain terminal, hydrophilic ethylene oxide units, and mixtures thereof; and optionally, (iv) an organic compound which comprises a member selected from the group consisting of monoisocyanates or diisocyanates which contain ionic group(s) or potential ionic group(s); and compounds which are monofunctional or difunctional in the isocyanate-polyaddition reaction and contain ionic group(s) or potential ionic group(s), wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.1 to 3.0 on an equivalent basis; component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of the prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units; and component (iv) is treated with a neutralizing agent either before, during or after formation of the prepolymer in an amount sufficient to provide up to about 120 milliequivalents of ionic groups per 100 grams of said prepolymers, the amount of component (iii) and the neutralized portion of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer; (b) forming a dispersion of said prepolymer in water; and subsequently (c) chain extending said prepolymer to form said cross-linked urea-urethane with a sufficient amount of a polyfunctional amine chain extender having an average functionality (number of amine nitrogens per molecule) between about 2.2 and 6.0 to provide a ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine of between about 1.0:0.6 and 1.0:1.1.

Claim 2

Dependent Claim 375 words

A process for the preparation of a stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which comprises (a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight of up to about 25,000 by reacting (i) an organic polyisocyanate which contains at least two aliphatically or cycloaliphatically bound isocyanate groups, (ii) an organic compound which has at least two isocyanate-reactive groups, (iii) an organic compound which comprises a member selected from the group consisting of diisocyanates which contain lateral, hydrophilic ethylene oxide units; compounds which are difunctional in the isocyanate-polyaddition reaction and contain lateral, hydrophilic ethylene oxide units; monoisocyanates which contain terminal, hydrophilic ethylene oxide units; compounds which are monofunctional in the isocyanate-polyaddition reaction and contain terminal, hydrophilic ethylene oxide units, and mixtures thereof; and optionally, (iv) an organic compound which comprises a member selected from the group consisting of monoisocyanates or diisocyanates which contain ionic group(s) or potential ionic group(s); and compounds which are monofunctional or difunctional in the isocyanate-polyaddition reaction and contain ionic group(s) or potential ionic group(s), wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.1 to 3.0 on an equivalent basis; component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of the prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units; and component (iv) is treated with a neutralizing agent either before, during or after formation of the prepolymer in an amount sufficient to provide up to about 120 milliequivalents of ionic groups per 100 grams of said prepolymers, the amount of component (iii) and the neutralized portion of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer; (b) forming a dispersion of said prepolymer in water; and subsequently (c) chain extending said prepolymer to form said cross-linked urea-urethane with a sufficient amount of a polyfunctional amine chain extender having an average functionality (number of amine nitrogens per molecule) between about 2.2 and 6.0 to provide a ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine of between about 1.0:0.6 and 1.0:1.1.

Claim 3

Dependent Claim 12 words

The process of claim 1 wherein component (i) is an organic diisocyanate.

Claim 4

Dependent Claim 24 words

The process of claim 1 wherein component (ii) comprises a high molecular weight organic compound having a molecular weight from about 300 to 6,000.

Claim 5

Dependent Claim 35 words

The process of claim 3 wherein said high molecular weight component is a difunctional compound comprising a member selected from the group consisting of polyesters, polylactones, polycarbonates, polyethers, polythioethers, polyacetals, polyether esters and mixtures thereof.

Claim 6

Dependent Claim 28 words

The process of claim 3 wherein said high molecular weight component is a dihydroxy compound comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates.

Claim 7

Dependent Claim 20 words

The process of claim 5 wherein said high molecular weight component has a molecular weight from about 300 to 3000.

Claim 8

Dependent Claim 23 words

The process of claim 1 wherein component (ii) comprises a low molecular weight component having a molecular weight of up to about 300.

Claim 9

Dependent Claim 25 words

The process of claim 1 wherein component (iii) comprises a compound which is difunctional in the isocyanate-polyaddition reaction and contains lateral, hydrophilic ethylene oxide units.

Claim 10

Dependent Claim 25 words

The process of claim 1 wherein component (iii) comprises a compound which is monofunctional in the isocyanate-polyaddition reaction and contains terminal, hydrophilic ethylene oxide units.

Claim 11

Dependent Claim 89 words

The process of claim 1 wherein component (iii) corresponds to the formula H--Y'--X--Y--R" wherein R" represents a monovalent hydrocarbon radical having from 1 to 12 carbon atoms; X represents the radical obtained by removal of the terminal oxygen atom from a polyalkylene oxide chain having from about 5 to 90 chain members of which at least about 40% comprises ethylene oxide units and the remainder comprises other alkylene oxide units; Y represents oxygen or --NR'''--; Y' represents oxygen, --NH-- or --NR'''--; and R''' has the same definition as R".

Claim 12

Dependent Claim 83 words

The process of claim 10 wherein R" represents an unsubstituted alkyl radical having from 1 to 4 carbon atoms; X represents the radical obtained by removal of the terminal oxygen atom from a polyalkylene oxide chain having from about 20 to 70 chain members of which at least about 65% comprises ethylene oxide units and the remainder comprises other alkylene oxide units selected from the group consisting of propylene oxide, butylene oxide, styrene oxide and mixtures thereof; and Y and Y' represent oxygen.

Claim 13

Dependent Claim 15 words

The process of claim 11 wherein said other alkylene oxide units are propylene oxide units.

Claim 14

Dependent Claim 24 words

The process of claim 9 wherein component (iii) is present in an amount from 0.8 to 10% based on the weight of the prepolymer.

Claim 15

Dependent Claim 25 words

The process of claim 1 wherein component (iv) comprises compounds which are monofunctional in the isocyanate-polyaddition reaction and contain ionic group(s) or potential ionic group(s).

Claim 16

Dependent Claim 25 words

The process of claim 1 wherein component (iv) comprises compounds which are difunctional in the isocyanate-polyaddition reaction and contain ionic group(s) or potential ionic group(s).

Claim 17

Dependent Claim 26 words

The process of claim 1 wherein the ionic groups of component (iv) comprise a member selected from the group consisting of --COO.sup.⊕, --SO 3 .sup.⊕, ##STR29##

Claim 18

Dependent Claim 36 words

The process of claim 1 wherein the ionic groups are introduced into the prepolymer by sulfonic acid-containing diols which may be neutralized to form the ionic groups either before, during or after formation of the prepolymer.

Claim 19

Dependent Claim 36 words

The process of claim 1 wherein the ionic groups are introduced into the prepolymer by tertiary nitrogen-containing diols which may be neutralized to form the ionic groups either before, during or after formation of the prepolymer.

Claim 20

Dependent Claim 65 words

The process of claim 1 wherein the ionic groups are introduced into the prepolymer by hydroxycarboxylic acids of the formula (HO).sub.x Q(COOH).sub.y wherein Q represents a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y represent values from 1 to 3, said acids being neutralized to form the ionic groups either before, during or after formation of the prepolymer.

Claim 21

Dependent Claim 54 words

The process of claim 1 wherein the ionic groups are introduced into the prepolymer by dihydroxy alkanoic acids of the formula ##STR30## wherein Q' represents hydrogen or an alkyl group containing 1 to 8 carbon atoms, said acids being neutralized to form the ionic groups either before, during or after formation of the prepolymer.

Claim 22

Dependent Claim 9 words

The process of claim 20 wherein Q' represents methyl.

Claim 23

Dependent Claim 34 words

The process of claim 1 wherein said polyfunctional amine comprises a member selected from the group consisting of ethylene diamine, bis-(4-aminocyclohexyl)-methane, bis-(4-amino-3-methyl-cyclohexyl)methane, 1,6-diaminohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine, tetraethylenepentamine, pentamethylene hexamine and mixtures thereof.

Claim 24

Dependent Claim 34 words

The process of claim 1 wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine is between about 1.0:0.8 and 1.0:0.98 on an equivalent basis.

Claim 25

Dependent Claim 19 words

The process of claim 1 wherein the average functionality of the polyfunctional amine is between about 2.2 and 4.0.

Claim 26

Dependent Claim 373 words

A process for the preparation of a stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which comprises (a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight of up to about 25,000 by reacting (i) an organic diisocyanate which contains aliphatically or cycloaliphatically bound isocyanate groups, (ii) an organic dihydroxy compound with a molecular weight from about 300 to 6,000 comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates, (iii) an organic compound which is monofunctional or difunctional in the context of the isocyanatepolyaddition reaction and contains lateral or terminal, hydrophilic ethylene oxide units, and optionally, (iv) an organic compound comprising a member selected from the group consisting of sulfonic acid-containing diols, tertiary nitrogen-containing diols and hydroxy-carboxylic acids of the formula (HO).sub.x Q(COOH).sub.y wherein Q represents a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y represent values from 1 to 3, wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.2 to 2.0 on an equivalent basis; component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units; and component (iv) is treated with a neutralizing agent either before, during or after formation of said prepolymer in an amount sufficient to provide about 0 to 120 milliequivalents of ionic groups per 100 grams of said prepolymer, the amount of component (iii) and the neutralized portion of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer; (b) forming a dispersion of said prepolymer in water; and subsequently, (c) chain-extending said prepolymer to form said cross-linked urea-urethane with a polyfunctional amine comprising a member selected from the group consisting of ethylene diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine, and mixtures thereof, wherein said polyfunctional amine has an average functionality (number of amine nitrogens per molecule) of about 2.2 and 4.0 and wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine is between about 1.0:0.6 and 1.0:1.1.

Claim 27

Dependent Claim 373 words

A process for the preparation of a stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which comprises (a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight of up to about 25,000 by reacting (i) an organic diisocyanate which contains aliphatically or cycloaliphatically bound isocyanate groups, (ii) an organic dihydroxy compound with a molecular weight from about 300 to 6,000 comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates, (iii) an organic compound which is monofunctional or difunctional in the context of the isocyanatepolyaddition reaction and contains lateral or terminal, hydrophilic ethylene oxide units, and optionally, (iv) an organic compound comprising a member selected from the group consisting of sulfonic acid-containing diols, tertiary nitrogen-containing diols and hydroxy-carboxylic acids of the formula (HO).sub.x Q(COOH).sub.y wherein Q represents a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y represent values from 1 to 3, wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.2 to 2.0 on an equivalent basis; component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units; and component (iv) is treated with a neutralizing agent either before, during or after formation of said prepolymer in an amount sufficient to provide about 0 to 120 milliequivalents of ionic groups per 100 grams of said prepolymer, the amount of component (iii) and the neutralized portion of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer; (b) forming a dispersion of said prepolymer in water; and subsequently, (c) chain-extending said prepolymer to form said cross-linked urea-urethane with a polyfunctional amine comprising a member selected from the group consisting of ethylene diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine, and mixtures thereof, wherein said polyfunctional amine has an average functionality (number of amine nitrogens per molecule) of about 2.2 and 4.0 and wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine is between about 1.0:0.6 and 1.0:1.1.

Claim 28

Dependent Claim 31 words

The process of claim 25 wherein component (iv) comprises a dihydroxy alkanoic acid of the formula ##STR31## wherein Q' represents hydrogen or an alkyl group containing 1 to 8 carbon atoms.

Claim 29

Dependent Claim 42 words

The process of claim 26 wherein component (iv) is neutralized with a sufficient amount of a tertiary amine either before, during or after formation of the prepolymer to provide about 10 to 60 milliequivalents of ionic groups per 100 g of prepolymer.

Claim 30

Dependent Claim 11 words

The process of claim 27 wherein said tertiary amine is triethylamine.

Claim 31

Dependent Claim 21 words

The process of claim 25 wherein said organic diisocyanate comprises a member selected from the group consisting of bis-(4-isocyanatocyclohexyl)-methane and 1-isocyanate-3-isocyanatomethyl-3,5,5-trimethylcyclohexane.

Claim 32

Dependent Claim 349 words

A process for the preparation of stable, colloidal, aqueous dispersions of cross-linked urea-urethanes which comprises (a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight between about 600 and 12,000 by reacting (i) an organic diisocyanate comprising a member selected from the group consisting of bis-(4-isocyanatocyclohexyl)-methane and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, (ii) an organic dihydroxy compound with a molecular weight from about 300 to 3,000 comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates, (iii) an organic compound which is monofunctional or difunctional in the context of the isocyanate-poly-addition reaction and contains lateral or terminal, hydrophilic ethylene oxide units and (iv) a dihydroxy alkanoic acid of the formula ##STR32## wherein Q' represents hydrogen or an alkyl group containing 1 to 8 carbon atoms, and wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.2 to 2.0 on an equivalent basis; component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of the prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units; and component (iv) is neutralized with a tertiary amine either before, during or after formation of said prepolymer in an amount sufficient to provide about 10 to 60 milliequivalents of ionic groups per 100 grams of prepolymer, the amount of component (iii) and the neutralized amount of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer; (b) forming a dispersion of said prepolymer in water and; subsequently, (c) chain extending said prepolymer to form said cross-linked urea-urethane with a polyfunctional amine comprising a member selected from the group consisting of ethylene diamine, bis-(4-aminocyclohexyl)methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine and mixtures thereof, wherein said polyfunctional amine has an average functionality (number of amine nitrogens per molecule) between about 2.2 and 4.0 and wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogen of the polyfunctional amine is between about 1.0:0.8 and 1.0:0.98.

Claim 33

Dependent Claim 349 words

A process for the preparation of stable, colloidal, aqueous dispersions of cross-linked urea-urethanes which comprises (a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight between about 600 and 12,000 by reacting (i) an organic diisocyanate comprising a member selected from the group consisting of bis-(4-isocyanatocyclohexyl)-methane and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, (ii) an organic dihydroxy compound with a molecular weight from about 300 to 3,000 comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates, (iii) an organic compound which is monofunctional or difunctional in the context of the isocyanate-poly-addition reaction and contains lateral or terminal, hydrophilic ethylene oxide units and (iv) a dihydroxy alkanoic acid of the formula ##STR32## wherein Q' represents hydrogen or an alkyl group containing 1 to 8 carbon atoms, and wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.2 to 2.0 on an equivalent basis; component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of the prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units; and component (iv) is neutralized with a tertiary amine either before, during or after formation of said prepolymer in an amount sufficient to provide about 10 to 60 milliequivalents of ionic groups per 100 grams of prepolymer, the amount of component (iii) and the neutralized amount of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer; (b) forming a dispersion of said prepolymer in water and; subsequently, (c) chain extending said prepolymer to form said cross-linked urea-urethane with a polyfunctional amine comprising a member selected from the group consisting of ethylene diamine, bis-(4-aminocyclohexyl)methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine and mixtures thereof, wherein said polyfunctional amine has an average functionality (number of amine nitrogens per molecule) between about 2.2 and 4.0 and wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogen of the polyfunctional amine is between about 1.0:0.8 and 1.0:0.98.

Claim 34

Dependent Claim 9 words

The process of claim 30 wherein Q' represents methyl.

Claim 35

Dependent Claim 11 words

The process of claim 30 wherein said tertiary amine comprises triethylamine.

Claim 36

Dependent Claim 13 words

The process of claim 1, 25 and 30 wherein component (i) comprises bis-(4-isocyanatocyclohexyl)-methane.

Claim 37

Dependent Claim 375 words

A stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which is prepared by (a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight of up to about 25,000 from the reaction product of (i) an organic polyisocyanate which contains at least two aliphatically or cycloaliphatically bound isocyanate groups, (ii) an organic compound which has at least two isocyanate-reactive groups, (iii) an organic compound which comprises a member selected from the group consisting of diisocyanates which contain lateral, hydrophilic ethylene oxide units; compound which are difunctional in the isocyanate-polyaddition reaction and contain lateral, hydrophilic ethylene oxide units; monoisocyanates which contain terminal, hydrophilic ethylene oxide units; compounds which are monofunctional in the iso- cyanate-polyaddition reaction and contain terminal, hydrophilic ethylene oxide units, and mixtures thereof; and optionally, (iv) an organic compound whch comprises a member selected from the group consisting of monoisocyanates or diisocyanates which contain ionic group(s) or potential ionic group(s); and compounds which are monofunctional or difunctional in the isocyanate-polyaddition reaction and contain ionic group(s) or potential ionic group(s), wherein components (i), (ii), (iii) and (iv) and reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.1 to 3.0 on an equivalent basis; component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of the prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units; and component (iv) is treated with a neutralizing agent either before, during or after formation of the prepolymer in an amount sufficient to provide up to about 120 milliequivalents of ionic groups per 100 grams of said prepolymers, the amount of component (iii) and the neutralized portion of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer; (b) forming a dispersion of said prepolymer in water; and subsequently (c) chain extending said prepolymer to form said cross-linked urea-urethane with a sufficient amount of a polyfunctional amine chain extender having an average functionality (number of amine nitrogens per molecule) between about 2.2 and 6.0 to provide a ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine of between about 1.0:0.6 and 1.0:1.1.

Claim 38

Dependent Claim 375 words

A stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which is prepared by (a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight of up to about 25,000 from the reaction product of (i) an organic polyisocyanate which contains at least two aliphatically or cycloaliphatically bound isocyanate groups, (ii) an organic compound which has at least two isocyanate-reactive groups, (iii) an organic compound which comprises a member selected from the group consisting of diisocyanates which contain lateral, hydrophilic ethylene oxide units; compound which are difunctional in the isocyanate-polyaddition reaction and contain lateral, hydrophilic ethylene oxide units; monoisocyanates which contain terminal, hydrophilic ethylene oxide units; compounds which are monofunctional in the iso- cyanate-polyaddition reaction and contain terminal, hydrophilic ethylene oxide units, and mixtures thereof; and optionally, (iv) an organic compound whch comprises a member selected from the group consisting of monoisocyanates or diisocyanates which contain ionic group(s) or potential ionic group(s); and compounds which are monofunctional or difunctional in the isocyanate-polyaddition reaction and contain ionic group(s) or potential ionic group(s), wherein components (i), (ii), (iii) and (iv) and reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.1 to 3.0 on an equivalent basis; component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of the prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units; and component (iv) is treated with a neutralizing agent either before, during or after formation of the prepolymer in an amount sufficient to provide up to about 120 milliequivalents of ionic groups per 100 grams of said prepolymers, the amount of component (iii) and the neutralized portion of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer; (b) forming a dispersion of said prepolymer in water; and subsequently (c) chain extending said prepolymer to form said cross-linked urea-urethane with a sufficient amount of a polyfunctional amine chain extender having an average functionality (number of amine nitrogens per molecule) between about 2.2 and 6.0 to provide a ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine of between about 1.0:0.6 and 1.0:1.1.

Claim 39

Dependent Claim 12 words

The product of claim 34 wherein component (i) is an organic diisocyanate.

Claim 40

Dependent Claim 24 words

The product of claim 34 wherein component (ii) comprises a high molecular weight organic compound having a molecular weight from about 300 to 6,000.

Claim 41

Dependent Claim 35 words

The product of claim 36 wherein said high molecular weight component is a difunctional compound comprising a member selected from the group consisting of polyesters, polylactones, polycarbonates, polyethers, polythioethers, polyacetals, polyether esters and mixtures thereof.

Claim 42

Dependent Claim 28 words

The product of claim 36 wherein said high molecular weight component is a dihydroxy compound comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates.

Claim 43

Dependent Claim 20 words

The product of claim 38 wherein said high molecular weight component has a molecular weight from about 300 to 3,000.

Claim 44

Dependent Claim 23 words

The product of claim 34 wherein component (ii) comprises a low molecular weight component having a molecular weight of up to about 300.

Claim 45

Dependent Claim 25 words

The product of claim 34 wherein component (iii) comprises a compound which is difunctional in the isocyanate-polyaddition reaction and contains lateral, hydrophilic ethylene oxide units.

Claim 46

Dependent Claim 25 words

The product of claim 34 wherein component (iii) comprises a compound which is monofunctional in the isocyanate-polyaddition reaction and contains terminal, hydrophilic ethylene oxide units.

Claim 47

Dependent Claim 89 words

The product of claim 34 wherein component (iii) corresponds to the formula H--Y'--X--Y--R" wherein R" represents a monovalent hydrocarbon radical having from 1 to 12 carbon atoms; X represents the radical obtained by removal of the terminal oxygen atom from a polyalkylene oxide chain having from about 5 to 90 chain members of which at least about 40% comprises ethylene oxide units and the remainder comprises other alkylene oxide units; Y represents oxygen or --NR'''--; Y' represents oxygen, --NH-- or --NR'''--; and R''' has the same definition as R".

Claim 48

Dependent Claim 83 words

The product of claim 43 wherein R" represents an unsubstituted alkyl radical having from 1 to 4 carbon atoms; X represents the radical obtained by removal of the terminal oxygen atom from a polyalkylene oxide chain having from about 20 to 70 chain members of which at least about 65% comprises ethylene oxide units and the remainder comprises other alkylene oxide units selected from the group consisting of propylene oxide, butylene oxide, styrene oxide and mixtures thereof; and Y and Y' represent oxygen.

Claim 49

Dependent Claim 15 words

The product of claim 44 wherein said other alkylene oxide units are propylene oxide units.

Claim 50

Dependent Claim 24 words

The product of claim 45 wherein component (iii) is present in an amount from 0.8 to 10% based on the weight of the prepolymer.

Claim 51

Dependent Claim 25 words

The process of claim 34 wherein component (iv) comprises compounds which are monofunctional in the isocyanate-polyaddition reaction and contain ionic group(s) or potential ionic group(s).

Claim 52

Dependent Claim 25 words

The product of claim 34 wherein component (iv) comprises compounds which are difunctional in the isocyanate-polyaddition reaction and contain ionic group(s) or potential ionic group(s).

Claim 53

Dependent Claim 27 words

The product of claim 34 wherein the ionic groups of component (iv) comprise a member selected from the group consisting of --COO.sup.⊖, --SO 3 .sup.⊖, ( ##STR33##

Claim 54

Dependent Claim 36 words

The product of claim 34 wherein the ionic groups are introduced into the prepolymer by sulfonic acid-containing diols which may be neutralized to form the ionic groups either before, during or after formation of the prepolymer.

Claim 55

Dependent Claim 36 words

The product of claim 34 wherein the ionic groups are introduced into the prepolymer by tertiary nitrogen-containing diols which may be neutralized to form the ionic groups either before, during or after formation of the prepolymer.

Claim 56

Dependent Claim 65 words

The product of claim 34 wherein the ionic groups are introduced into the prepolymer by hydroxycarboxylic acids of the formula (HO).sub.x Q(COOH).sub.y wherein Q represents a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y represent values from 1 to 3, said acids being neutralized to form the ionic groups either before, during or after formation of the prepolymer.

Claim 57

Dependent Claim 54 words

The product of claim 34 wherein the ionic groups are introduced into the prepolymer by dihydroxy alkanoic acids of the formula ##STR34## wherein Q' represents hydrogen or an alkyl group containing 1 to 8 carbon atoms, said acids being neutralized to form the ionic groups either before, during or after formation of the prepolymer.

Claim 58

Dependent Claim 9 words

The product of claim 53 wherein Q' represents methyl.

Claim 59

Dependent Claim 35 words

The product of claim 34 wherein said polyfunctional amine comprises a member selected from the group consisting of ethylene diamine, bis-(4-aminocyclohexyl)-methane, bis-(4-amino-3-methyl-cyclohexyl)-methane, 1,6-diaminohexane, 1-amino-3-amino-methyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentamethylene hexamine, and mixtures thereof.

Claim 60

Dependent Claim 34 words

The product of claim 34 wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine is between about 1.0:6.8 and 1.0:0.98 on an equivalent basis.

Claim 61

Dependent Claim 19 words

The product of claim 34 wherein the average functionality of the polyfunctional amine is between about 2.2 and 4.0.

Claim 62

Dependent Claim 371 words

A stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which is prepared by (a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight of up to about 25,000 from the reaction product of (i) an organic diisocyanate which contains aliphatically or cycloaliphatically bound isocyanate groups, (ii) an organic dihydroxy compound with a molecular weight from about 300 to 6,000 comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates, (iii) an organic compound which is monofunctional or difunctional in the context of the isocyanate-polyaddition reaction and contains lateral or terminal, hydrophilic ethylene oxide units, and optionally, (iv) an organic compound comprising a member selected from the group consisting of sulfonic acid-containing diols, tertiary nitrogen-containing diols and hydroxy-carboxylic acids of the formula (HO).sub.x Q(COOH).sub.y wherein Q represents a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y represent values from 1 to 3, wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.2 to 2.0 on an equivalent basis; component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units; and component (iv) is treated with a neutralizing agent either before, during or after formation of said prepolymer in an amount sufficient to provide about 0 to 120 milliequivalents of ionic groups per 100 grams of said prepolymer, the amount of component (iii) and the neutalized portion of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer; (b) forming a dispersion of said prepolymer in water and; subsequently, (c) chain-extending said prepolymer to form said cross-linked urea-urethane with a polyfunctional amine comprising a member selected from the group consisting of ethylene diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine, and mixtures thereof, wherein said polyfunctional amine has an average functionality (number of amine nitrogens per molecule) between about 2.2 and 4.0 and wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amines is between 1.0:0.6 and 1.0:1.1.

Claim 63

Dependent Claim 371 words

A stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which is prepared by (a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight of up to about 25,000 from the reaction product of (i) an organic diisocyanate which contains aliphatically or cycloaliphatically bound isocyanate groups, (ii) an organic dihydroxy compound with a molecular weight from about 300 to 6,000 comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates, (iii) an organic compound which is monofunctional or difunctional in the context of the isocyanate-polyaddition reaction and contains lateral or terminal, hydrophilic ethylene oxide units, and optionally, (iv) an organic compound comprising a member selected from the group consisting of sulfonic acid-containing diols, tertiary nitrogen-containing diols and hydroxy-carboxylic acids of the formula (HO).sub.x Q(COOH).sub.y wherein Q represents a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y represent values from 1 to 3, wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.2 to 2.0 on an equivalent basis; component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units; and component (iv) is treated with a neutralizing agent either before, during or after formation of said prepolymer in an amount sufficient to provide about 0 to 120 milliequivalents of ionic groups per 100 grams of said prepolymer, the amount of component (iii) and the neutalized portion of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer; (b) forming a dispersion of said prepolymer in water and; subsequently, (c) chain-extending said prepolymer to form said cross-linked urea-urethane with a polyfunctional amine comprising a member selected from the group consisting of ethylene diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine, and mixtures thereof, wherein said polyfunctional amine has an average functionality (number of amine nitrogens per molecule) between about 2.2 and 4.0 and wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amines is between 1.0:0.6 and 1.0:1.1.

Claim 64

Dependent Claim 31 words

The product of claim 58 wherein component (iv) comprises a dihydroxy alkanoic acid of the formula ##STR35## wherein Q' represents hydrogen or an alkyl group containing 1 to 8 carbon atoms.

Claim 65

Dependent Claim 41 words

The product of claim 59 wherein component (iv) is neutralized with a sufficient amount of a tertiary amine either before, during or after formation of the prepolymer to provide about 10 to 60 milliequivalents of ionic groups per 100 of prepolymer.

Claim 66

Dependent Claim 11 words

The product of claim 60 wherein said tertiary amine is triethylamine.

Claim 67

Dependent Claim 21 words

The product of claim 58 wherein said organic diisocyanate comprises a member selected from the group consisting of bis-(4-isocyanatocyclohexyl)-methane and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane.

Claim 68

Dependent Claim 349 words

A stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which is prepared by (a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight between about 600 and 12,000 from the reaction product of (i) an organic diisocyanate comprising a member selected from the group consisting of bis-(4-isocyanatocyclohexyl)-methane and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, (ii) an organic dihydroxy compound with a molecular weight from about 300 to 3,000 comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates, (iii) an organic compound which is monofunctional or difunctional in the context of the isocyanate-polyaddition reaction and contains lateral or terminal, hydrophilic ethylene oxide units, and (iv) a dihydroxy alkanoic acid of the formula ##STR36## wherein Q' represents hydrogen or an alkyl group containing 1 to 8 carbon atoms, and wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.2 to 2.0 on an equivalent basis; component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of the prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units; and component (iv) is neutralized with a tertiary amine either before, during or after formation of said prepolymer in an amount sufficient to provide about 10 to 60 milliequivalents of ionic group per 100 grams of prepolymer, the amount of component (iii) and the neutralized amount of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer; (b) forming a dispersion of said prepolymer in water; and subsequently, (c) chain extending said prepolymer to form said cross-linked urea-urethane with a polyfunctional amine comprising a member selected from the group consisting of ethylene diamine, bis-(4-aminocyclohexyl)-methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine, and mixtures thereof, wherein said polyfunctional amine has an average functionality (number of amine nitrogens per molecule) between about 2.2 and 4.0 and wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine is between about 1.0:0.8 and 1.0:0.98.

Claim 69

Dependent Claim 349 words

A stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which is prepared by (a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight between about 600 and 12,000 from the reaction product of (i) an organic diisocyanate comprising a member selected from the group consisting of bis-(4-isocyanatocyclohexyl)-methane and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, (ii) an organic dihydroxy compound with a molecular weight from about 300 to 3,000 comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates, (iii) an organic compound which is monofunctional or difunctional in the context of the isocyanate-polyaddition reaction and contains lateral or terminal, hydrophilic ethylene oxide units, and (iv) a dihydroxy alkanoic acid of the formula ##STR36## wherein Q' represents hydrogen or an alkyl group containing 1 to 8 carbon atoms, and wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.2 to 2.0 on an equivalent basis; component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of the prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units; and component (iv) is neutralized with a tertiary amine either before, during or after formation of said prepolymer in an amount sufficient to provide about 10 to 60 milliequivalents of ionic group per 100 grams of prepolymer, the amount of component (iii) and the neutralized amount of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer; (b) forming a dispersion of said prepolymer in water; and subsequently, (c) chain extending said prepolymer to form said cross-linked urea-urethane with a polyfunctional amine comprising a member selected from the group consisting of ethylene diamine, bis-(4-aminocyclohexyl)-methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine, and mixtures thereof, wherein said polyfunctional amine has an average functionality (number of amine nitrogens per molecule) between about 2.2 and 4.0 and wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine is between about 1.0:0.8 and 1.0:0.98.

Claim 70

Dependent Claim 9 words

The product of claim 63 wherein Q' represents methyl.

Claim 71

Dependent Claim 11 words

The product of claim 63 wherein said tertiary amine comprises triethylamine.

Claim 72

Dependent Claim 15 words

A coating on a substrate prepared from the product of claim 34, 59 or 63.

Claim 73

Dependent Claim 12 words

A film prepared from the product of claim 34, 59 or 63.

Claim 74

Dependent Claim 12 words

An adhesive prepared from the product of claim 34, 59 or 63.

Claim 75

Dependent Claim 10 words

The product of claim 1, wherein component (i) comprises bis-(4-isocyanatocyclohexyl)-methane.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1986-10-03	1987-04-04	1987-10-04	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1990-10-03	1991-04-04	1991-10-04	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1994-10-03	1995-04-04	1995-10-04	$7700.00	Window Closed / Lapsed

Stable, colloidal, aqueous dispersions of cross-linked urea-urethane polymers and their method of production

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