Aqueous dispersion, internally silylated and dispersed polyurethane resins, and surfaces containing same

Claim 2

Reaction product of Claim 1, wherein an additional reactant is present which is one or more hydrophilic additives selected from the group consisting of polyethers with a predominant amount of ethylene oxide moieties, polyoxyethylene homopolymer and monofunctional polyethers and polyether polyols and active hydrogen-containing organic compounds having one or two active hydrogens per molecule and having ionic groups or precursor ionic groups.

Claim 3

Reaction product of claim 2, wherein the monofunctional polyethers are selected from diisocyanates which contain lateral, hydrophilic ethylene oxide units, and organic compounds which are difunctional in the isocyanate-polyaddition reaction and contain lateral hydrophilic ethylene oxide units, monoisocyanates which contain terminal, hydrophilic ethylene oxide units, organic compounds which are monofunctional in the isocyanate-polyaddition reaction, and that have terminal hydrophilic ethylene oxide units and mixtures of these materials.

Claim 4

Reaction product of claim 2, which has an additional monomer which is a low molecular weight active hydrogen-containing compound having at least 2 active hydrogens per molecule and which constitutes at least 20 percent of the polymerized reaction product.

Claim 5

Reaction group of claim 2, wherein the ionic groups are selected from the group consisting of cationic groups, anionic groups, or mixtures thereof.

Claim 6

Reaction product of claim 2, wherein with the presence of the ionic hydrophilic additive the difunctional organosilane is nearly completely reacted with the polyisocyanate before the addition of the ionic hydrophilic additive.

Claim 7

Reaction product of claim 2, wherein with the presence of the hydrophilic additive, any ionic or precursor ionic hydrophilic additive on the reaction product is neutralized.

Claim 8

Reaction product of claim 2, wherein the hydrophilic agent is comprised of a polyoxyethylene polyol homopolymer and a divalent organic compound having anionic groups and the ratio of the ethylene oxide-containing hydrophilic agent to the anionic group-containing agent is such that the anionic-containing organic compound constitutes the major amount while the ethylene oxide-containing compound constitutes the minor amount.

Claim 9

Reaction product of claim 2, wherein the total amount of hydrophilic agent is at least around 3 weight percent and not greater than about 10 weight percent.

Claim 10

The reaction product of claim 2, wherein the total amount of isocyanate-reactive organosilanes have organic moieties having functionalities which react with the isocyanate where these functionalities are selected from the group consisting of hydroxyl, mercaptan: primary, secondary amine; and ureido.

Claim 11

Reaction product of claim 10, wherein the difunctional isocyanate reactive organosilane has saturated organic moieties.

Claim 12

Reaction product of claim 10, wherein the difunctional isocyanate organosilane reactant has the formula: where R y and R' z are organic moieties having 1 to 20 carbon atoms such as alkyls having 1 to 6 carbon atoms and aryls, alkylaryls and arylalkyls and y and z are integers so that y is equal to 0 or 1 and z is equal to 1 or 2, where both of R y and R' z organic moieties having one isocyanate reactable group or where R' z has two and/or more reactable isocyanate-reactable groups, when y = 0 or when the R y organic moiety has no such reactable groups and where (OR x ) is the hydrolyzable or hydrolyzed group such as alkoxy, alkyloxy, hydroxy, and the like and R x is methyl, ethyl, n-propyl or hydrogen.

Claim 13

Reaction product of claim 2, wherein the organic polyisocyanate is a cycloaliphatic diisocyanate.

Claim 14

Reaction product of claim 2, wherein the organic compound with difunctional active hydrogens is a polyester diol.

Claim 15

Reaction product of claim 2, wherein the polyoxyethylene polyol homopolymer has a molecular weight in the range of 1,000 to 4,000.

Claim 16

Reaction product of claim 2, where the organo diisocyanate is an excess amount to the organic compound with active hydrogens to produce a prepolymer capable of chain extension.

Claim 17

Reaction product of claim 1, wherein the organosilane with at least two isocyanate reactable groups is present in a predominant amount of the other silanes and in an amount greater than 0.05 weight percent of the total urethane formulation but less than the amount that causes threedimensional gelation.

Claim 18

Reaction product of claim 1, wherein an organic solvent is present that is unreactive towards isocyanate groups for the polymer and includes those selected from the group consisting of ketones, tertiary alcohols, esters, ethers, amides, hydrocarbons, chlorohydrocarbons and chlorocarbons.

Claim 19

An aqueous dispersion of an ungelled polyurethane reaction product having silyl groups formed from (a) organic polyisocyanate, (b) active hydrogen-containing material having at least two active hydrogens per molecule, (c) organosilane having at least one isocyanate reactable group on one or more organic moieties of the organosilane and having at least one hydrolyzed or hydrolyzable group associated with the silicon atom, and the dispersion comprises water in an effective amount to form an oil-in-water dispersion of the isocyanate containing polymer characterized in that a predominant amount of the organosilane has more than one isocyanate reactable group and the dispersion has one or more external emulsifiers with an effective HLB and in an effective amount to disperse the polymer in water, and where the dispersion has a pH of at least around 7 when the silyl concentration is greater than around 0.1 weight percent and to 8.5 and greater when the silyl concentration is greater than 0.4 percent where the weight percents are of water in the dispersion so that a substantial amount of the pendant lateral silyl groups predominantly extending from the backbone chain of the polyurethane reaction product, are present as siliconate anions to deter formation of the siloxanes, and wherein a predominant amount of said organic polyisocyanate and of said organic compound with at least two reactive hydrogens per molecule are difunctional in the isocyanate-polyaddition reaction, and wherein the organosilane is present as a comonomer in forming the polymer or as the chain-extender, where the polymer is a prepolymer.

Claim 20

An aqueous dispersion of an ungelled polyurethane reaction product having silyl groups being the reaction product of (1) an isocyanate-containing prepolymer formed from (a) organic polyisocyanate, (b) active hydrogen-containing material having at least two active hydrogens per molecule, (c) organosilane having at least one isocyanate reactable group on one or more organic moieties of the organosilane and having at least one hydrolyzed or hydrolyzable group associated with the silicon atom, a predominant amount of the organosilane having more than one isocyanate reactable group, (d) hydrophilic additives as further reactants selected from the group consisting of polyethers having a predominant amount of ethylene oxide moieties polyoxyethylene polyol homopolymers, monofunctional polyethers, monofunctional polyether polyols, diisocyanates having lateral hydrophilic ethylene oxide units, organic compounds which are difunctional in the isocyanate polyaddition reaction and contain lateral hydrophilic ethylene oxide units, monoisocyantes which contain terminal, hydrophilic ethylene oxide units, compounds which are monofunctional in the isocyanate polyaddition reaction and contain terminal hydrophilic ethylene oxide units, organic compounds having at least two active hydrogens per molecule having ionic or precursor ionic groups and mixtures thereof, and (2) a neutralizing agent in an effective amount to neutralize a substantial amount of precursor ionic groups of the hydrophilic agent into ionic groups, and (3) chain extender in an amount to react with a substantial number of the isocyanate groups on the isocyanate-containing prepolymer, wherein the dispersion comprises water in an effective amount to form an oil-in-water dispersion of the isocyanate containing polymer, wherein said organic polyisocyanate and said organic compound with at least two reactive hydrogens per molecule are predominantly difunctional in the isocyanate-polyaddition reaction and wherein the reaction product has pendant and lateral silyl groups, predominantly extending from the backbone chain of the polyurethane reaction product, so that when the reaction product is dispersed in water at a pH of at least around 7, when the silyl concentration is greater than around 0.1 weight percent of the water, a substantial number of silyl groups become siliconate anions selected from the group consisting of - (SiO⁻), - (SiO = ), (SiO₃ ≡ ) and mixtures thereof.

Claim 21

Aqueous dispersion of claim 19, wherein the external emulsifier is a hydrophilic additive selected from the group consisting of polyether having ethylene oxide moieties, polyoxyethylene polyol homopolymers, monofunctional polyethers, monofunctional polyether polyols, diisocyanate having lateral hydrophilic ethylene oxide units, organic compounds which are difunctional in the isocyanate polyaddition reaction and contain lateral hydrophilic ethylene oxide units, monoisocyanate which contain terminal, hydrophilic ethylene oxide units, compounds which are monofunctional in the isocyanate polyaddition reaction and contain terminal hydrophilic ethylene oxide units, organic compounds having at least two active hydrogens per molecule having ionic groups and mixtures thereof.

Claim 22

Aqueous dispersion of claim 19 or 20, wherein a pH modifier is present in an effective amount to give a pH of at least around 7 for amounts of silyl groups on the polymer greater than 0.1 weight percent and to 8.5 and greater for silyl amounts greater than 0.4 weight percent where the weight percents are based on water in the dispersion.

Claim 23

Aqueous dispersion of claims 19 or 20, wherein an organic solvent is present that is unreactive towards isocyanate groups and that is water soluble and includes those selected from the group consisting of ketones and alcohols.

Claim 24

Dispersion of claim 20, wherein the monofunctional polyethers are selected from diisocyanates which contain lateral, hydrophilic ethylene oxide units, and organic compounds which are difunctional in the isocyanate-polyaddition reaction and contain lateral, hydrophilic, ethylene oxide units, monoisocyanates which contain terminal hydrophilic ethylene oxide units, organic compounds which are monofunctional in the isocyanate-polyaddition reaction and have terminal, hydrophilic, ethylene oxide units and mixtures of these materials.

Claim 25

Dispersion of claim 20, which has an additional monomer which is a low molecular weight, active hydrogen-containing compound having at least 2 active hydrogens per molecule and which constitutes at least 20 percent by weight of the prepolymer reactants.

Claim 26

Dispersion of claim 20, wherein the ionic groups are selected from the group consisting of cationic groups, anionic groups, or mixtures thereof.

Claim 27

Dispersion of claim 20, wherein the hydrophilic additive is comprised of a polyoxyethylene polyol homopolymer and a divalent organic compound having anionic groups and the ratio of the ethylene oxide-containing hydrophilic agent to the anionic group containing agent is such that the anionic containing organic compound constitutes the major amount while the ethylene oxide-containing compound constitutes the minor amount.

Claim 28

Dispersion of claim 20, wherein the total amount of hydrophilic additive is at least 3 weight percent and not greater than 10 weight percent.

Claim 29

Dispersion of claims 19 to 28, wherein the organosilane with at least two isocyanate groups is present in an amount greater than 0.05 weight percent of the total urethane formulation but less than the amount that causes threedimensional gelation.

Claim 30

Dispersion of claims 19 or 20, wherein the isocyanate reactive organosilanes having functionalities on the organic moiety which react with the isocyanate are selected from the group consisting of hydroxyl, mercaptan, primary, secondary or tertiary amine and ureido.

Claim 31

Dispersion of claim 30, wherein the difunctional isocyanate organosilane has the formula: where R y and R' z are organic moieties having 1 to 20 carbon atoms such as alkyls having 1 to 6 carbon atoms and aryls, alkylaryls and arylalkyls and y and z are integers so that y is equal to 0 or 1 and z is equal to 1 or 2, where one or both of R y and R' z organic moieties having one isocyanate reactable group or where R' z has two and/or more isocyanate-reactable groups, when y = 0 or when the R y organic moiety has no such reactable groups and where (OR x ) is the hydrolyzable or hydrolyzed group such as alkoxy, acyloxy, hydroxy, and the like and R x is methyl, ethyl, n-propyl or hydrogen.

Claim 32

A process of preparing an aqueous dispersion of ungelled silylated polyurethane reaction product by preparing polymer from (a) organic polyisocyanate, (b) active hydrogen-containing material (c) organosilane having at least one isocyanate reactable group on one or more organic moieties of the organosilane and having at least one hydrolyzed or hydrolyzable group associated with the silicon atom, wherein the materials are reacted at a reaction temperature less than 200 o C in non-aqueous environment for a period of time to obtain a predominantly linear polymer, combining the polymer with a sufficient amount of water to form an oil-in-water dispersion, characterized in that a predominant amount of the organosilane has more than one isocyanate reactable group, and by maintaining the pH of the aqueous dispersion to of at least about 7 when the amount of silyl groups on the polymer is greater than about 0.1 weight percent to 8.5 and greater when the silyl concentration is greater than 0.4 weight percent, where the weight percents are of the water in the dispersion so that a substantial amount of the pendant and lateral silyl groups predominantly extending from the backbone chain of the polyurethane reaction product, are converted to siliconate ions and wherein the organic polyisocyanate and the hydrogen containing material are predominantly difunctional in the isocyanate polyaddition reaction.

Claim 33

A process of preparing an aqueous dispersion of claim 32 by preparing a polymer from (a) organic polyisocyanate, (b) active hydrogen-containing material having at least two active hydrogens per molecule (c) organosilane having at least one isocyanate reactable group on one or more organic moieties of the organosilane and having at least one hydrolyzed or hydrolyzable group associated with the silicon atom, wherein the materials are reacted at a reaction temperature less than 200 o C in non-aqueous environment for a period to obtain a predominantly linear polymer, combining the polymer with a sufficient amount of water to form an oil- in-water dispersion characterized by using as a further reactant a hydrophilic additive neutralizing any precursor ionic groups of the hydrophilic additive prior combining the polymer with water, maintaining the pH of the aqueous dispersion to at least about 7 when the amount of silyl groups on the polymer is greater than about 0.1 weight percent of the water in the dispersion so that a substantial amount of pendant and lateral silyl groups predominantly extending from the backbone chain of the polyurethane reaction product are converted to siliconate ions and wherein the organic polyisocyanate and the hydrogen-containing material are predominantly difunctional in the isocyanate polyaddition reaction.

Claim 34

Process of claim 33, wherein the hydrophilic additive is used as a dual hydrophilic additive system having a major amount of the ionic containing organic compound having at least two active hydrogens and a minor amount of the polyoxyethylene polyol homopolymer wherein the total amount of the hydrophilic additive is in the range of about 3 to about 10 weight percent of the prepolymer.

Claim 35

Process of claims 32 or 33, wherein an organic solvent is present that is unreactive towards isocyanate groups and that is water soluble and includes those selected from the group consisting of ketones and alcohols.