CA2266207A1 - Aqueous two-component coating compositions - Google Patents
Aqueous two-component coating compositions Download PDFInfo
- Publication number
- CA2266207A1 CA2266207A1 CA002266207A CA2266207A CA2266207A1 CA 2266207 A1 CA2266207 A1 CA 2266207A1 CA 002266207 A CA002266207 A CA 002266207A CA 2266207 A CA2266207 A CA 2266207A CA 2266207 A1 CA2266207 A1 CA 2266207A1
- Authority
- CA
- Canada
- Prior art keywords
- groups
- composition
- weight
- polyisocyanate
- compounds
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
- C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
- C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
Abstract
The present invention relates to aqueous two-component compositions containing a) compounds which are substantially free from isocyanate groups, have an alkoxysilane group content (calculated as Si, MW 28) of 1 to 6% by weight, based on the weight of the compounds, and contain sufficient chemically incorporated hydrophilic groups to form a stable dispersion with water, wherein the alkoxysilane groups are incorporated as the reaction products of i) a polyisocyanate component having a minimum average functionality of 2.4 and containing at least 50% by weight of polyisocyanate adducts and ii) compounds containing secondary amino groups and alkoxysilane groups, and b) polyhydroxy compounds containing ester and/or carbonate groups and having a urethane group content of less than 5% by weight, based on the weight of the polyhydroxy compounds.
The present invention also relates to coatings, adhesives and sealants prepared from these aqueous compositions and to compounds a) containing urea and alkoxysilane groups.
The present invention also relates to coatings, adhesives and sealants prepared from these aqueous compositions and to compounds a) containing urea and alkoxysilane groups.
Description
Mo4795 AQUEOUS TWO-COMPONENT
COATING COMPOSITIONS
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to aqueous two-component coating compositions containing water dispersible compounds, which contain alkoxysilane groups and are substantially free from isocyanate groups, and aqueous polyhydroxy polyesters.
Description of the Prior Art Two-component aqueous compositions containing a water dispersible polyisocyanate component and various water dispersible or water soluble polyhydroxy components are known and described in U.S.
Patents 5,075,370, 5,389,718, 5,387,642, 5,372,875, 5,336,711, 5,344,873 and 5,459,197. The aqueous compositions may be used for a wide range of commercial applications such as adhesives, sealants or coatings for various substrates including textile fabrics, plastic, wood, glass fibers and metals. Chemical resistance, abrasion resistance, toughness, tensile strength) elasticity and durability are among the many desirable properties of these coatings.
One of the known two-component compositions is based on water dispersible polyisocyanates and aqueous polyhydroxy compounds containing ester and/or carbonate groups. One disadvantage of these systems is that the resulting coatings do not possess adequate hardness for certain applications. In addition, it is advantageous in certain applications to avoid the use of polyisocyanate resins for environmental and industrial hygiene reasons.
Accordingly, it is an object of the present invention to provide two-component aqueous compositions containing new non-isocyanate co-Mo4795 _2_ reactants, which can be used to prepare coatings having improved hardness.
This object may be achieved with the aqueous two-component coating compositions according to the present invention, which are based on water dispersible compounds containing urea and alkoxysilane groups and an aqueous polyhydroxy compound containing ester and/or carbonate groups. These compounds containing urea and alkoxysilane groups may be prepared by reacting a polyisocyanate component with compounds containing secondary amino groups and alkoxysilane groups.
SUMMARY OF THE INVENTION
The present invention relates to aqueous two-component compositions containing a) compounds which are substantially free from isocyanate groups, have an alkoxysilane group content (calculated as Si, MW 28) of 1 to 6% by weight, based on the weight of the compounds, and contain sufficient chemically incorporated hydrophilic groups to form a stable dispersion with water, wherein the alkoxysilane groups are incorporated as the reaction products of i) a polyisocyanate component having a minimum average functionality of 2.4 and containing at least 50% by weight of polyisocyanate adducts and ii) amino compounds corresponding to the formula I
(I) HN-(CH2)~ Si-(X~
wherein Mo4795 _3_ X represents identical or different organic groups which are inert to isocyanate groups below 100°C, provided that at least one of these groups is an alkoxy group, R, represents an organic group which is inert to isocyanate groups at a temperature of 100°C or less, and n is an integer from 1 to 8, and a) polyhydroxy compounds containing ester and/or carbonate groups and having a urethane group content of less than 5% by weight, based on the weight of the polyhydroxy compounds.
The present invention also relates to coatings, adhesives and sealants prepared from these aqueous compositions and to compounds a) containing urea and alkoxysilane groups.
DETAILED DESCRIPTION OF THE INVENTION
Compounds a) containing urea and alkoxysilane groups are based on the reaction products of polyisocyanates, amino-functional silanes and compounds containing hydrophilic groups, such as non-ionic, anionic and/or cationic groups. The silanes are incorporated through the formation of urea groups, while the hydrophilic groups are preferably incorporated through the formation of urethane groups. The compounds according to the invention are substantially free from isocyanate groups, which means that they contain less than 0.1 % by weight of isocyanate groups, based on the weight of the compounds.
Suitable compounds containing alkoxysilane groups and amino groups include those corresponding to formula I wherein X represents identical or different organic groups which are inert to isocyanate groups below 100°C, provided that at least one of these groups is an alkoxy or acyloxy group, preferably alkyl or alkoxy groups having 1 to 4 carbon atoms and more preferably alkoxy groups, Mo4795 -4-R, represents an organic group which is inert to isocyanate groups at a temperature of 100°C or less, preferably an alkyl, cycloalkyl or aromatic group having 1 to 12, preferably 1 to 8 carbon atoms, or a group corresponding to the formula -(CH2)~ Si-(X)3 (II) and n is an integer from 1 to 8, preferably 2 to 4 and more preferably 3.
Especially preferred are compounds in which X represents methoxy, ethoxy groups or propoxy groups, more preferably methoxy or ethoxy groups and most preferably methoxy groups, and n is 3.
Examples of suitable aminoalkyl alkoxysilanes of formula I
containing secondary amino groups include N-phenylaminopropyl-trimethoxysilane (available as A-9669 from OSI Specialties, Witco), bis-(y-trimethoxysilylpropyl)amine (available as A-1170 from OSI Specialties, Witco), N-cyclohexylaminopropyltriethoxy-silane, N-methylaminopropyl-trimethoxysilane and the corresponding alkyl diethyoxy and dimethoxy silanes.
A special group of compounds containing alkoxysilane groups are those which also contain aspartate groups, such as those corresponding to formula III
Z-CHR3 CR4 NH-(CH2)~ Si-(X)3 (III) wherein Mo4795 -5-X and n are as defined above, Z represents COORS or an aromatic ring, preferably COORS, RZ and RS are identical or different and represent organic groups which are inert to isocyanate groups at a temperature of 100°C or less, preferably alkyl groups having 1 to 9 carbon atoms, more preferably methyl, ethyl or butyl groups and R3 and R4 are identical or different and represent hydrogen or organic groups which are inert to isocyanate groups at a temperature of 100°C or less, preferably hydrogen.
The compounds of formula III are prepared by reacting aminoalkyl alkoxysilanes corresponding to the formula H2N-(CH2)n Si-(X)3 (N) with malefic, fumaric or cinnamic acid esters corresponding to the formula Z-CR3=CR4-COOR2 (V).
Examples of suitable aminoalkyl alkoxysilanes of formula IV include 2-aminoethyl-dimethylrnethoxy-silane; 6-aminohexyl-tributoxysilane; 3-aminopropyl-trimethoxysilane; 3-aminopropyl-triethoxysilane; 3-aminopropyl-methyldiethoxysilane; 5-aminopentyl-trimethoxysilane; 5-aminopentyl-triethoxysilane and 3-aminopropyl-triisopropoxysilane. 3-aminopropyl-trimethoxysilane and 3-aminopropyl-triethoxysilane are particularly preferred.
Examples of optionally substituted malefic, fumaric or cinnamic acid esters suitable for use in the preparation of the polyaspartates include Mo4795 -6-dimethyl, diethyl, dibutyl (e.g., di-n-butyl), diamyl, di-2-ethylhexyl esters and mixed esters based on mixture of these and/or other alkyl groups of malefic acid and fumaric acid; the methyl, ethyl and butyl esters of cinnamic acid; and the corresponding malefic, fumaric and cinnamic acid esters substituted by methyl in the 2- and/or 3-position. The dimethyl esters of malefic acid are preferred and the diethyl and dibutyl esters are especially preferred.
The reaction of primary amines with malefic) fumaric or cinnamic acid esters to form the aspartates of formula III is known and described, e.g. in U.S. Patent 5,364,955, which is herein incorporated by reference.
The preparation of the aspartates may be carried out, for example, at a temperature of 0 to 100°C using the starting materials in such proportions that ~at least 1, preferably 1, olefinic double bond is present for each primary amino group. Excess starting materials may be removed by distillation after the reaction. The reaction may be carried out with or without a solvent, but the use of a solvent is less preferred. If a solvent is used, dioxane is an example of a suitable solvent.
The compounds containing alkoxysilane groups and amino groups are reacted in an amount sufficient to incorporate 1 to 6% by weight, preferably 2 to 6% by weight and more preferably 2 to 5% by weight of alkoxysilane groups (calculated as Si, MW 28), based on the weight of the compounds containing urea and alkoxysilane groups. The compounds of formula III are colorless to pale yellow. They may be reacted with polyisocyanate component i) to form the compounds containing urea and alkoxysilane groups without further purification.
In accordance with the present invention the special type of urea groups formed by the reaction of the compounds containing alkoxysilane groups and aspartate groups with the polyisocyanate component may be converted to hydantoin groups in known manner by heating the Mo4795 -7-compounds at elevated temperatures, optionally in the presence of a catalyst. Therefore, the term "urea groups" is also intended to include other compounds containing the group, N-CO-N, such as hydantoin groups.
The polyisocyanate component for preparing the compounds containing urea and alkoxysilane groups has a minimum average functionality of 2.4, preferably to 2.6 and more preferably 2.8, and a maximum average functionality of 6 more preferably 5. The polyisocyanate component may contain monomeric diisocyanates or polyisocyanate adducts having functionalities which do not satisfy these requirements, provided that the average functionality of the polyisocyanate component satisfies these requirements.
The polyisocyanate component contains at least 50% by weight, preferably at least 70% by weight) more preferably at least 95% by weight of polyisocyanates adducts containing isocyanurate, uretdione, biuret, urethane, allophanate, carbodiimide and/or oxadiazine-trione, preferably isocyanurate, uretdione, biuret and/or allophanate groups. In addition to the polyisocyanate adducts the polyisocyanate component may optionally contain either monomeric polyisocyanates or other polyisocyanate adducts.
Suitable monomeric diisocyanates, which may be present in the polyisocyanate component in the form of monomers or which may be used to prepare the polyisocyanate adducts, are represented by the formula R(NCO)2 in which R represents an organic group obtained by removing the isocyanate groups from an organic diisocyanate having a molecular weight of about 112 to 1,000, preferably about 140 to 400. Diisocyanates preferred for the process according to the invention are those in which R
represents a divalent aliphatic hydrocarbon group having 4 to 40, Mo4795 -8-preferably 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.
Examples of the suitable organic diisocyanates include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-2-isocyanatomethyl cyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis-(4-iso-cyanatocyclohexyl)-methane, 2,4'-dicyclohexyl-methane diisocyanate, 1,3- and 1,4-bis-(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, a,a,a',a'-tetramethyl-1,3- and/or -1,4-xylylene diisocyanate, 1-isocyanato-1-methyl-4(3)-isocyanatomethyl cyclohexane, 2,4- and/or 2,6-hexahydrotoluylene diisocyanate, 1,3- and/or 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, 2,4-and/or 4,4'-diphenyl-methane diisocyanate, 1,5-diisocyanato naphthalene and mixtures thereof.
Monomeric polyisocyanates containing 3 or more isocyanate groups such as 4-isocyanantomethyl-1,8-octamethylene diisocyanate and aromatic polyisocyanates such as 4,4',4"-triphenylmethane triisocyanate and polyphenyl polymethylene polyisocyanates obtained by phosgenating aniline/formaldehyde condensates may also be present in the polyisocyanate component or used to prepare the polyisocyanate adducts.
Preferred organic diisocyanates include 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis-(4-isocyanato-cyclohexyl)-methane, 1-isocyanato-1-methyl-4(3)-isocyanatomethyl Mo4795 -9-cyclohexane, 2,4- and/or 2,6-toluylene diisocyanate, and 2,4- and/or 4,4'-diphenyl-methane diisocyanate.
In accordance with the present invention at least a portion of the polyisocyanate component is in the form of a polyisocyanate adduct having an average functionality of 2 to 6 and an NCO content of 5 to 30%
by weight. Examples include:
1 ) Isocyanurate group-containing polyisocyanates which may be prepared as set forth in DE-PS 2,616,416, EP-OS 3,765) EP-OS 10,589, EP-OS 47,452, US-PS 4,288,586 and US-PS 4,324,879.
The isocyanato-isocyanurates generally have an average NCO
functionality of 3 to 3.5 and an NCO content of 5 to 30%, preferably 10 to 25% and most preferably 15 to 25% by weight.
2) Uretdione diisocyanates which may be prepared by oligomerizing a portion of the isocyanate groups of a diisocyanate in the presence of a suitable catalyst, e.g, a trialkyl phosphine catalyst, and which may be used in admixture with other aliphatic and/or cycloaliphatic polyisocyanates, particularly the isocyanurate group-containing polyisocyanates set forth under (1 ) above.
COATING COMPOSITIONS
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to aqueous two-component coating compositions containing water dispersible compounds, which contain alkoxysilane groups and are substantially free from isocyanate groups, and aqueous polyhydroxy polyesters.
Description of the Prior Art Two-component aqueous compositions containing a water dispersible polyisocyanate component and various water dispersible or water soluble polyhydroxy components are known and described in U.S.
Patents 5,075,370, 5,389,718, 5,387,642, 5,372,875, 5,336,711, 5,344,873 and 5,459,197. The aqueous compositions may be used for a wide range of commercial applications such as adhesives, sealants or coatings for various substrates including textile fabrics, plastic, wood, glass fibers and metals. Chemical resistance, abrasion resistance, toughness, tensile strength) elasticity and durability are among the many desirable properties of these coatings.
One of the known two-component compositions is based on water dispersible polyisocyanates and aqueous polyhydroxy compounds containing ester and/or carbonate groups. One disadvantage of these systems is that the resulting coatings do not possess adequate hardness for certain applications. In addition, it is advantageous in certain applications to avoid the use of polyisocyanate resins for environmental and industrial hygiene reasons.
Accordingly, it is an object of the present invention to provide two-component aqueous compositions containing new non-isocyanate co-Mo4795 _2_ reactants, which can be used to prepare coatings having improved hardness.
This object may be achieved with the aqueous two-component coating compositions according to the present invention, which are based on water dispersible compounds containing urea and alkoxysilane groups and an aqueous polyhydroxy compound containing ester and/or carbonate groups. These compounds containing urea and alkoxysilane groups may be prepared by reacting a polyisocyanate component with compounds containing secondary amino groups and alkoxysilane groups.
SUMMARY OF THE INVENTION
The present invention relates to aqueous two-component compositions containing a) compounds which are substantially free from isocyanate groups, have an alkoxysilane group content (calculated as Si, MW 28) of 1 to 6% by weight, based on the weight of the compounds, and contain sufficient chemically incorporated hydrophilic groups to form a stable dispersion with water, wherein the alkoxysilane groups are incorporated as the reaction products of i) a polyisocyanate component having a minimum average functionality of 2.4 and containing at least 50% by weight of polyisocyanate adducts and ii) amino compounds corresponding to the formula I
(I) HN-(CH2)~ Si-(X~
wherein Mo4795 _3_ X represents identical or different organic groups which are inert to isocyanate groups below 100°C, provided that at least one of these groups is an alkoxy group, R, represents an organic group which is inert to isocyanate groups at a temperature of 100°C or less, and n is an integer from 1 to 8, and a) polyhydroxy compounds containing ester and/or carbonate groups and having a urethane group content of less than 5% by weight, based on the weight of the polyhydroxy compounds.
The present invention also relates to coatings, adhesives and sealants prepared from these aqueous compositions and to compounds a) containing urea and alkoxysilane groups.
DETAILED DESCRIPTION OF THE INVENTION
Compounds a) containing urea and alkoxysilane groups are based on the reaction products of polyisocyanates, amino-functional silanes and compounds containing hydrophilic groups, such as non-ionic, anionic and/or cationic groups. The silanes are incorporated through the formation of urea groups, while the hydrophilic groups are preferably incorporated through the formation of urethane groups. The compounds according to the invention are substantially free from isocyanate groups, which means that they contain less than 0.1 % by weight of isocyanate groups, based on the weight of the compounds.
Suitable compounds containing alkoxysilane groups and amino groups include those corresponding to formula I wherein X represents identical or different organic groups which are inert to isocyanate groups below 100°C, provided that at least one of these groups is an alkoxy or acyloxy group, preferably alkyl or alkoxy groups having 1 to 4 carbon atoms and more preferably alkoxy groups, Mo4795 -4-R, represents an organic group which is inert to isocyanate groups at a temperature of 100°C or less, preferably an alkyl, cycloalkyl or aromatic group having 1 to 12, preferably 1 to 8 carbon atoms, or a group corresponding to the formula -(CH2)~ Si-(X)3 (II) and n is an integer from 1 to 8, preferably 2 to 4 and more preferably 3.
Especially preferred are compounds in which X represents methoxy, ethoxy groups or propoxy groups, more preferably methoxy or ethoxy groups and most preferably methoxy groups, and n is 3.
Examples of suitable aminoalkyl alkoxysilanes of formula I
containing secondary amino groups include N-phenylaminopropyl-trimethoxysilane (available as A-9669 from OSI Specialties, Witco), bis-(y-trimethoxysilylpropyl)amine (available as A-1170 from OSI Specialties, Witco), N-cyclohexylaminopropyltriethoxy-silane, N-methylaminopropyl-trimethoxysilane and the corresponding alkyl diethyoxy and dimethoxy silanes.
A special group of compounds containing alkoxysilane groups are those which also contain aspartate groups, such as those corresponding to formula III
Z-CHR3 CR4 NH-(CH2)~ Si-(X)3 (III) wherein Mo4795 -5-X and n are as defined above, Z represents COORS or an aromatic ring, preferably COORS, RZ and RS are identical or different and represent organic groups which are inert to isocyanate groups at a temperature of 100°C or less, preferably alkyl groups having 1 to 9 carbon atoms, more preferably methyl, ethyl or butyl groups and R3 and R4 are identical or different and represent hydrogen or organic groups which are inert to isocyanate groups at a temperature of 100°C or less, preferably hydrogen.
The compounds of formula III are prepared by reacting aminoalkyl alkoxysilanes corresponding to the formula H2N-(CH2)n Si-(X)3 (N) with malefic, fumaric or cinnamic acid esters corresponding to the formula Z-CR3=CR4-COOR2 (V).
Examples of suitable aminoalkyl alkoxysilanes of formula IV include 2-aminoethyl-dimethylrnethoxy-silane; 6-aminohexyl-tributoxysilane; 3-aminopropyl-trimethoxysilane; 3-aminopropyl-triethoxysilane; 3-aminopropyl-methyldiethoxysilane; 5-aminopentyl-trimethoxysilane; 5-aminopentyl-triethoxysilane and 3-aminopropyl-triisopropoxysilane. 3-aminopropyl-trimethoxysilane and 3-aminopropyl-triethoxysilane are particularly preferred.
Examples of optionally substituted malefic, fumaric or cinnamic acid esters suitable for use in the preparation of the polyaspartates include Mo4795 -6-dimethyl, diethyl, dibutyl (e.g., di-n-butyl), diamyl, di-2-ethylhexyl esters and mixed esters based on mixture of these and/or other alkyl groups of malefic acid and fumaric acid; the methyl, ethyl and butyl esters of cinnamic acid; and the corresponding malefic, fumaric and cinnamic acid esters substituted by methyl in the 2- and/or 3-position. The dimethyl esters of malefic acid are preferred and the diethyl and dibutyl esters are especially preferred.
The reaction of primary amines with malefic) fumaric or cinnamic acid esters to form the aspartates of formula III is known and described, e.g. in U.S. Patent 5,364,955, which is herein incorporated by reference.
The preparation of the aspartates may be carried out, for example, at a temperature of 0 to 100°C using the starting materials in such proportions that ~at least 1, preferably 1, olefinic double bond is present for each primary amino group. Excess starting materials may be removed by distillation after the reaction. The reaction may be carried out with or without a solvent, but the use of a solvent is less preferred. If a solvent is used, dioxane is an example of a suitable solvent.
The compounds containing alkoxysilane groups and amino groups are reacted in an amount sufficient to incorporate 1 to 6% by weight, preferably 2 to 6% by weight and more preferably 2 to 5% by weight of alkoxysilane groups (calculated as Si, MW 28), based on the weight of the compounds containing urea and alkoxysilane groups. The compounds of formula III are colorless to pale yellow. They may be reacted with polyisocyanate component i) to form the compounds containing urea and alkoxysilane groups without further purification.
In accordance with the present invention the special type of urea groups formed by the reaction of the compounds containing alkoxysilane groups and aspartate groups with the polyisocyanate component may be converted to hydantoin groups in known manner by heating the Mo4795 -7-compounds at elevated temperatures, optionally in the presence of a catalyst. Therefore, the term "urea groups" is also intended to include other compounds containing the group, N-CO-N, such as hydantoin groups.
The polyisocyanate component for preparing the compounds containing urea and alkoxysilane groups has a minimum average functionality of 2.4, preferably to 2.6 and more preferably 2.8, and a maximum average functionality of 6 more preferably 5. The polyisocyanate component may contain monomeric diisocyanates or polyisocyanate adducts having functionalities which do not satisfy these requirements, provided that the average functionality of the polyisocyanate component satisfies these requirements.
The polyisocyanate component contains at least 50% by weight, preferably at least 70% by weight) more preferably at least 95% by weight of polyisocyanates adducts containing isocyanurate, uretdione, biuret, urethane, allophanate, carbodiimide and/or oxadiazine-trione, preferably isocyanurate, uretdione, biuret and/or allophanate groups. In addition to the polyisocyanate adducts the polyisocyanate component may optionally contain either monomeric polyisocyanates or other polyisocyanate adducts.
Suitable monomeric diisocyanates, which may be present in the polyisocyanate component in the form of monomers or which may be used to prepare the polyisocyanate adducts, are represented by the formula R(NCO)2 in which R represents an organic group obtained by removing the isocyanate groups from an organic diisocyanate having a molecular weight of about 112 to 1,000, preferably about 140 to 400. Diisocyanates preferred for the process according to the invention are those in which R
represents a divalent aliphatic hydrocarbon group having 4 to 40, Mo4795 -8-preferably 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.
Examples of the suitable organic diisocyanates include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-2-isocyanatomethyl cyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis-(4-iso-cyanatocyclohexyl)-methane, 2,4'-dicyclohexyl-methane diisocyanate, 1,3- and 1,4-bis-(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, a,a,a',a'-tetramethyl-1,3- and/or -1,4-xylylene diisocyanate, 1-isocyanato-1-methyl-4(3)-isocyanatomethyl cyclohexane, 2,4- and/or 2,6-hexahydrotoluylene diisocyanate, 1,3- and/or 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, 2,4-and/or 4,4'-diphenyl-methane diisocyanate, 1,5-diisocyanato naphthalene and mixtures thereof.
Monomeric polyisocyanates containing 3 or more isocyanate groups such as 4-isocyanantomethyl-1,8-octamethylene diisocyanate and aromatic polyisocyanates such as 4,4',4"-triphenylmethane triisocyanate and polyphenyl polymethylene polyisocyanates obtained by phosgenating aniline/formaldehyde condensates may also be present in the polyisocyanate component or used to prepare the polyisocyanate adducts.
Preferred organic diisocyanates include 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI), bis-(4-isocyanato-cyclohexyl)-methane, 1-isocyanato-1-methyl-4(3)-isocyanatomethyl Mo4795 -9-cyclohexane, 2,4- and/or 2,6-toluylene diisocyanate, and 2,4- and/or 4,4'-diphenyl-methane diisocyanate.
In accordance with the present invention at least a portion of the polyisocyanate component is in the form of a polyisocyanate adduct having an average functionality of 2 to 6 and an NCO content of 5 to 30%
by weight. Examples include:
1 ) Isocyanurate group-containing polyisocyanates which may be prepared as set forth in DE-PS 2,616,416, EP-OS 3,765) EP-OS 10,589, EP-OS 47,452, US-PS 4,288,586 and US-PS 4,324,879.
The isocyanato-isocyanurates generally have an average NCO
functionality of 3 to 3.5 and an NCO content of 5 to 30%, preferably 10 to 25% and most preferably 15 to 25% by weight.
2) Uretdione diisocyanates which may be prepared by oligomerizing a portion of the isocyanate groups of a diisocyanate in the presence of a suitable catalyst, e.g, a trialkyl phosphine catalyst, and which may be used in admixture with other aliphatic and/or cycloaliphatic polyisocyanates, particularly the isocyanurate group-containing polyisocyanates set forth under (1 ) above.
3) Biuret group-containing polyisocyanates which may be prepared according to the processes disclosed in U.S. Patent Nos.
3,124,605; 3,358,010; 3,644,490; 3,862,973; 3,906,126; 3,903,127;
3,124,605; 3,358,010; 3,644,490; 3,862,973; 3,906,126; 3,903,127;
4,051,165; 4,147,714; or 4,220,749 by using co-reactants such as water, tertiary alcohols, primary and secondary monoamines, and primary and/or secondary diamines. These polyisocyanates preferably have an NCO
content of 18 to 22% by weight and an average NCO functionality of 3 to 3.5.
4) Urethane group-containing polyisocyanates which may be prepared in accordance with the process disclosed in U.S. Patent No.
3,183,112 by reacting excess quantities of polyisocyanates, preferably Mo4795 -10-diisocyanates, with low molecular weight glycols and polyols having molecular weights of less than 400, such as trimethylol propane, glycerine, 1,2-dihydroxy propane and mixtures thereof. The urethane group-containing polyisocyanates have a most preferred NCO content of 12 to 20% by weight and an (average) NCO functionality of 2.5 to 3.
content of 18 to 22% by weight and an average NCO functionality of 3 to 3.5.
4) Urethane group-containing polyisocyanates which may be prepared in accordance with the process disclosed in U.S. Patent No.
3,183,112 by reacting excess quantities of polyisocyanates, preferably Mo4795 -10-diisocyanates, with low molecular weight glycols and polyols having molecular weights of less than 400, such as trimethylol propane, glycerine, 1,2-dihydroxy propane and mixtures thereof. The urethane group-containing polyisocyanates have a most preferred NCO content of 12 to 20% by weight and an (average) NCO functionality of 2.5 to 3.
5) Allophanate group-containing polyisocyanates which may be prepared according to the processes disclosed in U.S. Patent Nos.
3,769,318, 4,160,080 and 4,177,342. The allophanate group-containing polyisocyanates have a most preferred NCO content of 12 to 21 % by weight and an (average) NCO functionality of 2 to 4.5.
3,769,318, 4,160,080 and 4,177,342. The allophanate group-containing polyisocyanates have a most preferred NCO content of 12 to 21 % by weight and an (average) NCO functionality of 2 to 4.5.
6) Isocyanurate and allophanate group-containing polyiso-cyanates which may be prepared in accordance with the processes set forth in U.S. Patents 5,124,427, 5,208,334 and 5,235,018, the disclosures of which are herein incorporated by reference, preferably polyisocyanates containing these groups in a ratio of monoisocyanurate groups to mono-allophanate groups of about 10:1 to 1:10, preferably about 5:1 to 1:7.
7) Carbodiimide group-containing polyisocyanates which may be prepared by oligomerizing di- or polyisocyanates in the presence of known carbodiimidization catalysts as described in DE-PS 1,092,007, US-PS 3,152,162 and DE-OS 2,504,400, 2,537,685 and 2,552,350.
8) Polyisocyanates containing oxadiazinetrione groups and containing the reaction product of two moles of a diisocyanate and one mole of carbon dioxide.
Preferred polyisocyanate adducts are the polyisocyanates containing isocyanurate groups, biuret groups, allophanate groups and/or uretdione groups.
Suitable hydrophilic compounds which can be used to enable the compounds containing urea and alkoxysilane groups to be stably dispersed in an aqueous medium are compounds containing lateral or Mo4795 -11-terminal, hydrophilic ethylene oxide units and/or compounds containing ionic or potential ionic groups. The ionic or potential ionic groups may be either anionic or cationic groups, preferably anionic groups. Examples of anionic groups include carboxylate and sulfonate groups, while examples of cationic groups include ammonium and sulfonium groups.
Compounds which are stably dispersed are those that remain mixed with water, either in the form of an oil-in-water emulsion or a water-in-oil emulsion, without settling, coagulation or separation for a period of time sufficient to use the dispersion for its intended purpose. In accordance with the present invention the compounds containing urea and alkoxysilane groups also contain a minimum of 2.5% of hydrophilic ethylene oxide units, based on the weight of the compounds containing urea and alkoxysilane groups, or a minimum of 5 milliequivalents of ionic groups, per 100 parts of the compounds containing urea and alkoxysilane groups.
When only hydrophilic ethylene oxide units are used to provide hydrophilicity, they are generally incorporated in an amount of 5 to 35%, preferably 10 to 30% and more preferably about 12 to 25% by weight, based on the weight of the compounds containing urea and alkoxysilane groups.
Suitable compounds for incorporating the lateral or terminal, hydrophilic ethylene oxide units are known and disclosed in U.S. Patents 3,905,929, 3,920,598 and 4,190,566 (the disclosures of which are herein incorporated by reference). Preferred hydrophilic components are the monohydroxy polyethers having terminal hydrophilic chains containing ethylene oxide units. These hydrophilic components may be produced as described in the preceding patents by alkoxylating a monofunctional starter, such as methanol or n-butanol, using ethylene oxide and optionally another alkylene oxide, for example, propylene oxide.
Mo4795 -12-When only ionic groups are used to provide hydrophilicity, they are incorporated in an amount sufficient to provide an ionic group content of 10 to 200 milliequivalents, preferably 10 to 100 milliequivalents and more preferably 25 to 50 milliequivalents, per 100 g of the compounds containing urea and alkoxysilane groups.
The ionic groups are formed by neutralizing the corresponding potential ionic groups either prior to, during or after formation of the compounds containing urea and alkoxysilane groups. When the potential ionic groups are neutralized prior to their incorporation into the these compounds) the ionic groups are incorporated directly. When neutralization is performed subsequent to forming these compounds, potential ionic groups are incorporated.
Suitable compounds for incorporating the carboxylate, sulfonate and quaternary nitrogen groups are described in U.S. Patents 3,479,310, 4,108,814 and 4,303,774) the disclosures of which are herein incorporated by reference. Suitable compounds for incorporating tertiary sulfonium groups are described in U.S. Patent 3,419,533, also incorporated by reference. The preferred sulfonate groups for incorporation into the NCO
prepolymer are the diol sulfonic acids or the diol sulfonates disclosed in U.S. Patent 4,108,814.
The neutralizing agents for converting the potential ionic groups to ionic groups are described in the preceding U.S. patents. Within the context of this invention, the term "neutralizing agents" is meant to embrace all types of agents which are useful for converting potential ionic groups to ionic groups.
The compounds containing urea and alkoxysilane groups according to the invention are prepared by reacting the polyisocyanate component with the amino-functional silanes and the hydrophilic compounds at a ratio of isocyanate groups to isocyanate-reactive groups of approximately 1:1, Mo4795 -13-such that the resulting product is substantially free of isocyanate groups.
The reaction is preferably carried out by incrementally adding the isocyanate-reactive compound to the polyisocyanate. The amino-functional silane and an isocyanate-reactive hydrophilic compound may be added sequentially or in admixture, preferably the hydrophilic compound is added first, followed by the amino-functional silane.
The reaction to form the urea groups is conducted at a temperature of 10 to 100°C, preferably 20 to 80°C and more preferably 20 to 50°C, while the reaction to incorporate isocyanate-reactive hydrophilic compounds is conducted at a temperature of 20 to 150°C, preferably 50 to 120°C and more preferably 60 to 100°C.
The aqueous, two-component, coating, sealing or adhesive compositions also contain polyhydroxy compounds b), which contain ester and/or carbonate groups and have a number average molecular weight (M", which may be calculated by end group analysis) of 400 to 10,000 preferably 600 to 5,000 and more preferably 700 to 3,000. These polyhydroxy polyesters are known from two-component, polyurethane waterborne technology and are described in U.S. Patents 5,372,875, 5,344,873 and 5,459,197 (all of which are herein incorporated by reference). The polyhydroxy compounds may be rendered water dispersible or water soluble by the use of external emulsifiers, by the incorporation of nonionic hydrophilic groups or by the incorporation of ionic groups, such as anionic or cationic groups. Chemically incorporated hydrophilic groups are preferred, especially ionic groups and more preferably anionic groups.
The aqueous two-component compositions may be prepared by simply mixing the compounds containing urea and alkoxy silane groups with the polyhydroxy compounds. If desired, the compounds containing urea and alkoxy silane groups can be mixed with water prior to mixing Mo4795 -14-these compounds with the polyhydroxy compounds. The amount of water may be sufficient to form either a water-in-oil emulsion or an oil-in-water emulsion. Either before, during or after the two-components have been mixed additional water can be added to obtain the final solids content.
The aqueous coating compositions of the present invention may optionally contain acidic or basic catalysts to accelerate the curing reaction.
Examples include acids such as paratoluene sulfonic acid; metallic salts such as dibutyl tin dilaurate; tertiary amines such as triethylamine or triethylene diamine; and mixtures of these catalysts. Low molecular weight, basic aminoalkyl trialkoxysilanes, such as those represented by formula IV, also accelerate hardening of the compounds according to the invention.
The two-component compositions generally have a solids content of to 60%, preferably 30 to 50% and more preferably 35 to 45%, based on 15 the weight of the two-component composition. The compositions may also contain known additives, such as leveling agents, wetting agents, flow control agents, antiskinning agents, antifoaming agents, fillers (such as silica, aluminum silicates and high-boiling waxes)) viscosity regulators, plasticizers, pigments, dyes, UV absorbers and stabilizers against thermal 20 and oxidative degradation.
The two-component compositions may be applied to any desired substrates, such as wood, plastics) leather, paper, textiles, glass, ceramics, plaster, masonry, metals and concrete. They may be applied by standard methods, such as spray coating, spread coating, flood coating, casting, dip coating or roll coating. The coating compositions may be clear or pigmented lacquers.
The two-component compositions may be cured at ambient temperature, although it is preferred to cure these compositions at elevated Mo4795 -15-temperatures of 120 to 180°C, preferably 130 to 150°C, for approximately 30 minutes in order to obtain optimum properties.
Coatings prepared from these compositions have improved hardness when compared to coatings prepared from the known two-component compositions, which contain polyisocyanate resins instead of the compounds containing urea and alkoxysilane groups. The improvement is surprising because the same improvement in hardness is not obtained when the compounds containing urea and alkoxysilane groups are reacted with other types of polyhydroxy compounds as demonstrated in the following examples.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
Polyisocyanate 1 An isocyanurate group-containing polyisocyanate prepared from 1,6-hexamethylene diisocyanate and having an isocyanate content of 21.6%, a monomeric diisocyanate content of <0.2% and a viscosity at 20°C of 3000 mPa.s (available from Bayer Corporation as Desmodur N 3300).
Polyether 1 A polyethylene oxide monool prepared by the ethoxylation of methanol and having a molecular weight of 750 (available from Union Carbide as Carbowax 750).
Polyether 2 A polyethylene oxide monool prepared by the ethoxylation of methanol and having a molecular weight of 550 (available from Union Carbide as Carbowax 550).
Mo4795 -16-Agueous Polyol 1 A water dispersible polyester polyol having a resin solids content of 30% and an OH no. of 49.2 mg KOH/g solution (Desmophen XP-7093) available from Bayer Corp.).
Aqueous Polyol 2 A water dispersible polyol having a urethane group content of 12.8%, based on solids, a resin solids content of 40% and an OH no. of 25.5 KOH/g solution (Bayhydrol XP-7044) available from Bayer Corp.).
Aqueous Polyol 3 A water dispersible polyacrylate polyol having a resin solids content of 42% and an OH no. of 18.1 mg KOH/g solution (Roshield 3275, available from Rohm and Haas).
Example 1 - Preparation of N-(3-trimethoxysilylpropyl) aspartic acid diethyl ester 1438 parts (8.27 equiv.) of 3-aminopropyltrimethoxysilane were added to a 5 liter flask fitted with agitator, thermocouple, nitrogen inlet and addition funnel with condenser. 1423.2 parts (8.27 equiv.) of diethyl maleate were added dropwise over a period of 2 hours. The temperature of the reactor was maintained at 25°C during the addition. The reactor was maintained at 25°C for an additional 5 hours at which time the product was poured into glass containers and sealed under a blanket of nitrogen. After one week the unsaturation number was 0.6 indicating the reaction was ~99% complete. The product, N-(3-trimethoxysilylpropyl) aspartic acid diethyl ester, had a viscosity of 11 mPa.s at 25°C.
Example 2 - Preparation of water dispersible resin 1 195 parts (1 equiv) of polyisocyanate 1 were added at ambient temperature to a three neck, 5 liter, round bottom flask equipped with an agitator, nitrogen inlet, thermocouple and condenser. The reaction flask was heated to 60°C. 90 parts (0.12 equiv.) of polyether 1, heated to 60°C, Mo4795 -17-was added to the reaction flask through the addition funnel over a twenty minute period in order to control the exotherm for the formation of the urethane. The reaction was maintained at 60°C for 4 hours, at which time the isocyanate content was 13.8% (theoretical NCO 13.0%).
The reaction was cooled to 40°C and 341 parts (0.93 equiv.) of N-(3-trimethoxysilylpropyl) aspartic acid diethyl ester were added through an addition funnel to control the exotherm. The reaction was heated for an additional 3 hours until no isocyanate groups remained as determined by IR spectroscopy. After cooling to room temperature, the resulting product had a viscosity of >100,000 mPa.s at 25°C.
parts of this product was combined with 10 parts of water and stirred at high speed with a lightning mixer. A stable dispersion resulted.
Example 3 - Preparation of water dispersible resin 2 195 parts (1 equiv) of polyisocyanate 1 were added at ambient 15 temperature to a three neck, 5 liter, round bottom flask equipped with an agitator, nitrogen inlet, thermocouple and addition funnel with condenser.
The reaction flask was heated to 60°C. 82.5 parts (0.15 equiv.) of polyether 2, heated to 60°C, was added to the reaction flask through the addition funnel over a twenty minute period in order to control the exotherm 20 for the formation of the urethane. The reaction was maintained at 60°C for 4 hours, at which time the isocyanate content was 14.4% (theoretical NCO
14.1 %).
The reaction was cooled to 40°C and 312 parts (0.85 equiv.) of N-(3-trimethoxysilylpropyl) aspartic acid diethyl ester were added through an addition funnel to control the exotherm. The reaction was heated for an additional 3 hours until no isocyanate groups remained as determined by IR spectroscopy. After cooling to room temperature, the resulting product had a viscosity of >100,000 mPa.s at 25°C.
Mo4795 -18-20 parts of this product was combined with 10 parts of water and stirred at high speed with a lightning mixer. A stable dispersion resulted.
Example 4 - (Comparison) - Preparation of water dispersible resin 3 Example 3 was repeated with the exception that no aminosilane was added. The resulting product was a hydrophilically modified polyisocyanate.
Example 5 - (Comparison) - Water dispersible resin 4 A water dispersible polyisocyanate having an isocyanate content of 17.3% and an equivalent weight of 243, based on solids. (Bayhydur XP-7063, available from Bayer Corp.).
Example 6 - Preparation of coatings 10 parts of water dispersible resin 1 were mixed with 10 parts of water, 5.4 parts of aqueous polyol 1 and 0.5 parts of catalyst (a proprietary titanate chelate, available as Tyzor 131 from DuPont). Films were drawn down on 4"x12" steel panels with a #30 wire-wound rod in a wet film thickness sufficient to provide a dry film thickness of 0.4 mils. The films were cured at 120°C and 140°C for 30 and 60 minutes as set forth in Table 1. The films had no adhesion before baking, but good adhesion after baking.
Curing Conditions Pencil Hardness MEK Double Rubs 120C, 30 minutes 3H 100 120C, 60 minutes 3H 100 140C, 30 minutes 5H 100 140C, 60 minutes 4H 100 Example 7 - Preparation of coating Water dispersible resin 2 was dispersed in an equal amount of water on a high speed mixer and then mixed with aqueous polyol 1 and with the Mo4795 -19-catalyst described in Example 6. The resulting mixtures were used to prepare films which were drawn down on cold rolled steel at a wet film thickness sufficient to provide a dry film thickness of 1 to 1.5 mils and cured either at room temperature or at elevated temperature as set forth in Table 2. The amounts of the various components and the properties of the resulting coatings are also set forth in Table 2.
Example 6 Ingredients Amounts in parts Water dispersible resin 2 10 Water 10 Aqueous Polyol 1 5.4 Catalyst 0.5 Cure at 25C/55% RH
Gardner Dry Time, days 5 MEK Double Rubs 100 Pencil Hardness F
Cure at 130C/ 30 min.
MEK Double Rubs 100 Pencil Hardness F
Dry times were determined with a Gardner Dry Time meter as described in Pacific Scientific Instruction manuals DG-9600 and DG-9300.
MEK double rubs was determined by wetting a cloth with methyl ethyl ketone and then rubbing each panel up to 100 times. A double rub consists of one back and forth rub against the coated panel. Values of less Mo4795 -20-than 100 indicate the number of double rubs before the coatings was destroyed.
Pencil hardness was determined in accordance with ASTM D-3363.
The order of hardnesses are as follows from softest to hardest: 6B to 1 B, HB, F, 1 H to 8H.
Examples 8-17 - Preparation of Coatings The water dispersible resin, the aqueous polyol, optionally a catalyst and sufficient water to provide a resin solids content of 40 to 43%, based on the resulting composition, were mixed with a high speed mixer.
The catalyst, if used, was the catalyst described in Example 6 and was used in an amount of 4.3%, based on resin solids. The resulting mixtures were used to prepare films which were drawn down on cold rolled steel at a wet film thickness of 3 mils (dry film thickness - 0.4 mils) and air dried for 16 hours at 25°C and 55% relative humidity and then at 140°C for minutes. The water dispersible resin, the aqueous polyol, the presence of catalyst, the silane or NCO to OH equivalent ratio and the pencil hardness of the resulting films are set forth in Table 3.
Mo4795 -21-Example Water Aqueous Silane Catalyst Pencil Dispers- Polyol or Hardness ible resin NCO to OH ratio 8 2 1 3:1 No 6H
Preferred polyisocyanate adducts are the polyisocyanates containing isocyanurate groups, biuret groups, allophanate groups and/or uretdione groups.
Suitable hydrophilic compounds which can be used to enable the compounds containing urea and alkoxysilane groups to be stably dispersed in an aqueous medium are compounds containing lateral or Mo4795 -11-terminal, hydrophilic ethylene oxide units and/or compounds containing ionic or potential ionic groups. The ionic or potential ionic groups may be either anionic or cationic groups, preferably anionic groups. Examples of anionic groups include carboxylate and sulfonate groups, while examples of cationic groups include ammonium and sulfonium groups.
Compounds which are stably dispersed are those that remain mixed with water, either in the form of an oil-in-water emulsion or a water-in-oil emulsion, without settling, coagulation or separation for a period of time sufficient to use the dispersion for its intended purpose. In accordance with the present invention the compounds containing urea and alkoxysilane groups also contain a minimum of 2.5% of hydrophilic ethylene oxide units, based on the weight of the compounds containing urea and alkoxysilane groups, or a minimum of 5 milliequivalents of ionic groups, per 100 parts of the compounds containing urea and alkoxysilane groups.
When only hydrophilic ethylene oxide units are used to provide hydrophilicity, they are generally incorporated in an amount of 5 to 35%, preferably 10 to 30% and more preferably about 12 to 25% by weight, based on the weight of the compounds containing urea and alkoxysilane groups.
Suitable compounds for incorporating the lateral or terminal, hydrophilic ethylene oxide units are known and disclosed in U.S. Patents 3,905,929, 3,920,598 and 4,190,566 (the disclosures of which are herein incorporated by reference). Preferred hydrophilic components are the monohydroxy polyethers having terminal hydrophilic chains containing ethylene oxide units. These hydrophilic components may be produced as described in the preceding patents by alkoxylating a monofunctional starter, such as methanol or n-butanol, using ethylene oxide and optionally another alkylene oxide, for example, propylene oxide.
Mo4795 -12-When only ionic groups are used to provide hydrophilicity, they are incorporated in an amount sufficient to provide an ionic group content of 10 to 200 milliequivalents, preferably 10 to 100 milliequivalents and more preferably 25 to 50 milliequivalents, per 100 g of the compounds containing urea and alkoxysilane groups.
The ionic groups are formed by neutralizing the corresponding potential ionic groups either prior to, during or after formation of the compounds containing urea and alkoxysilane groups. When the potential ionic groups are neutralized prior to their incorporation into the these compounds) the ionic groups are incorporated directly. When neutralization is performed subsequent to forming these compounds, potential ionic groups are incorporated.
Suitable compounds for incorporating the carboxylate, sulfonate and quaternary nitrogen groups are described in U.S. Patents 3,479,310, 4,108,814 and 4,303,774) the disclosures of which are herein incorporated by reference. Suitable compounds for incorporating tertiary sulfonium groups are described in U.S. Patent 3,419,533, also incorporated by reference. The preferred sulfonate groups for incorporation into the NCO
prepolymer are the diol sulfonic acids or the diol sulfonates disclosed in U.S. Patent 4,108,814.
The neutralizing agents for converting the potential ionic groups to ionic groups are described in the preceding U.S. patents. Within the context of this invention, the term "neutralizing agents" is meant to embrace all types of agents which are useful for converting potential ionic groups to ionic groups.
The compounds containing urea and alkoxysilane groups according to the invention are prepared by reacting the polyisocyanate component with the amino-functional silanes and the hydrophilic compounds at a ratio of isocyanate groups to isocyanate-reactive groups of approximately 1:1, Mo4795 -13-such that the resulting product is substantially free of isocyanate groups.
The reaction is preferably carried out by incrementally adding the isocyanate-reactive compound to the polyisocyanate. The amino-functional silane and an isocyanate-reactive hydrophilic compound may be added sequentially or in admixture, preferably the hydrophilic compound is added first, followed by the amino-functional silane.
The reaction to form the urea groups is conducted at a temperature of 10 to 100°C, preferably 20 to 80°C and more preferably 20 to 50°C, while the reaction to incorporate isocyanate-reactive hydrophilic compounds is conducted at a temperature of 20 to 150°C, preferably 50 to 120°C and more preferably 60 to 100°C.
The aqueous, two-component, coating, sealing or adhesive compositions also contain polyhydroxy compounds b), which contain ester and/or carbonate groups and have a number average molecular weight (M", which may be calculated by end group analysis) of 400 to 10,000 preferably 600 to 5,000 and more preferably 700 to 3,000. These polyhydroxy polyesters are known from two-component, polyurethane waterborne technology and are described in U.S. Patents 5,372,875, 5,344,873 and 5,459,197 (all of which are herein incorporated by reference). The polyhydroxy compounds may be rendered water dispersible or water soluble by the use of external emulsifiers, by the incorporation of nonionic hydrophilic groups or by the incorporation of ionic groups, such as anionic or cationic groups. Chemically incorporated hydrophilic groups are preferred, especially ionic groups and more preferably anionic groups.
The aqueous two-component compositions may be prepared by simply mixing the compounds containing urea and alkoxy silane groups with the polyhydroxy compounds. If desired, the compounds containing urea and alkoxy silane groups can be mixed with water prior to mixing Mo4795 -14-these compounds with the polyhydroxy compounds. The amount of water may be sufficient to form either a water-in-oil emulsion or an oil-in-water emulsion. Either before, during or after the two-components have been mixed additional water can be added to obtain the final solids content.
The aqueous coating compositions of the present invention may optionally contain acidic or basic catalysts to accelerate the curing reaction.
Examples include acids such as paratoluene sulfonic acid; metallic salts such as dibutyl tin dilaurate; tertiary amines such as triethylamine or triethylene diamine; and mixtures of these catalysts. Low molecular weight, basic aminoalkyl trialkoxysilanes, such as those represented by formula IV, also accelerate hardening of the compounds according to the invention.
The two-component compositions generally have a solids content of to 60%, preferably 30 to 50% and more preferably 35 to 45%, based on 15 the weight of the two-component composition. The compositions may also contain known additives, such as leveling agents, wetting agents, flow control agents, antiskinning agents, antifoaming agents, fillers (such as silica, aluminum silicates and high-boiling waxes)) viscosity regulators, plasticizers, pigments, dyes, UV absorbers and stabilizers against thermal 20 and oxidative degradation.
The two-component compositions may be applied to any desired substrates, such as wood, plastics) leather, paper, textiles, glass, ceramics, plaster, masonry, metals and concrete. They may be applied by standard methods, such as spray coating, spread coating, flood coating, casting, dip coating or roll coating. The coating compositions may be clear or pigmented lacquers.
The two-component compositions may be cured at ambient temperature, although it is preferred to cure these compositions at elevated Mo4795 -15-temperatures of 120 to 180°C, preferably 130 to 150°C, for approximately 30 minutes in order to obtain optimum properties.
Coatings prepared from these compositions have improved hardness when compared to coatings prepared from the known two-component compositions, which contain polyisocyanate resins instead of the compounds containing urea and alkoxysilane groups. The improvement is surprising because the same improvement in hardness is not obtained when the compounds containing urea and alkoxysilane groups are reacted with other types of polyhydroxy compounds as demonstrated in the following examples.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
Polyisocyanate 1 An isocyanurate group-containing polyisocyanate prepared from 1,6-hexamethylene diisocyanate and having an isocyanate content of 21.6%, a monomeric diisocyanate content of <0.2% and a viscosity at 20°C of 3000 mPa.s (available from Bayer Corporation as Desmodur N 3300).
Polyether 1 A polyethylene oxide monool prepared by the ethoxylation of methanol and having a molecular weight of 750 (available from Union Carbide as Carbowax 750).
Polyether 2 A polyethylene oxide monool prepared by the ethoxylation of methanol and having a molecular weight of 550 (available from Union Carbide as Carbowax 550).
Mo4795 -16-Agueous Polyol 1 A water dispersible polyester polyol having a resin solids content of 30% and an OH no. of 49.2 mg KOH/g solution (Desmophen XP-7093) available from Bayer Corp.).
Aqueous Polyol 2 A water dispersible polyol having a urethane group content of 12.8%, based on solids, a resin solids content of 40% and an OH no. of 25.5 KOH/g solution (Bayhydrol XP-7044) available from Bayer Corp.).
Aqueous Polyol 3 A water dispersible polyacrylate polyol having a resin solids content of 42% and an OH no. of 18.1 mg KOH/g solution (Roshield 3275, available from Rohm and Haas).
Example 1 - Preparation of N-(3-trimethoxysilylpropyl) aspartic acid diethyl ester 1438 parts (8.27 equiv.) of 3-aminopropyltrimethoxysilane were added to a 5 liter flask fitted with agitator, thermocouple, nitrogen inlet and addition funnel with condenser. 1423.2 parts (8.27 equiv.) of diethyl maleate were added dropwise over a period of 2 hours. The temperature of the reactor was maintained at 25°C during the addition. The reactor was maintained at 25°C for an additional 5 hours at which time the product was poured into glass containers and sealed under a blanket of nitrogen. After one week the unsaturation number was 0.6 indicating the reaction was ~99% complete. The product, N-(3-trimethoxysilylpropyl) aspartic acid diethyl ester, had a viscosity of 11 mPa.s at 25°C.
Example 2 - Preparation of water dispersible resin 1 195 parts (1 equiv) of polyisocyanate 1 were added at ambient temperature to a three neck, 5 liter, round bottom flask equipped with an agitator, nitrogen inlet, thermocouple and condenser. The reaction flask was heated to 60°C. 90 parts (0.12 equiv.) of polyether 1, heated to 60°C, Mo4795 -17-was added to the reaction flask through the addition funnel over a twenty minute period in order to control the exotherm for the formation of the urethane. The reaction was maintained at 60°C for 4 hours, at which time the isocyanate content was 13.8% (theoretical NCO 13.0%).
The reaction was cooled to 40°C and 341 parts (0.93 equiv.) of N-(3-trimethoxysilylpropyl) aspartic acid diethyl ester were added through an addition funnel to control the exotherm. The reaction was heated for an additional 3 hours until no isocyanate groups remained as determined by IR spectroscopy. After cooling to room temperature, the resulting product had a viscosity of >100,000 mPa.s at 25°C.
parts of this product was combined with 10 parts of water and stirred at high speed with a lightning mixer. A stable dispersion resulted.
Example 3 - Preparation of water dispersible resin 2 195 parts (1 equiv) of polyisocyanate 1 were added at ambient 15 temperature to a three neck, 5 liter, round bottom flask equipped with an agitator, nitrogen inlet, thermocouple and addition funnel with condenser.
The reaction flask was heated to 60°C. 82.5 parts (0.15 equiv.) of polyether 2, heated to 60°C, was added to the reaction flask through the addition funnel over a twenty minute period in order to control the exotherm 20 for the formation of the urethane. The reaction was maintained at 60°C for 4 hours, at which time the isocyanate content was 14.4% (theoretical NCO
14.1 %).
The reaction was cooled to 40°C and 312 parts (0.85 equiv.) of N-(3-trimethoxysilylpropyl) aspartic acid diethyl ester were added through an addition funnel to control the exotherm. The reaction was heated for an additional 3 hours until no isocyanate groups remained as determined by IR spectroscopy. After cooling to room temperature, the resulting product had a viscosity of >100,000 mPa.s at 25°C.
Mo4795 -18-20 parts of this product was combined with 10 parts of water and stirred at high speed with a lightning mixer. A stable dispersion resulted.
Example 4 - (Comparison) - Preparation of water dispersible resin 3 Example 3 was repeated with the exception that no aminosilane was added. The resulting product was a hydrophilically modified polyisocyanate.
Example 5 - (Comparison) - Water dispersible resin 4 A water dispersible polyisocyanate having an isocyanate content of 17.3% and an equivalent weight of 243, based on solids. (Bayhydur XP-7063, available from Bayer Corp.).
Example 6 - Preparation of coatings 10 parts of water dispersible resin 1 were mixed with 10 parts of water, 5.4 parts of aqueous polyol 1 and 0.5 parts of catalyst (a proprietary titanate chelate, available as Tyzor 131 from DuPont). Films were drawn down on 4"x12" steel panels with a #30 wire-wound rod in a wet film thickness sufficient to provide a dry film thickness of 0.4 mils. The films were cured at 120°C and 140°C for 30 and 60 minutes as set forth in Table 1. The films had no adhesion before baking, but good adhesion after baking.
Curing Conditions Pencil Hardness MEK Double Rubs 120C, 30 minutes 3H 100 120C, 60 minutes 3H 100 140C, 30 minutes 5H 100 140C, 60 minutes 4H 100 Example 7 - Preparation of coating Water dispersible resin 2 was dispersed in an equal amount of water on a high speed mixer and then mixed with aqueous polyol 1 and with the Mo4795 -19-catalyst described in Example 6. The resulting mixtures were used to prepare films which were drawn down on cold rolled steel at a wet film thickness sufficient to provide a dry film thickness of 1 to 1.5 mils and cured either at room temperature or at elevated temperature as set forth in Table 2. The amounts of the various components and the properties of the resulting coatings are also set forth in Table 2.
Example 6 Ingredients Amounts in parts Water dispersible resin 2 10 Water 10 Aqueous Polyol 1 5.4 Catalyst 0.5 Cure at 25C/55% RH
Gardner Dry Time, days 5 MEK Double Rubs 100 Pencil Hardness F
Cure at 130C/ 30 min.
MEK Double Rubs 100 Pencil Hardness F
Dry times were determined with a Gardner Dry Time meter as described in Pacific Scientific Instruction manuals DG-9600 and DG-9300.
MEK double rubs was determined by wetting a cloth with methyl ethyl ketone and then rubbing each panel up to 100 times. A double rub consists of one back and forth rub against the coated panel. Values of less Mo4795 -20-than 100 indicate the number of double rubs before the coatings was destroyed.
Pencil hardness was determined in accordance with ASTM D-3363.
The order of hardnesses are as follows from softest to hardest: 6B to 1 B, HB, F, 1 H to 8H.
Examples 8-17 - Preparation of Coatings The water dispersible resin, the aqueous polyol, optionally a catalyst and sufficient water to provide a resin solids content of 40 to 43%, based on the resulting composition, were mixed with a high speed mixer.
The catalyst, if used, was the catalyst described in Example 6 and was used in an amount of 4.3%, based on resin solids. The resulting mixtures were used to prepare films which were drawn down on cold rolled steel at a wet film thickness of 3 mils (dry film thickness - 0.4 mils) and air dried for 16 hours at 25°C and 55% relative humidity and then at 140°C for minutes. The water dispersible resin, the aqueous polyol, the presence of catalyst, the silane or NCO to OH equivalent ratio and the pencil hardness of the resulting films are set forth in Table 3.
Mo4795 -21-Example Water Aqueous Silane Catalyst Pencil Dispers- Polyol or Hardness ible resin NCO to OH ratio 8 2 1 3:1 No 6H
9 2 1 3:1 Yes 6H
(comp) 3 1 2:1 No F
5 11 (comp) 4 1 2:1 No 3H
12 2 2 3:1 No 5H
13 2 2 3:1 Yes 5H
14 (comp) 4 2 2:1 No 5H
2 3 3:1 No B
(comp) 3 1 2:1 No F
5 11 (comp) 4 1 2:1 No 3H
12 2 2 3:1 No 5H
13 2 2 3:1 Yes 5H
14 (comp) 4 2 2:1 No 5H
2 3 3:1 No B
10 16 2 3 3:1 Yes H
17 (comp) 4 3 2:1 No 5H
The pencil hardness values set forth in the preceding table demonstrate that only coatings prepared from the compositions according 15 to the present invention possess higher hardnesses when compared to prior art coating compositions containing polyhydroxy polyesters and water dispersible polyisocyanates. This can be seen by comparing the pencil hardnesses for Examples 7 and 8 with those for Comparison Examples 9 and 10. The hardnesses for Examples 11-13, which were based on urethane group-containing polyols, were unaffected by the type of cross linking agent. To the contrary the hardnesses for Examples 14-16, which were based on polyacrylate polyols, decreased when the compounds containing urea and alkoxysilane groups were used in place of the known water dispersible polyisocyanates.
The examples also demonstrate that the improvements in hardness for the aqueous coating compositions according to the invention were not Mo4795 -22-dependent on the presence of catalyst, nor were they affected by the ratio of silane or isocyanate groups to hydroxy groups.
Although the invention has been described in detail 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.
17 (comp) 4 3 2:1 No 5H
The pencil hardness values set forth in the preceding table demonstrate that only coatings prepared from the compositions according 15 to the present invention possess higher hardnesses when compared to prior art coating compositions containing polyhydroxy polyesters and water dispersible polyisocyanates. This can be seen by comparing the pencil hardnesses for Examples 7 and 8 with those for Comparison Examples 9 and 10. The hardnesses for Examples 11-13, which were based on urethane group-containing polyols, were unaffected by the type of cross linking agent. To the contrary the hardnesses for Examples 14-16, which were based on polyacrylate polyols, decreased when the compounds containing urea and alkoxysilane groups were used in place of the known water dispersible polyisocyanates.
The examples also demonstrate that the improvements in hardness for the aqueous coating compositions according to the invention were not Mo4795 -22-dependent on the presence of catalyst, nor were they affected by the ratio of silane or isocyanate groups to hydroxy groups.
Although the invention has been described in detail 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.
Claims (18)
1. An aqueous two-component composition comprising a) a compound having an alkoxysilane group content (calculated as Si, MW 28) of 1 to 6% by weight, based on the weight of the compound, and containing sufficient chemically incorporated hydrophilic groups to form a stable dispersion with water, wherein the alkoxysilane groups are incorporated as the reaction product of i) a polyisocyanate component having a minimum average functionality of 2.4 and containing at least 50% by weight of a polyisocyanate adduct and ii an amino compound corresponding to the formula I
wherein X represents identical or different organic groups which are inert to isocyanate groups below 100°C, provided that at least one of these groups is an alkoxy group, R1 represents an organic group which is inert to isocyanate groups at a temperature of 100°C or less, and n is an integer from 1 to 8, and b) a polyhydroxy compound containing ester and/or carbonate groups and having a urethane group content of less than 5% by weight, based on the weight of the polyhydroxy compound.
wherein X represents identical or different organic groups which are inert to isocyanate groups below 100°C, provided that at least one of these groups is an alkoxy group, R1 represents an organic group which is inert to isocyanate groups at a temperature of 100°C or less, and n is an integer from 1 to 8, and b) a polyhydroxy compound containing ester and/or carbonate groups and having a urethane group content of less than 5% by weight, based on the weight of the polyhydroxy compound.
2. The composition of Claim 1 wherein said amino compound corresponds to formula III
wherein Z represents COOR5 or an aromatic ring, R2 and R5 are identical or different and represent organic groups which are inert to isocyanate groups at a temperature of 100°C or less, and R3 and R4 are identical or different and represent hydrogen or organic groups which are inert to isocyanate groups at a temperature of 100°C or less.
wherein Z represents COOR5 or an aromatic ring, R2 and R5 are identical or different and represent organic groups which are inert to isocyanate groups at a temperature of 100°C or less, and R3 and R4 are identical or different and represent hydrogen or organic groups which are inert to isocyanate groups at a temperature of 100°C or less.
3. The composition of Claim 2 wherein X represents identical or different alkyl or alkoxy groups having 1 to 4 carbon atoms, Z represents COOR5, R2 and R5 are identical or different and represent alkyl groups having 1 to 9 carbon atoms, R3 and R4 represent hydrogen and n is an integer from 2 to 4.
4. The composition of Claim 2 wherein X represents identical or different alkoxy groups having 1 to 4 carbon atoms, Z represents COOR5, R2 and R5 are identical or different and represent methyl, ethyl or butyl, R3 and R4 represent hydrogen and n is 3.
5. The composition of Claim 1 wherein the polyisocyanate component has a minimum average functionality of at least 2.8 and contains at least 70 % by weight of a polyisocyanate adduct.
6. The composition of Claim 2 wherein the polyisocyanate component has a minimum average functionality of at least 2.8 and contains at least 70 % by weight of a polyisocyanate adduct.
7. The composition of Claim 3 wherein the polyisocyanate component has a minimum average functionality of at least 2.8 and contains at least 70 % by weight of a polyisocyanate adduct.
8. The composition of Claim 4 wherein the polyisocyanate component has a minimum average functionality of at least 2.8 and contains at least 70 % by weight of a polyisocyanate adduct.
9. The composition of Claim 5 wherein said polyisocyanate adduct contains isocyanurate groups, biuret groups, allophanate groups and/or uretdione groups.
10. The composition of Claim 6 wherein said polyisocyanate adduct contains isocyanurate groups, biuret groups, allophanate groups and/or uretdione groups.
11. The composition of Claim 7 wherein said polyisocyanate adduct contains isocyanurate groups, biuret groups, allophanate groups and/or uretdione groups.
12. The composition of Claim 8 wherein said polyisocyanate adduct contains isocyanurate groups, biuret groups, allophanate groups and/or uretdione groups.
13. The composition of Claim 9 wherein said polyhydroxy compound contains ester groups.
14. The composition of Claim 10 wherein said polyhydroxy compound contains ester groups.
15. The composition of Claim 11 wherein said polyhydroxy compound contains ester groups.
16. The composition of Claim 12 wherein said polyhydroxy compound contains ester groups.
17. A coating, sealant or adhesive prepared from the composition of Claim 1.
18. A coating prepared from the composition of Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/058,390 | 1998-04-09 | ||
| US09/058,390 US5945476A (en) | 1998-04-09 | 1998-04-09 | Aqueous two-component coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2266207A1 true CA2266207A1 (en) | 1999-10-09 |
Family
ID=22016522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002266207A Abandoned CA2266207A1 (en) | 1998-04-09 | 1999-03-18 | Aqueous two-component coating compositions |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5945476A (en) |
| EP (1) | EP0949283B1 (en) |
| JP (1) | JP2000119594A (en) |
| AT (1) | ATE294200T1 (en) |
| CA (1) | CA2266207A1 (en) |
| DE (1) | DE69924910T2 (en) |
| ES (1) | ES2242322T3 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19855999A1 (en) * | 1998-12-04 | 2000-06-15 | Bayer Ag | Lacquer preparation containing alkoxysilane |
| US6265517B1 (en) * | 1999-09-07 | 2001-07-24 | Bostik, Inc. | Silylated polyether sealant |
| DE10025304A1 (en) * | 2000-05-22 | 2001-11-29 | Bayer Ag | Mixtures of aqueous binders |
| US6444325B1 (en) * | 2000-12-22 | 2002-09-03 | Bayer Corporation | Two-component coating compositions containing silane adhesion promoters |
| US6596402B2 (en) * | 2000-12-29 | 2003-07-22 | Kimberly-Clark Worldwide, Inc. | Absorbent, lubricious coating and articles coated therewith |
| US7115321B2 (en) | 2002-07-26 | 2006-10-03 | Kimberly-Clark Worldwide, Inc. | Absorbent binder coating |
| US7205259B2 (en) * | 2002-07-26 | 2007-04-17 | Kimberly-Clark Worldwide, Inc. | Absorbent binder desiccant composition and articles incorporating it |
| DE60322923D1 (en) | 2002-09-24 | 2008-09-25 | Du Pont | WATER DISPERSIBLE POLYTHIOPHENE MANUFACTURES |
| US7390438B2 (en) | 2003-04-22 | 2008-06-24 | E.I. Du Pont De Nemours And Company | Water dispersible substituted polydioxythiophenes made with fluorinated polymeric sulfonic acid colloids |
| US20050137374A1 (en) * | 2003-12-17 | 2005-06-23 | Roesler Richard R. | Two-component water-borne adhesive |
| US20050137322A1 (en) * | 2003-12-17 | 2005-06-23 | Roesler Richard R. | Silane modified two-component polyurethane coating |
| US20050186427A1 (en) * | 2004-02-19 | 2005-08-25 | The Procter & Gamble Company | Lubricious coated applicator |
| US7312286B2 (en) * | 2005-12-02 | 2007-12-25 | Stockhausen, Inc. | Flexible superabsorbent binder polymer composition |
| US7335713B2 (en) | 2005-12-02 | 2008-02-26 | Stockhausen, Inc. | Method for preparing a flexible superabsorbent binder polymer composition |
| US7619131B2 (en) | 2005-12-02 | 2009-11-17 | Kimberly-Clark Worldwide, Inc. | Articles comprising transparent/translucent polymer composition |
| KR100995514B1 (en) * | 2007-12-21 | 2010-11-19 | (주)엘지하우시스 | Recording woven fabrics and manufacturing method thereof |
| MX2012010550A (en) * | 2010-04-21 | 2012-11-16 | Basf Coatings Gmbh | Coating materials with high solids content and good levelling, multi-coat paint systems produced therefrom and use thereof. |
| CN102173602B (en) * | 2011-01-21 | 2012-10-03 | 黄淮学院 | Glass fiber subjected to surface treatment, preparation method and application |
| JP2013151645A (en) * | 2011-12-27 | 2013-08-08 | Sumika Bayer Urethane Kk | Aqueous urethane resin composition |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3737245A1 (en) * | 1987-11-03 | 1989-05-18 | Bayer Ag | AQUEOUS SOLUTIONS OR DISPERSIONS OF POLYURETHANES, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS COATING AGENTS OR FOR THE PRODUCTION OF COATING AGENTS |
| DE3829587A1 (en) * | 1988-09-01 | 1990-03-15 | Bayer Ag | COATING AGENT, A PROCESS FOR THE PRODUCTION THEREOF, AND THE USE OF SELECTED TWO-COMPONENT POLYURETHANE SYSTEMS AS BINDER FOR SUCH COATING AGENTS |
| US5389718A (en) * | 1990-07-30 | 1995-02-14 | Miles Inc. | Two-component aqueous polyurethane dispersions |
| US5387642A (en) * | 1991-01-19 | 1995-02-07 | Bayer Aktiengesellschaft | Aqueous binder composition and a process for its preparation |
| CA2072693C (en) * | 1991-07-23 | 2003-04-22 | Peter H. Markusch | Aqueous two-component polyurethane-forming compositions and a process for their preparation |
| DE4134064A1 (en) * | 1991-10-15 | 1993-04-22 | Bayer Ag | BINDER COMBINATION, A METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DE4137896A1 (en) * | 1991-11-18 | 1993-05-19 | Bayer Ag | AQUEOUS BINDER COMBINATION AND THEIR USE |
| US5459197A (en) * | 1992-02-07 | 1995-10-17 | Bayer Aktiengesellschaft | Coating compositions, a process for their production and their use for coating water-resistant substrates |
| DE4237468A1 (en) * | 1992-11-06 | 1994-05-11 | Bayer Ag | Compounds containing alkoxysilane and amino groups |
| DE4413562A1 (en) * | 1994-04-19 | 1995-10-26 | Herberts Gmbh | Aqueous dispersion of polyurethanes containing siloxane bridges, their production and use in coating compositions |
| DE19624972C2 (en) * | 1996-06-22 | 1998-06-04 | Herberts Gmbh | Aqueous dispersion of silane-functional polyurethane resins, their production and use |
| DE19715427A1 (en) * | 1997-04-14 | 1998-10-15 | Bayer Ag | Aqueous 2-component binders and their use |
-
1998
- 1998-04-09 US US09/058,390 patent/US5945476A/en not_active Expired - Fee Related
-
1999
- 1999-03-18 CA CA002266207A patent/CA2266207A1/en not_active Abandoned
- 1999-03-29 DE DE69924910T patent/DE69924910T2/en not_active Expired - Lifetime
- 1999-03-29 AT AT99106419T patent/ATE294200T1/en active
- 1999-03-29 EP EP99106419A patent/EP0949283B1/en not_active Expired - Lifetime
- 1999-03-29 ES ES99106419T patent/ES2242322T3/en not_active Expired - Lifetime
- 1999-04-07 JP JP11100178A patent/JP2000119594A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ATE294200T1 (en) | 2005-05-15 |
| EP0949283B1 (en) | 2005-04-27 |
| US5945476A (en) | 1999-08-31 |
| EP0949283A1 (en) | 1999-10-13 |
| JP2000119594A (en) | 2000-04-25 |
| DE69924910T2 (en) | 2006-02-16 |
| DE69924910D1 (en) | 2005-06-02 |
| ES2242322T3 (en) | 2005-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6057415A (en) | Water dispersible polyisocyanates containing alkoxysilane groups | |
| CA2266211C (en) | Water dispersible compounds containing alkoxysilane groups | |
| CA2285776C (en) | Silane-modified polyurethane resins, a process for their preparation and their use as moisture-curable resins | |
| EP0949283B1 (en) | Aqueous two-component coating compositions | |
| US6005047A (en) | Moisture-curable compounds containing isocyanate and alkoxysilane groups | |
| US5932652A (en) | Aqueous polyurethane/urea dispersions containing alkoxysilane groups | |
| US6077902A (en) | Moisture-curable compounds containing isocyanate and alkoxysilane groups | |
| US6111010A (en) | Aqueous compounds containing alkoxysilane and/or silanol groups | |
| US6096823A (en) | Moisture-curable compounds containing isocyanate and alkoxysilane groups | |
| US6077901A (en) | Aqueous compositions containing mixtures of silane-functional resins | |
| US6063863A (en) | Aqueous compositions containing colloidal silica and compounds with alkoxysilane and/or silanol groups | |
| US6169140B1 (en) | Moisture-curable compositions containing polyisocyanates and polyacrylates having alkoxysilane groups | |
| CA2220326C (en) | Compounds containing alkoxysilane groups and hydantoin groups | |
| MXPA99009361A (en) | Compounds curable by humidity containing isocyanate and alcoxisil groups | |
| MXPA99009362A (en) | Compounds curable by humidity containing isocyanate and alcoxisil groups |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |