CA1161179A - Polyurethane resin coating composition - Google Patents
Polyurethane resin coating compositionInfo
- Publication number
- CA1161179A CA1161179A CA000369225A CA369225A CA1161179A CA 1161179 A CA1161179 A CA 1161179A CA 000369225 A CA000369225 A CA 000369225A CA 369225 A CA369225 A CA 369225A CA 1161179 A CA1161179 A CA 1161179A
- Authority
- CA
- Canada
- Prior art keywords
- article
- coating composition
- solid substrate
- polymer
- composition
- 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.)
- Expired
Links
Classifications
-
- 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
- C08G18/83—Chemically modified polymers
- C08G18/833—Chemically modified polymers by nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/906—Multipackage compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/31576—Ester monomer type [polyvinylacetate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31605—Next to free metal
Abstract
Abstract of the Disclosure Two-package waterborne polyurethane resin coating compositions which, when applied to a solid substrate produce an adherent, abrasion resistant coating thereon, are disclosed herein.
The coating compositions essentially include a small amount of N-methylpyrrolidone to improve adhesion to non-polar thermoplastic substrates and are prepared by providing a carboxyl group-containing polyurethane in aqueous dispersion and, optionally, a water dispersible acrylic, as a first part; and using a trifunctional aziridine compound to make the second part of the two package system.
The coating compositions essentially include a small amount of N-methylpyrrolidone to improve adhesion to non-polar thermoplastic substrates and are prepared by providing a carboxyl group-containing polyurethane in aqueous dispersion and, optionally, a water dispersible acrylic, as a first part; and using a trifunctional aziridine compound to make the second part of the two package system.
Description
1 60~IN588 POLYURETHANE RESIN COATING COMPOSITION
This invention relates to a protective coating composition. More particularly, it relates to a two-package polyurethane resin coating composi~ion which, when applied to a substrate, forms a protective, abrasion-resist nt, adherent coating thereon.
Background Of The Invention At present, two-package solvent-based polyurethane coatings are widely used as coatings for substrates, such as metals, wood and plastics.
These two-package solvent-base urethanes can be cured at room temperature or cured at relatively lower temperature. Such urethanes yield coatings with high levels of mar resistance and chemical resistance. They are so good that they often give more protection than is needed by the~substrate.
Because these coating compositions are made with organic solvents, which must be liberated into the atmosphere, the~ cause environmental problems which makes desirable a switch to non-toxic, e.g., aqueous-based compositions. Moreover, because the solvent-containing compositions are often reduced (i.e.,thinned) with strong non-polar to medium polar solvents, they often attack and degrade plastic substrates to an undesirable degree. Non-polar thermoplastics, such as aromatic polycarbonates, e.g., of bisphenol-A and phosgene, or polyphenylene ethers, e.g., poly(2,6~dimethyl-1,4-phenylene)ethers, are capable of being dissolved and/or attacked by such non-polar solvents, and they can be distorted with excessive heatO From the foregoing it follows that ideal coating compositions should be water-based, fairly polar, and capable of curing at room temperature or only slightly higher temperatures.
A series of two-package waterborne polyurethanes meeting all three requirements has now been developed, and is the subjec~ matter of this invention. The coating compositions are based on a prepolymerized polyurethane dispersed in water, the particles of the prepolymer having carboxyl and other ionic functional groups. These are further reacted with a trifunctional aziridine compound to yield a reactive composition which, when coated by conventional means on a substrate, produces a macro-polymeric coating with excellent chemical resistance and good durability. Good substrate protection can be achieved with these waterborne systems without the use of any organic solvent whatsoever. The coatings can also be formulated to include waterborne thermoplastic carboxylated acrylics, to reduce the amount of more expensive polyurethane and without greatly affecting physical properties. In an essential aspect, to provide adhesion to non-polar plastic substrates, it is an essential feature of the invention to add to the composition a small, effective amount, e.g., 1-7%
of N-methylpyrrolidone. Surprisingly, the plastic substrate is not all degraded in so-doing.
Protective coatings for metals, birght or dull, are also needed. For example, bright metallized plastics, wherein small amounts of metal ~0-IN588 are vacuum sputtered or vacuum metallized over the plastic, now popular with the auto industry because of their light weight, need protective layers -to prevent scratching and marring of the brilliant surface. Metal wheel covers (hub caps) also require protective coatings for their preservation and lasting beauty. In addition, protective coatings are widely used on the surfaces of rigid, formed thermoplastics.
Description Of The Invention According to the present invention there are provided two-package aqueous coating compositions comprlslng as:
Part A
(i) a carboxyl group-containing urethane prepolymer, said prepolymer being dispersed in (ii) a medium comprising predominantly water; and as, Part B
(i) a trifunctional aziridine compound, said compound being adapted to react with said urethane prepolymer to cross-link the same; and, a minor, effective amount of N-methylpyrrolidone, sufficient to enhance the adhesion of a coating prepared from such composition to a non-polar thermoplastic substrate.
Also contemplated are solid substrates having at least one surface coated with an aqueous coating composition as defined above.
Component A comprises an aqueous dispersion of a conventional carboxyl group-containing urethane prepolymer, such as made from a polyisocyanate and a polyol. Such are available commercially from a number of sources, such as Polyvinyl Chemcials, Inc., Wilmington, Massachusetts under the trade name Neorez, R-960.
Component B is a trifunctional aziridine compound, which is a derivative of ethyleneimi~e, having the formu1a: H2C / lH2 H C - C~
This is a~ailable from Cordova Chemlcal Co., Sacramento, California under the trade name XAMA-7.
If desired, there can be added to Part A, a proportion, of up to 74.0% by weight, solids basis, of a thermoplastic carboxylated acrylic resin.
~uitable commercial sources of such products are ~ohm and Haas Co., Philadelphia, Penn., produce designation Rhoplex WL-91; Union Carbide Co., New York, N.Y. Ucar 4431 and Stanley Chemicals, Stacryl 200.
Mixtures can also be used.
N-methylpyrrolidone, used in all of the embodiments, is commercially available.
Although water can be used exclusively, other polar liquid solvents can replace part of the water, e.g., for volatility control, Alcohols are suitable for such purposes, including lower aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and t-butyl alcohol.
Mixtures of such alcohols can be used, too. The solids content of the coating compositions of this invention after mixing Parts A and B is generally preferred to be in the range of from about 30 to 45~, most preferably, about 40%, by weight of the total composition. The pH of the resultant coating composition is in the range of from about 7.8 to about 8.5, preferably higher than 7.5. If necessary, dilute hase, such as ammonium hydroxide, can be added to the composition to adjust the final pH to this desired range.
Conventional additives and other modifying agents, such as thickeners, pigments, dyes, and the like, may be added to the composition at any time.
The coating compositions of this invention will cure on a substrate at temperatures of from 25C to about 93C and are applied within a short time after mixing, as is done with the conventional two-package organic solvent compositions.
The coating compositions of the present invention can be applied to a variety of solid substrates by conventional methods, such as flowing, spraying or dipping, to form a continuous surface film. Substrates which are especially contemplated herein are metals and solid or foamed, transparent, as well as non-transparent, plastics, wood, and the like. More particularly, the plastics can be synthetic organic polymeric substrates such as acrylic polymers, like poly(methylmethacrylate), polyesters, such as poly(ethylene terephthalate), poly(butylene terephthalate), etc., polyamides, polyimides, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene copolymers, polyvinyl chloride, butyrates, polyethylene and the like. As noted above, the coating compositions of this invention are especially useful as coatings for polycarbonates, such as those polycarbonates know~ as LEXAN, sold by General Electric Company, and for polyphenylene ethers and compositions thereof such as NORYL, sold by General Electric Company. The metal substrates on which the present protective coatings are utilized include bright and dull metals like aluminum and bright metallized surfaces like sputtered chromium alloy, and treated metals, such as Bonderites. Other solid substrates contemplated herein include painted wood surfaces, leather, glass, ceramics and the like.
A hard coating having all of the aforementioned characteristics and advantages is obtained by the removal of the solvent and volatile materials. The coating composition will air-dry to a tack-free condition, but heating in the range of 66C to 93C
for 10 to 20 minutes is necessary to obtain final cure.
In order -that those skilled in the art may better understand how to prackice the present invention, the following examples are given by way of illustration and not by way of limitation.
Part A is made by milling the following:
Component Parts by Weight Carboxylated acrylic (42% solids in water) 43.6 Water 3-7 Green pigment package 15.0 Syloid 244 3.3 The milled product is rinsed with a small amount of water into a mixing vessel to which is added:
Carboxylated urethane prepolymer (33% solids in water) 21.3 Carnauba wax 2.1 The pH is adjusted to 7.8-8.2 with aqueous ammonia. To the mixture then is added a premix of Butyl cellosolve 5.0 N~methylpyrrolidone 2.7 Viscosity is adjusted with a small amount of water and the composition is filtered. The carboxylated acrylic is a product of Rohm and Elaas, Rhoplex WL-91;
the Syloid 244 is a product of W.R. Grace Co.;
the carboxylated urethane prepolymer i5 a product of Polyvinyl Chemicals, Inc., NebRex R-960.
Part B comprises 100% by weight solids of a trifunctional aziridine compound sold by Cordova Chemical Co., trade designation XAMA-7.
- To produce a coating, mix 92 parts OI A
and 2.0 parts of B, by weight, with agitation.
Reduce with water to a #2 Zahn viscosity of 40+5 seconds and apply to a Bonderite B-100 surface by spraying. Permit the solvent to flash off for 10 minutesr then bake at 65C for 15 minutes. The cured film is green with a pencil hardness of F-~, a Gardner Gloss of 10+2, and an adhesion by cross-hatch of 95%+. Impact, both reverse and direct is greater than 160 inch pounds.
The coating is remarkably adherent to non-polar thermoplastic substrates, such as the aromatic polycarbonate of bisphenol-A and phosgene, and to compositions containing poly(2,6-dimethyl-1, 4-phenylene)ether. Adhesion to these substrates is directly dependent upon the amount of N-methylpyrrolidone added.
Part A is made by milling the following:
ComponentParts by Weight Carboxylated acrylic (42~ solids in water)41.8 Water 3.4 Black pigment package 3.7 Syloid 244 3.5 The milled product is rinsed with a small amount of water into a mixing vessel to which is added a premixture comprising:
Carboxylated acrylic (42~ solids in water) 5.5 Carboxylated urethane (33~ solids in water) 16.2 Carnauba wax l.9 Polyethylene (40% solids i~)1.9 Acrylic polymer (Stacryl 200)6.5 The pH is adjusted in 7.8 with a~ueous ammonia. To the mixture then is added a premix of:
Propylene glycol 4.4 Butyl cellosolve 6.6 N-methylpyrrolidone 1.4 The sources of the components are as set forth in Example 1.
Part B comprises 100~ by weight solids of a trifunctional aziridine compound sold by Cordova Chemical Co., trade designation XAMA-7.
To produce a coating, mix 89 parts by weight of Part A with 1.9 parts of Part B and reduce the viscosity with water to Zahn #2, 23 seconds.
Apply to Bonderite B-1000, air dry 10 minutes, then bake at 74C for 15 minutes to produce a 1 mil thick film, having a pencil hardness of F, a Gardner gloss of 10-2 units and a cross-hatch adhesion of 100~.
Impact both reverse and direct is 160 inch-lbs.
Obsiously, other modifications and variations of the present invention are possible in the light of the above teachings. It is therefore to be understood that changes may be made in the particular embodiments described above which are within the full intended scope of the invention as defined in the appended claims.
This invention relates to a protective coating composition. More particularly, it relates to a two-package polyurethane resin coating composi~ion which, when applied to a substrate, forms a protective, abrasion-resist nt, adherent coating thereon.
Background Of The Invention At present, two-package solvent-based polyurethane coatings are widely used as coatings for substrates, such as metals, wood and plastics.
These two-package solvent-base urethanes can be cured at room temperature or cured at relatively lower temperature. Such urethanes yield coatings with high levels of mar resistance and chemical resistance. They are so good that they often give more protection than is needed by the~substrate.
Because these coating compositions are made with organic solvents, which must be liberated into the atmosphere, the~ cause environmental problems which makes desirable a switch to non-toxic, e.g., aqueous-based compositions. Moreover, because the solvent-containing compositions are often reduced (i.e.,thinned) with strong non-polar to medium polar solvents, they often attack and degrade plastic substrates to an undesirable degree. Non-polar thermoplastics, such as aromatic polycarbonates, e.g., of bisphenol-A and phosgene, or polyphenylene ethers, e.g., poly(2,6~dimethyl-1,4-phenylene)ethers, are capable of being dissolved and/or attacked by such non-polar solvents, and they can be distorted with excessive heatO From the foregoing it follows that ideal coating compositions should be water-based, fairly polar, and capable of curing at room temperature or only slightly higher temperatures.
A series of two-package waterborne polyurethanes meeting all three requirements has now been developed, and is the subjec~ matter of this invention. The coating compositions are based on a prepolymerized polyurethane dispersed in water, the particles of the prepolymer having carboxyl and other ionic functional groups. These are further reacted with a trifunctional aziridine compound to yield a reactive composition which, when coated by conventional means on a substrate, produces a macro-polymeric coating with excellent chemical resistance and good durability. Good substrate protection can be achieved with these waterborne systems without the use of any organic solvent whatsoever. The coatings can also be formulated to include waterborne thermoplastic carboxylated acrylics, to reduce the amount of more expensive polyurethane and without greatly affecting physical properties. In an essential aspect, to provide adhesion to non-polar plastic substrates, it is an essential feature of the invention to add to the composition a small, effective amount, e.g., 1-7%
of N-methylpyrrolidone. Surprisingly, the plastic substrate is not all degraded in so-doing.
Protective coatings for metals, birght or dull, are also needed. For example, bright metallized plastics, wherein small amounts of metal ~0-IN588 are vacuum sputtered or vacuum metallized over the plastic, now popular with the auto industry because of their light weight, need protective layers -to prevent scratching and marring of the brilliant surface. Metal wheel covers (hub caps) also require protective coatings for their preservation and lasting beauty. In addition, protective coatings are widely used on the surfaces of rigid, formed thermoplastics.
Description Of The Invention According to the present invention there are provided two-package aqueous coating compositions comprlslng as:
Part A
(i) a carboxyl group-containing urethane prepolymer, said prepolymer being dispersed in (ii) a medium comprising predominantly water; and as, Part B
(i) a trifunctional aziridine compound, said compound being adapted to react with said urethane prepolymer to cross-link the same; and, a minor, effective amount of N-methylpyrrolidone, sufficient to enhance the adhesion of a coating prepared from such composition to a non-polar thermoplastic substrate.
Also contemplated are solid substrates having at least one surface coated with an aqueous coating composition as defined above.
Component A comprises an aqueous dispersion of a conventional carboxyl group-containing urethane prepolymer, such as made from a polyisocyanate and a polyol. Such are available commercially from a number of sources, such as Polyvinyl Chemcials, Inc., Wilmington, Massachusetts under the trade name Neorez, R-960.
Component B is a trifunctional aziridine compound, which is a derivative of ethyleneimi~e, having the formu1a: H2C / lH2 H C - C~
This is a~ailable from Cordova Chemlcal Co., Sacramento, California under the trade name XAMA-7.
If desired, there can be added to Part A, a proportion, of up to 74.0% by weight, solids basis, of a thermoplastic carboxylated acrylic resin.
~uitable commercial sources of such products are ~ohm and Haas Co., Philadelphia, Penn., produce designation Rhoplex WL-91; Union Carbide Co., New York, N.Y. Ucar 4431 and Stanley Chemicals, Stacryl 200.
Mixtures can also be used.
N-methylpyrrolidone, used in all of the embodiments, is commercially available.
Although water can be used exclusively, other polar liquid solvents can replace part of the water, e.g., for volatility control, Alcohols are suitable for such purposes, including lower aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and t-butyl alcohol.
Mixtures of such alcohols can be used, too. The solids content of the coating compositions of this invention after mixing Parts A and B is generally preferred to be in the range of from about 30 to 45~, most preferably, about 40%, by weight of the total composition. The pH of the resultant coating composition is in the range of from about 7.8 to about 8.5, preferably higher than 7.5. If necessary, dilute hase, such as ammonium hydroxide, can be added to the composition to adjust the final pH to this desired range.
Conventional additives and other modifying agents, such as thickeners, pigments, dyes, and the like, may be added to the composition at any time.
The coating compositions of this invention will cure on a substrate at temperatures of from 25C to about 93C and are applied within a short time after mixing, as is done with the conventional two-package organic solvent compositions.
The coating compositions of the present invention can be applied to a variety of solid substrates by conventional methods, such as flowing, spraying or dipping, to form a continuous surface film. Substrates which are especially contemplated herein are metals and solid or foamed, transparent, as well as non-transparent, plastics, wood, and the like. More particularly, the plastics can be synthetic organic polymeric substrates such as acrylic polymers, like poly(methylmethacrylate), polyesters, such as poly(ethylene terephthalate), poly(butylene terephthalate), etc., polyamides, polyimides, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene copolymers, polyvinyl chloride, butyrates, polyethylene and the like. As noted above, the coating compositions of this invention are especially useful as coatings for polycarbonates, such as those polycarbonates know~ as LEXAN, sold by General Electric Company, and for polyphenylene ethers and compositions thereof such as NORYL, sold by General Electric Company. The metal substrates on which the present protective coatings are utilized include bright and dull metals like aluminum and bright metallized surfaces like sputtered chromium alloy, and treated metals, such as Bonderites. Other solid substrates contemplated herein include painted wood surfaces, leather, glass, ceramics and the like.
A hard coating having all of the aforementioned characteristics and advantages is obtained by the removal of the solvent and volatile materials. The coating composition will air-dry to a tack-free condition, but heating in the range of 66C to 93C
for 10 to 20 minutes is necessary to obtain final cure.
In order -that those skilled in the art may better understand how to prackice the present invention, the following examples are given by way of illustration and not by way of limitation.
Part A is made by milling the following:
Component Parts by Weight Carboxylated acrylic (42% solids in water) 43.6 Water 3-7 Green pigment package 15.0 Syloid 244 3.3 The milled product is rinsed with a small amount of water into a mixing vessel to which is added:
Carboxylated urethane prepolymer (33% solids in water) 21.3 Carnauba wax 2.1 The pH is adjusted to 7.8-8.2 with aqueous ammonia. To the mixture then is added a premix of Butyl cellosolve 5.0 N~methylpyrrolidone 2.7 Viscosity is adjusted with a small amount of water and the composition is filtered. The carboxylated acrylic is a product of Rohm and Elaas, Rhoplex WL-91;
the Syloid 244 is a product of W.R. Grace Co.;
the carboxylated urethane prepolymer i5 a product of Polyvinyl Chemicals, Inc., NebRex R-960.
Part B comprises 100% by weight solids of a trifunctional aziridine compound sold by Cordova Chemical Co., trade designation XAMA-7.
- To produce a coating, mix 92 parts OI A
and 2.0 parts of B, by weight, with agitation.
Reduce with water to a #2 Zahn viscosity of 40+5 seconds and apply to a Bonderite B-100 surface by spraying. Permit the solvent to flash off for 10 minutesr then bake at 65C for 15 minutes. The cured film is green with a pencil hardness of F-~, a Gardner Gloss of 10+2, and an adhesion by cross-hatch of 95%+. Impact, both reverse and direct is greater than 160 inch pounds.
The coating is remarkably adherent to non-polar thermoplastic substrates, such as the aromatic polycarbonate of bisphenol-A and phosgene, and to compositions containing poly(2,6-dimethyl-1, 4-phenylene)ether. Adhesion to these substrates is directly dependent upon the amount of N-methylpyrrolidone added.
Part A is made by milling the following:
ComponentParts by Weight Carboxylated acrylic (42~ solids in water)41.8 Water 3.4 Black pigment package 3.7 Syloid 244 3.5 The milled product is rinsed with a small amount of water into a mixing vessel to which is added a premixture comprising:
Carboxylated acrylic (42~ solids in water) 5.5 Carboxylated urethane (33~ solids in water) 16.2 Carnauba wax l.9 Polyethylene (40% solids i~)1.9 Acrylic polymer (Stacryl 200)6.5 The pH is adjusted in 7.8 with a~ueous ammonia. To the mixture then is added a premix of:
Propylene glycol 4.4 Butyl cellosolve 6.6 N-methylpyrrolidone 1.4 The sources of the components are as set forth in Example 1.
Part B comprises 100~ by weight solids of a trifunctional aziridine compound sold by Cordova Chemical Co., trade designation XAMA-7.
To produce a coating, mix 89 parts by weight of Part A with 1.9 parts of Part B and reduce the viscosity with water to Zahn #2, 23 seconds.
Apply to Bonderite B-1000, air dry 10 minutes, then bake at 74C for 15 minutes to produce a 1 mil thick film, having a pencil hardness of F, a Gardner gloss of 10-2 units and a cross-hatch adhesion of 100~.
Impact both reverse and direct is 160 inch-lbs.
Obsiously, other modifications and variations of the present invention are possible in the light of the above teachings. It is therefore to be understood that changes may be made in the particular embodiments described above which are within the full intended scope of the invention as defined in the appended claims.
Claims (11)
1. A two-package aqueous coating composition comprising as Part A
(i) a carboxyl group-containing urethane prepolymer, said prepolymer being dispersed in (ii) a polar liquid medium comprising pre-dominantly water; and as Part B
a trifunctional aziridine compound, said compound being adapted to react with said urethane prepolymer to cross-link the same; and a minor, effective amount of N-methylpyrrolidone, sufficient to enhance the adhesion of a coating prepared from such composition to a non-polar thermoplastic substrate.
(i) a carboxyl group-containing urethane prepolymer, said prepolymer being dispersed in (ii) a polar liquid medium comprising pre-dominantly water; and as Part B
a trifunctional aziridine compound, said compound being adapted to react with said urethane prepolymer to cross-link the same; and a minor, effective amount of N-methylpyrrolidone, sufficient to enhance the adhesion of a coating prepared from such composition to a non-polar thermoplastic substrate.
2. A coating composition as defined in claim 1 wherein the amount of N-methylpyrrolidone comprises from about 1 to about 7 parts by weight per 100 parts by weight of the total composition.
3. A coating composition as defined in claim 1 wherein Part A also includes up to 74.0% by weight, solids basis, of (iii) a water dispersible thermoplastic carboxylated acrylic polymer.
4. An article comprising solid substrate having at least one surface coated with the aqueous coating composition of claim 1.
5. An article as defined in claim 4 wherein the solid substrate is comprised of a synthetic organic polymer.
6. An article as defined in claim 5 wherein said polymer is an aromatic polycarbonate or a polyphenylene ether.
7. An article as defined in claim 4 wherein said solid substrate is a metal.
8. An article as defined in claim 5 wherein said polymer is a foamed polymer.
9. An article as defined in claim 6 wherein said aromatic polycarbonate is a poly(bisphenol-A carbonate).
10. An article as defined in claim 6 wherein said polyphenylene ether is poly(2,6-dimethyl-1,4-phenylene)-ether.
11. An article as defined in claim 6 wherein the aqueous coating composition has been cured on said surface of said solid substrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US116,925 | 1980-01-29 | ||
| US06/116,925 US4301053A (en) | 1980-01-29 | 1980-01-29 | Polyurethane resin coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1161179A true CA1161179A (en) | 1984-01-24 |
Family
ID=22370073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000369225A Expired CA1161179A (en) | 1980-01-29 | 1981-01-23 | Polyurethane resin coating composition |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4301053A (en) |
| CA (1) | CA1161179A (en) |
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| JPS576767A (en) * | 1980-06-16 | 1982-01-13 | Teijin Ltd | Easily adhesive polyester film |
| US4335187A (en) * | 1981-03-02 | 1982-06-15 | Ppg Industries, Inc. | Method for bonding polycarbonate to metal |
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| US4444846A (en) * | 1981-12-02 | 1984-04-24 | Lord Corporation | Thermally-responsive polymeric materials |
| US4540633A (en) * | 1983-04-20 | 1985-09-10 | Textron, Inc. | Water dispersible polyurethane adhesive compositions and adhesive layer formed therefrom |
| DE3316550C2 (en) * | 1983-05-03 | 1985-07-25 | Chemulack Chemische- Und Lackfabrik Gmbh & Co Kg, 1000 Berlin | Process for priming plastics |
| US4515919A (en) * | 1983-05-09 | 1985-05-07 | Lockheed Corporation | Protective coating composition and process for aluminum and aluminum alloys |
| WO1986002655A1 (en) * | 1984-11-02 | 1986-05-09 | Chemulack Chemische-Und Lackfabrik Gmbh & Co. Kg | Process for providing plastics with a primer |
| US4822685A (en) * | 1987-12-10 | 1989-04-18 | Ppg Industries, Inc. | Method for preparing multi-layered coated articles and the coated articles prepared by the method |
| US5026607A (en) * | 1989-06-23 | 1991-06-25 | C. R. Bard, Inc. | Medical apparatus having protective, lubricious coating |
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| DE69002295T2 (en) * | 1989-09-25 | 1993-11-04 | Schneider Usa Inc | MULTILAYER EXTRUSION AS A METHOD FOR PRODUCING BALLOONS FOR VESSEL PLASTICS. |
| US5091239A (en) * | 1990-03-07 | 1992-02-25 | Cms Gilbreth Packaging Systems, Inc. | Methods and adhesives for bonding polyolefin film |
| ZA913801B (en) * | 1990-05-21 | 1993-01-27 | Dow Chemical Co | Latent catalysts,cure-inhibited epoxy resin compositions and laminates prepared therefrom |
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| US5133997A (en) * | 1991-01-16 | 1992-07-28 | Union Carbide Marble Care, Inc. | Surface coating and method for applying same |
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| AT398979B (en) * | 1992-10-05 | 1995-02-27 | Vianova Kunstharz Ag | WATER-THINNABLE BINDING COMPOSITIONS AND THEIR USE FOR THE FORMULATION OF THICK-LAYER COATING MATERIALS |
| US5300325A (en) * | 1993-07-02 | 1994-04-05 | Lisco, Inc. | Method of finishing a golf ball or the like |
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| US6896842B1 (en) | 1993-10-01 | 2005-05-24 | Boston Scientific Corporation | Medical device balloons containing thermoplastic elastomers |
| US5554673A (en) * | 1993-11-29 | 1996-09-10 | Polygenex International, Inc. | Dip molded polyurethane film compositions |
| US6001906A (en) * | 1997-08-04 | 1999-12-14 | Golumbic; Harvey J. | Water based plasticizer free poly urethane-wax coating & repair composition & method |
| AU6681198A (en) | 1997-10-15 | 1999-05-03 | Minnesota Mining And Manufacturing Company | Abrasion-resistant ink compositions and methods of use |
| DE69827142T2 (en) * | 1998-11-11 | 2006-03-09 | Minnesota Mining And Manufacturing Co., St. Paul | Multilayer film containing a polyurethane protective layer |
| TW502043B (en) * | 1999-08-09 | 2002-09-11 | Chinese Petroleum Corp | Process for preparing self-emulsified aqueous epoxy resin dispersion, single-pack double curable aqueous resin composition comprising the same and single-pack curable composition of aqueous hybrid resin comprising the same |
| WO2001098392A1 (en) * | 2000-06-22 | 2001-12-27 | Pohang Iron & Steel Co., Ltd. | Preparation of aqueous urethane resin composition |
| US7297742B2 (en) * | 2004-05-11 | 2007-11-20 | Basf Corporation | Low VOC waterborne primer with high film smoothness |
| US20050288430A1 (en) * | 2004-06-25 | 2005-12-29 | Gindin Lyubov K | Polyurethane dispersions with high acid content |
| US20050288431A1 (en) * | 2004-06-25 | 2005-12-29 | Gindin Lyubov K | Polyurethane dispersion prepared from a high acid functional polyester |
| JP2009510194A (en) * | 2005-09-22 | 2009-03-12 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Adhesive coating composition for resin substrates |
| US7727134B2 (en) * | 2005-11-10 | 2010-06-01 | Canon Kabushiki Tokyo | Developing roller, process for its production, developing assembly and image forming apparatus |
| WO2008048778A2 (en) * | 2006-10-21 | 2008-04-24 | Fountainhead, Llc | Highly buoyant and semi-rigid floating islands |
| US20090298989A1 (en) * | 2008-05-28 | 2009-12-03 | Funston Sr Randall A | 2K Waterborne Polyurethane Coating System and Methods Thereof |
| US20100015456A1 (en) * | 2008-07-16 | 2010-01-21 | Eastman Chemical Company | Thermoplastic formulations for enhanced paintability toughness and melt process ability |
| KR100985274B1 (en) * | 2008-07-22 | 2010-10-04 | 이성민 | Aqueous coating composition for painting plastic substrate, and method of fabricating plastic case using the same |
| DE102009035807A1 (en) * | 2009-08-01 | 2011-02-03 | Bayer Materialscience Ag | Improved adhesion between thermoplastics and polyurethane |
| TW201107130A (en) * | 2009-08-18 | 2011-03-01 | guo-rui Huang | Composite material which lubricates during machinery processing |
| US8865261B2 (en) | 2012-12-06 | 2014-10-21 | Eastman Chemical Company | Extrusion coating of elongated substrates |
| TWI480299B (en) * | 2013-09-23 | 2015-04-11 | Univ Tamkang | Non-fluoro hydrophobic aqueous polyurethane resin dispersion, and production method and use thereof |
| US9920526B2 (en) | 2013-10-18 | 2018-03-20 | Eastman Chemical Company | Coated structural members having improved resistance to cracking |
| US9744707B2 (en) | 2013-10-18 | 2017-08-29 | Eastman Chemical Company | Extrusion-coated structural members having extruded profile members |
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|---|---|---|---|---|
| US3632556A (en) * | 1967-10-13 | 1972-01-04 | Us Agriculture | Treatment of textiles with aziridinemodified polyurethanes |
| US4183836A (en) * | 1978-02-06 | 1980-01-15 | E. I. Du Pont De Nemours And Company | Aqueous polyurethane dispersions |
-
1980
- 1980-01-29 US US06/116,925 patent/US4301053A/en not_active Expired - Lifetime
-
1981
- 1981-01-23 CA CA000369225A patent/CA1161179A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US4301053A (en) | 1981-11-17 |
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