CA2234421C - Coating compositions of an acrylic fluorocarbon polymer and a fluorinated polyisocyanate - Google Patents
Coating compositions of an acrylic fluorocarbon polymer and a fluorinated polyisocyanate Download PDFInfo
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- CA2234421C CA2234421C CA002234421A CA2234421A CA2234421C CA 2234421 C CA2234421 C CA 2234421C CA 002234421 A CA002234421 A CA 002234421A CA 2234421 A CA2234421 A CA 2234421A CA 2234421 C CA2234421 C CA 2234421C
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- 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
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/8087—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
- C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
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- 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]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
-
- 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]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
- Y10T428/31544—Addition polymer is perhalogenated
Abstract
A coating composition containing about 45-80 % by weight of a binder and 20-55 % by weight of an organic liquid; wherein the binder contains (A) about 40-90 % by weight, based on the weight of the binder, of an acrylic polymer containing polymerized hydroxyl containing monomers of the following group of hydroxy alkyl acrylate or methacrylates having 1-4 carbon atoms in the alkyl group, and polymerized alkyl acrylates and methacrylates having 1-18 carbon atoms in the alkyl groups, or styrene or any mixtures of the above and 0.1-5.0 R'o by weight, based on the weight of the acrylic polymer, of polymerized fluoroalkyl containing monomer represented by formula (I) where R is hydrogen or an alkyl group having 1-2 carbon atoms, n is an integer of 1-11 and R f is a fluoroalkyl containing group having at least 4 carbon atoms and (B) about 10-60 % by weight, based on the weight of the binder, of a fluorinated organic polyisocyanate cross-linking agent.
Description
COATING COMPOSITIONS OF AN ACRYLIC FLUOROCARBON
POLYMER AND A FLUORINATED POLYISOCYANATE
s BACKGROUND OF TAE INVENTION
1. Field of the Invention This invention is directed to coating compositions of acrylic fluorocarbon polymers and fluorinated polyisocyanates that remain relatively dirt free under exterior use conditions and are easily cleaned for 1 o example by washing with water when soiled.
POLYMER AND A FLUORINATED POLYISOCYANATE
s BACKGROUND OF TAE INVENTION
1. Field of the Invention This invention is directed to coating compositions of acrylic fluorocarbon polymers and fluorinated polyisocyanates that remain relatively dirt free under exterior use conditions and are easily cleaned for 1 o example by washing with water when soiled.
2. Description of the Prior Art Acrylic fluorocarbon polymer containing coating compositions that contain relatively small amounts of fluorocarbon constituents having resistance to cratering are shown in Chang US Patent i5 4,371,657 issued February 1, 1983 and Chang US Patent 4,396,680 issued August 2, 1983. Coating compositions of blends of acrylic polymers and acrylic polymer containing fluorocarbon constituents that form antiicing coatings are well known. Clear coats containing acrylic polymers having small amounts of fluorocarbon constituents that are applied over metallic a o base coats to provide auto finishes that have good weatherability, have high water and oil repellence and stain resistance are shown in Sugimura et al US Patent 4,812,337 issued March 14, 1989.
Fluorinated polyurethanes that are used as soil release agents are shown in Gresham US Patent 3,759,874 issued September 18, 1973.
25 Polyurethanes of fluorinated isocyanates that are used as adhesives are shown in Mitsch.US Patent 3,972,856 issued August 3, 1976. Protective coatings of fluorinated polyurethanes of fluorinated diols or triols are shown in Re et al US Patent 4,782, I30 issued November 1, 1988.
There is a need for a coating composition that provides for 3o soil resistance, is easily cleaned, has a low content of fluorocarbon constituents which reduces the cost of the composition since fluorocarbon monomers are expensive, and gives a coating that is high in solids that can be applied with conventional equipment and cures to a hard, tough, durable and weatherable finish without baking at elevated temperatures.
Fluorinated polyurethanes that are used as soil release agents are shown in Gresham US Patent 3,759,874 issued September 18, 1973.
25 Polyurethanes of fluorinated isocyanates that are used as adhesives are shown in Mitsch.US Patent 3,972,856 issued August 3, 1976. Protective coatings of fluorinated polyurethanes of fluorinated diols or triols are shown in Re et al US Patent 4,782, I30 issued November 1, 1988.
There is a need for a coating composition that provides for 3o soil resistance, is easily cleaned, has a low content of fluorocarbon constituents which reduces the cost of the composition since fluorocarbon monomers are expensive, and gives a coating that is high in solids that can be applied with conventional equipment and cures to a hard, tough, durable and weatherable finish without baking at elevated temperatures.
A coating composition containing about 45-80% by weight of a binder and 20-SS% by weight of an organic liquid; wherein the binder contains (A) about 40-90% by weight, based on the weight of the binder, of an acrylic polymer containing about 20-45% by weight, based on the weight of the acrylic polymer, of polymerized hydroxyl containing monomers selected from the following group of hydroxy alkyl acrylate or methacrylates Zo having 1-4 carbon atoms in the alkyl group, about 50-79.9%
by weight, based on the weight of the acrylic polymer, of polymerized alkyl acrylates and methacrylates having 1-18 carbon atoms in the alkyl groups, or styrene or any mixtures of the above and 0.1 - 5.0% by weight, based on the weight of is the acrylic polymer, of polymerized fluoroalkyl containing monomer represented by the formula CHZ=CR-~-p-(CH2)n-Rf where R is hydrogen or an alkyl group having 1-2 carbon atoms, n is an integer of 1-11 and Rfis a ffuoroalkyl 2 o containing group having at least 4 carbon atoms and the acrylic polymer has a weight average molecular weight of about 2,000-20,000 determined by gel permeation chromatography and as (B) about 10-60% by weight, based on the weight of the binder, of a fluorinated organic polyisocyanate crosslinking agent.
Articles coated with the composition also are part of this 3 o invention.
DETAILED DESCRIPTION OF TFIE INVENTION
The coating composition of this invention primarily is used as a clear coat over a pigmented base coat containing solid color pigments or s5 metallic flake pigments or mixtures thereof. The coating composition also can be used as a conventional pigmented composition. The coating composition can be applied with conventional spray equipment and cured at ambient temperatures or slightly elevated temperatures which decrease drying time. The resulting finish has excellent gloss and distinctness of image.
Preferably, the coating composition is a clear coating s composition, i.e. containing no pigments or a small amount of transparent pigment. The composition has a relatively high solids content of about 45-80% by weight of binder and about 20-55% by weight of an organic carrier which can be a solvent for the binder or a mixture of solvents and non solvent which would form a non aqueous dispersion. The composition has i o a low VOC (volatile organic content) and meets current pollution regulations.
The acrylic polymer used in the coating composition is prepared by conventional polymerization techniques in which the monomers, solvent, and polymerization initiator are charged over a 1-24 15 hour period of time, preferably in a 2-8 hour time period, into a conventional polymerization reactor in which the constituents are heated to about 60-175°C, preferably about 140 - 170°C. The polymer formed has a weight average molecular weight of about 2,000 - 20,000, preferably about 5,000 - 10,000.
2 o Molecular weight is determined by gel permeation chromatography using polystyrene as the standard.
In a preferred process for forming the acrylic polymer, the fluoroalkyl containing monomers are not added over an extended period of time with the other monomers but at any time during the polymerization 25 process such as the begirming, end or middle. The polymerizable fluoroalkyl containing monomers usually are blended with solvent and then added to the reactor. The ffuoroalkyl containing monomers are added in about 0.01-10% of the total time of polymerization of the polymer.
Preferably, the fluoroalkyl containing monomers are added after at least so some of the other monomers have been added and polymerized to some extent.
Typical polymerization initiators that are used in the process are azo type initiators such as azo-bis-isobutyronitrile, 1,1'-azo-bis(cyanocyclohexane), peroxy acetates such as t-butyl peracetate, ss peroxides such as di-t-butyl peroxide, benzoates such as t-butyl perbenzoate, octoates such as t-butyl peroctoate and the like.
Typical solvents that can be used in the process are ketones such as methyl amyl ketone, methyl isobutyl ketone, methyl ethyl ketone, aromatic hydrocarbons such as toluene, xylene, alkylene carbonates such as propylene carbonate, n-methyl pyrrolidone, ethers, esters, acetates and mixture of any of the above.
Typical polymerizable monomers that are used to form the s acrylic polymer are alkyl (meth)acrylates, meaning alkyl acrylates and alkyl methacrylates, having 1-18 carbon atoms in the alkyl group such as methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl methacrylate, butyl acrylate, isobutyl methacrylate, butyl methacrylate, t-butyl methacrylate, pentyl acrylate, pentyl i o methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate; other useful monomers are styrene, alpha methyl styrene, acrylamide, methacrylamide, acrylonitrile, hydroxy methacrylamide and the is like or any mixtures of these monomers, and hydroxy alkyl (meth)acrylates meaning hydroxy alkyl acrylates and hydroxy alkyl methacrylates having 1-4 carbon atoms in the alkyl groups such as hydroxy methyl acrylate, hydroxy methyl methacrylate, hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl methacrylate, hydroxy propyl acrylate, a o hydroxy butyl acrylate, hydroxy butyl methacrylate and the like.
The fluoroalkyl containing monomers are used in amounts of about 0.1-5.0% by weight, based on the weight of the acrylic polymer.
Useful fluorocarbon monomers are represented by the formula O
CH2=CR-~-p-(CHZ)n-Rf 2s where R is hydrogen or an alkyl group having 1-2 carbon atoms, n is an integer of 1-18 and Rfis a fluoroalkyl containing group having at least 4 carbon atoms and preferably a straight chain or branched chain ffuoroalkyl group having 4-20 carbon atoms which optionally can contain an oxygen atom.
s o Typically useful perfluoroalkyl containing monomers are perfluoro methyl ethyl methacrylate, pertluoro ethyl ethyl methacrylate, perfluoro butyl ethyl methacrylate, perfluoro pentyl ethyl methacrylate, perfluoro hexyl ethyl methacrylate, perfluoro octyl ethyl methacrylate, perfluoro decyl ethyl methacrylate, perfluoro lauryl ethyl methacrylate, 35 pertluoro stearyl ethyl methacrylate, perfluoro methyl ethyl acrylate, pertluoro ethyl ethyl acrylate, perfluoro butyl ethyl acrylate, perfluoro pentyl ethyl acrylate, perfluoro hexyl ethyl acrylate, perffuoro octyl ethyl acrylate, perfluoro decyt ethyl acrylate, perfluoro lauryl ethyl acrylate, perfluoro stearyl ethyl acrylate, and the like. Preferred are perffuoro alkyl ethyl methacrylates wherein the fluoroalkyl group contains 4-20 carbon atoms.
' s Other useful fluoroalkyl containing monomers are represented by the formula R~-S02 N-(CH2)~ O-~-CR=CH2 where R is as defined above, to Rl is a fluoroalkyl group having 4-12 carbon atoms, R2 is an alkyl group having 1-4 carbon atoms and n is an integer of 1-4.
Typical of these monomers are the following:
C8F~7S02N(CH2)2-O-~-CH=CHZ
CH3 ~ . CH3 C$F~7S02N(CH2)2-O-~-~-CH2 C$F~7S02N(Cti2)2-~-~-CH=CH2 CgF~7S02N(Cti2)2-O-C-C=CH2 C8F17S02N(CH2)i O-OC-CI-I-CH2 WO 97/14733 PC'r/L1S96/16289 Preferred acrylic polymers which form high quality coatings contain polymerized monomers of an alkyl methacrylate having 2-6 carbon atoms in the alkyl group, an alkyl acrylate having 2-8 carbon atoms in the alkyl group, a hydroxy alkyl acrylate having 2-4 carbon atoms in the alkyl s group, styrene and fluoroalkyl ethyl methacrylate having 4-20 carbon atoms in the alkyl group. One particularly preferred polymer contains butyl methacrylate, butyl acrylate, styrene, hydroxy propyl acrylate and the above fluoroalkyl containing monomer.
Another preferred acrylic polymer contains polymerized i o monomers of an alkyl methacrylate having 2-6 carbon atoms in the alkyl group, an alkyl acrylate having 2-8 carbon atoms in the alkyl group, styrene, an alkylene glycol methacrylate and a fluoroalkyl ethyl methacrylate having 4-20 carbon atoms in the alkyl group. One particularly preferred polymer contains butyl methacrylate, butyl acrylate, hydroxy propyl acrylate, i5 ethylene triglycol methacrylate and the above ffuoroalkyl ethyl methacrylate monomer.
The coating composition contains about 10-60% by weight of a fluorinated organic polyisocyanate crosslinking agent which is an adduct of a fluorinated monofunctional alcohol and a conventional organic ao polyisocyanate. About 0.1-33 mole percent of active isocysnate groups are reacted with the fluorinated monofnnctionai alcohol to form a fluorinated organic polyisocyanate. Typically, the constituents are reacted with a catalyst for about 0.1-4 hours at temperatures of about 50-120°C to form the adduct.
Any of the conventional aromatic, aliphatic, cycloaliphatic di and trifunctional polyisocyanates can be used. Typically useful diisocyanates are 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-biphenylene diisocyanate, toluene diisocyanate, bis cyclohexyl diisocyanate, tetramethylene xylene diisocyanate, ethyl ethylene so diisocyanate, 2,3-dimethyl ethylene diisocyanate, 1-methyltrimethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-phenylene diisocyanate, 1,5-naphthalene diisocyanate, bis-(4-isocyanatocyclohexyl)-methane, 4,4'-diisocyanatodiphenyl ether and the like.
35 Typical trifunctional isocyanates that can be used are triphenylmethane triisocyanate, 1,3,5-benzene triisocyanate, 2,4,5-toluene triisocyanate and the like. Oligomers of diisocyanates also can be used such as the trimer of hexamethylene diisocyanate which is sold under the tradename "Desmodur" N. One particularly preferred oligomer is "Desmodur" N-3390.
Typical fluorinated monofunctional alcohols used to form the isocyanate functional adducts are represented by the formula Ra I
Rf-(X)n (CHZCH-O)m H
where R f is as defined above, a fluoroalkyl containing group having at least 4 carbon atoms and preferably a straight chain or branched chain fluoroalkyl group having 4-20 carbon atoms which optionally can contain oxygen atoms as ether groups or can contain 1-5 chlorine atoms or i o I-S hydrogen atoms. Preferably, R f is a perfluoroalkyl group having 4-20 carbon atoms and most preferably, R f is a perfluoroalkyl group containing 6-12 carbon atoms. X is a divalent radical, preferably -CH2CH20-, -S02N(R4)CH2CH20-, -CH2-, -O-, -CH20- where R4 is an alkyl group preferably having 1-4. carbon atoms. R3 is H or an alkyl group having 1-4 is carbon atoms, H and methyl being preferred, n is 0-1 and m is 0-30, provided that if n is 0, then m must be greater than or equal to l, if m is 0, then n is 1; if X is -O-, m must be greater than or equal to 1; and m preferably 1-20.
The following are preferred fluorinated monofunctional a o alcohols:
Rf-~CH2--CHZ O ~H
where R f is a perfluoroalkyl group having 6-12 carbon atoms and n is 5-15;
H-ECF2CF2)n-CH20H
as where n is 1-6;
Rs I
CgF~7-SO2 N-(CHZ-CH2-O~H
where RS is an alkyl group having 1-4 carbon atoms and n is 1-30;
CF3-(-O-C-CF2 nO-ECH2-CH2 O- nH
F
so where n is 0-10 and m is 1-20; and Rp-CHZ--CH2--OH where R f is described above.
To improve weatherability of a clear coating composition about 0.1-10% by weight, based on the weight of the binder , of ultraviolet light stabilizers, screeners, quenchers and antioxidants usually are added.
Typical ultraviolet light screeners and stabilizers include the following:
Benzophenones such as hydroxy dodecyl oxy benzophenone, 2,4-dihydroxy benzophenone, hydroxy benzophenones containing sulfonic acid groups and the like.
io Benzoates such as dibenzoate of diphenylol propane, tertiary butyl benzoate of diphenylol propane and the like.
Triazines such as 3,5-dialkyl-4-hydroxy phenyl derivatives of triazine, sulfur containing derivatives of dialkyl-4-hydroxy phenyl triazine, hydroxy phenyl-1,3,5-triazine and the like.
15 Triazoles such as 2-phenyl-4-(2,2'-dihydroxybenzoyl)-triazole, substituted benzotriazoles such as hydroxy-phenyltaiazole and the like.
Hindered amines such as bis(1,2,2,6,6 pentamethyl-4-piperidinyl sebacate), di[4(2,2,6,6,tetramethyl piperidinyl)] sebacate and the 2 0 like and any mixtures of any of the above.
The coating composition contains a sufficient amount of a catalyst to cure the composition at ambient temperatures. Generally, about 0.01-2% by weight, based on the weight of the binder, of catalyst is used.
Typically useful catalysts are triethylene diamine and alkyl tin laurates such 2 s as dibutyl tin dilaurate, dibutyl tin diacetate, tertiary amines and the like.
Preferred is dibutyl tin dilaurate.
Generally, flow control agents are used in the composition in amounts of about 0.1-5% by weight, based on the weight of the binder, such as polyacrylic acid, polyalkylacrylates, polyether modified dimethyl s o polysiloxane copolymers and polyester modified polydimethyl siloxane.
When the coating composition is used as a clear coating composition usually over a pigmented base coat, it may be desirable to use pigments in the coating composition which have the same refractive index as the dried coating. Typically useful pigments have a particle size of about 35 0.015-50 micron and are used in a pigment to binder weight ratio of about 1:100 to 10:100 and are inorganic siliceous pigments such as silica pigment having a refractive index of about 1.4-1.6.
It is highly desirable to use at least some fluorinated organic polyisocyanate crosslinking agent, as described above, in the pigmented base coat over which the clear coat of this invention is applied to significantly reduce cratering of the base coat. Usually, about 10-40% by s weight, based on the weight of the binder, of the fluorinated polyisocyanate is used in the base coat.
When the coating composition is used as a clear coating on a vehicle such as a car, truck, bus, train, or on construction equipment, industrial equipment, structures such as tanks, bridges, exterior or interior i o of buildings, a basecoating which may be either a solvent based or waterbased composition is first applied and then the clear coating is applied usually by conventional means such as spraying or electrostatic spraying.
The clear coating is dried and cures at ambient temperatures but moderately high temperatures of up to about 90°C can be used to shorten drying time.
i5 The coating composition can be used as a conventional pigmented coating composition containing pigments in a pigment to binder weight ratio of about 0.1-100. The composition can be used to coat any of the aforementioned items and substrates and provides a finish that has good gloss and is weatherable, tough and hard.
2 o The following examples illustrate the invention. All parts and percentages are on a weight basis unless otherwise specified. Molecular weight was determined by gel permeation chromatography using polystyrene as the standard.
An acrylic polymer I solution was prepared in which the acrylic polymer has fluoroalkyl groups by charging the following constituents into a reactor equipped with a heat source, a thermometer and a stirrer:
Portion 1 Parts By Wei It Methyl amyl ketone 699.20 Portion 2 Butyl methacrylate monomer (BMA) 583.80 Styrene monomer (S) 307.28 Butyl acrylate monomer (BA) 343.20 Hydroxy propyl acrylate monomer (HPA)783.60 Methyl amyl ketone 4.72 Portion 3 Fluoroalkyl ethyl methacrylate monomer (FAMA) 30.73 -(fluoroalkyl group containing C-4. about 4%, C-6 about 30%, C-8 about 30%, C-10 about 20%, C-12 about 10% C-14 and above about 5%) Methyl amyl ketone 30.00 Portion 4 T-butyl peroxy acetate 69.01 Methyl amyl ketone 114.59 Portion 5 Methyl amyl ketone 33.28 Total 2999.99 Portion 1 was charged into the reaction vessel and blanketed with nitrogen and Portion 2 was premixed and added over a 360 minute period while holding the resulting mixture at its reflex temperature of about 150°C. Portion 3 was premixed and then added at one time to the reaction s mixture 350 minutes after the start of the addition of Portion 2. Portion 4 was premixed and added at the same time as Portion 2 to the reaction mixture over a 375 minute period and then Portion 5 was added and the reaction mixture was held at its reflex temperature for an additional 60 minutes. The resulting polymer solution was cooled to room temperature.
1 o The resulting acrylic polymer solution I had a weight solids content of about 70%, a polymer of BMA/SBAIHPA/FAMA in the following percentages 28.5%/15.0%/16.75%/38.25%/1.5% and the polymer had a weight average molecular weight of about 7,000.
Fluorinated polyisocyanate solution I was prepared by mixing is the following constituents in a reaction vessel equipped with a mechanical stirrer, condenser, nitrogen inlet and a thermocouple:
Portion 1 Parts by Weight Aliphatic isocyanate resin - trimer of hexamethylene 3000.00 diisocyanate (98.9% solids) Butyl acetate 275.00 Ethyl acetate 550.00 Ethylene glycol monobutyl ether acetate 175.00 Portion 2 Fluoroalkyl alcohol 27.20 [F(CF2)nCH2CH20(CH2CH20~H where n is an average of 6 and m is an average of 7.5]
Di-n-butyl tin dilaurate solution (2% solids in ethyl 0.50 acetate) Total 4027.70 Portions 1 and 2 were each added to the reaction vessel under ' a positive pressure of nitrogen and heated to about 75-80°C and held at this temperature for about 2 hours and allowed to cool overnight. The resulting fluorinated polyisocyanate solution I contained about 1% of the fluorinated s component.
Fluorinated polyisocyanate solution II was prepared as above except the amount of the fluorinating component was reduced by 50%
which resulted in a fluorinated polyisocyanate that contained 0.5% of the fluorinated component.
i o A clear acrylic composition I was prepared as follows:
Parts by Weight Portion 1 Methyl ethyl ketone 2.54 Toluene 2.67 Dibasic acid ester (ester mixture of adipic acid, glutaric1.79 acid and succinic acid) Butyl Cellosolve Acetate 4.96 Poz'tion 2 Acrylic polymer I solution (prepared above) 72.79 Portion 3 Resiflow S (Acrylic polymer flow additive) 0.35 "Tinuvin" 328 -. 2-(2-hydroxy-3,5-ditertiary amyl phenol)5.58 -2H-benzotriazole) "Tinuvin" 292 - (1,2,2,6,6-pentamethyl-4-piperidinyl) 0.87 sebacate Dibutyl tin dilaurate 0.92 PM acetate 7.38 Total 100.00 The constituents of Portion 1 were charged int o a mixing vessel in the order shown with continuous mixing. Portion 2 was added and mixed for 15 minutes. The constituents of Portion 3 were charged into the i5 mixing vessel in the order shown with constant mixing.
The resulting composition had a solids content of about 53.5%.
A clear coating composition I was prepared by mixing the above clear acrylic composition I with a the above prepared fluorinated polyisocyanate solution I in a 3/1 volume ratio. Clear coating composition II was prepared by mixing the above clear acrylic composition I with the s above prepared fluorinated polyisocyanate solution II in a 3/1 volume ratio.
A first set of two phosphated cold rolled steel panels that had.
been coated with a cured electrocoating composition of a polyepoxy hydroxy ether resin crosslinked with a polyisocyanate were spray coated with a white basecoat coating composition of an acrylic polymer containing io an organic polyisocyanate crosslinking agent to a dry film thickness of about 18-23 microns. The basecoat was allowed to stand for about 10 minutes to allow solvent to evaporate and then the above prepared clear coating composition I was spray applied. Two coats were applied with a solvent evaporation time of 2 minutes between the application of each coat.
i5 The resulting film was dried at about 83°C for about 30 minutes. The dry film thickness of the clear coat was about 44-56 microns. The resulting clear coat was smooth and essentially free of craters and had an excellent appearance.
A second set of two panels was prepared. Phosphated cold 2 o rolled steel panel electrocoated with the same above described electrocoating composition were coated with a black basecoat coating composition identical to the white basecoat coating composition except black pigmentation was used instead of white pigment and coated with the clear coating composition I as above and dried and cured as above. The a s resulting clear coat was smooth and essentially free of craters and had an excellent appearance. The following properties of the clear coated panel of 20° Gloss and Distinctness of Image (DOI) were measured and the results are shown in Table I.
A third and fourth set of panels were prepared identical to the 3 o above first and second set of panels except that clear coating composition II
was used in place of clear coating composition I. The results are shown in Table I.
Calculated ClearBase 20 PPM
Coat Coat oss OI Fluorine in Com osition I black 80.2 81.3 6500 I black 86.6 89.2 6500 I white 77.2 60.2 6500 I white 83.2 67.4 6500 II black 77.5 90.7 5600 II black 85.3 91.3 5600 II white 85.8 96.8 5600 II white 86.1 89.2 _ I ~ ~ I 5600 Fluorinated polyisocyanate solution III was prepared by s mixing the following constituents in a reaction vessel equipped with a mechanical stirrer, condenser, nitrogen inlet and a thermocouple:
Portion 1 Parts By Wei;~ht Aliphatic isocyanate resin (described in Example 1) 3,626.0 Butyl acetate 332.0 Ethyl acetate 665.0 Ethylene glycol monobutyl ether acetate 212.0 Portion 2 Fluoroalkyl alcohol 116.0 [F(CF2CF2)nCH2CH20H which is a blend of homologuous series where 1-2% n =2, 27-34% n = 3, 29-34% n = 4, 17-21% n = 5, 6-9% n = 6, 2-5% n = 7 and 1-2% n = 8]
Di-n-butyl tin dilaurate (2% solids in ethyl acetate) 0.5 Total 4951.5 Portions 1 and 2 were each added to the reaction vessel under a positive pressure of nitrogen and heated to about 75-85°C and held at this temperature for about 2 hours and allowed to cool overnight. The resulting to fluorinated polyisocyanate solution III contained about 2.5% of the fluorinated component.
A clear coating composition III was prepared by mixing the clear acrylic composition I, described in Example l, with the above fluorinated polyisocyanate solution III in a 3/1 volume ratio. Two phosphated cold rolled steel panels electrocoated as described in Example 1 were spray coated with a white base coat described in Example 1 and coated with the clear coating composition III and cured following the procedure of Example 1. The resulting clear coat was smooth and s essentially free of craters and had an excellent appearance.
EXAMP~,E 3 "
Fluorinated polyisocyanate solution IV was prepared by mixing the following constituents in a reaction vessel equipped with a io mechanical stirrer, condenser, nitrogen inlet and a thermocouple:
Portioxi 1 Parts Bv Weight Aliphatic isocyanate resin (described in Example 1) 3,064.0 Butyl acetate 281.0 Ethyl acetate 562.0 Ethylene glycol monobutyl ether acetate 179.0 Portion 2 Fluoroalkyl alcohol 27.8 [Rf CH2CH2-O-(CH2CH20)n-H where Rf is approximately 1% CF9, 50-60% C6F13, 20-40%
C8F17, 5-15% C10F21, 1-S% C12F25, n is 15-20]
Di-n-butyl tin dilaurate (2% solids in ethyl acetate) 0.5 Total 4114.3 Portions l and 2 were each added to the reaction vessel under a positive pressure of nitrogen and heated to about 75-85°C and held at this temperature for about 2 hours and allowed to cool overnight.
A clear coating composition IV was prepared by mixing the is clear acrylic composition I, described in Example 1, with the above fluorinated polyisocyanate solution IV in a 3/1 volume ratio. Two phosphated cold rolled steel panels electrocoated as described in Example 1 were spray coated with a white base coat described in Example 1 and coated with the clear coating composition IV and cured following the z o procedure of Example I. The resulting clear coat was smooth and essentially free of craters and had an excellent appearance.
by weight, based on the weight of the acrylic polymer, of polymerized alkyl acrylates and methacrylates having 1-18 carbon atoms in the alkyl groups, or styrene or any mixtures of the above and 0.1 - 5.0% by weight, based on the weight of is the acrylic polymer, of polymerized fluoroalkyl containing monomer represented by the formula CHZ=CR-~-p-(CH2)n-Rf where R is hydrogen or an alkyl group having 1-2 carbon atoms, n is an integer of 1-11 and Rfis a ffuoroalkyl 2 o containing group having at least 4 carbon atoms and the acrylic polymer has a weight average molecular weight of about 2,000-20,000 determined by gel permeation chromatography and as (B) about 10-60% by weight, based on the weight of the binder, of a fluorinated organic polyisocyanate crosslinking agent.
Articles coated with the composition also are part of this 3 o invention.
DETAILED DESCRIPTION OF TFIE INVENTION
The coating composition of this invention primarily is used as a clear coat over a pigmented base coat containing solid color pigments or s5 metallic flake pigments or mixtures thereof. The coating composition also can be used as a conventional pigmented composition. The coating composition can be applied with conventional spray equipment and cured at ambient temperatures or slightly elevated temperatures which decrease drying time. The resulting finish has excellent gloss and distinctness of image.
Preferably, the coating composition is a clear coating s composition, i.e. containing no pigments or a small amount of transparent pigment. The composition has a relatively high solids content of about 45-80% by weight of binder and about 20-55% by weight of an organic carrier which can be a solvent for the binder or a mixture of solvents and non solvent which would form a non aqueous dispersion. The composition has i o a low VOC (volatile organic content) and meets current pollution regulations.
The acrylic polymer used in the coating composition is prepared by conventional polymerization techniques in which the monomers, solvent, and polymerization initiator are charged over a 1-24 15 hour period of time, preferably in a 2-8 hour time period, into a conventional polymerization reactor in which the constituents are heated to about 60-175°C, preferably about 140 - 170°C. The polymer formed has a weight average molecular weight of about 2,000 - 20,000, preferably about 5,000 - 10,000.
2 o Molecular weight is determined by gel permeation chromatography using polystyrene as the standard.
In a preferred process for forming the acrylic polymer, the fluoroalkyl containing monomers are not added over an extended period of time with the other monomers but at any time during the polymerization 25 process such as the begirming, end or middle. The polymerizable fluoroalkyl containing monomers usually are blended with solvent and then added to the reactor. The ffuoroalkyl containing monomers are added in about 0.01-10% of the total time of polymerization of the polymer.
Preferably, the fluoroalkyl containing monomers are added after at least so some of the other monomers have been added and polymerized to some extent.
Typical polymerization initiators that are used in the process are azo type initiators such as azo-bis-isobutyronitrile, 1,1'-azo-bis(cyanocyclohexane), peroxy acetates such as t-butyl peracetate, ss peroxides such as di-t-butyl peroxide, benzoates such as t-butyl perbenzoate, octoates such as t-butyl peroctoate and the like.
Typical solvents that can be used in the process are ketones such as methyl amyl ketone, methyl isobutyl ketone, methyl ethyl ketone, aromatic hydrocarbons such as toluene, xylene, alkylene carbonates such as propylene carbonate, n-methyl pyrrolidone, ethers, esters, acetates and mixture of any of the above.
Typical polymerizable monomers that are used to form the s acrylic polymer are alkyl (meth)acrylates, meaning alkyl acrylates and alkyl methacrylates, having 1-18 carbon atoms in the alkyl group such as methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl methacrylate, butyl acrylate, isobutyl methacrylate, butyl methacrylate, t-butyl methacrylate, pentyl acrylate, pentyl i o methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate; other useful monomers are styrene, alpha methyl styrene, acrylamide, methacrylamide, acrylonitrile, hydroxy methacrylamide and the is like or any mixtures of these monomers, and hydroxy alkyl (meth)acrylates meaning hydroxy alkyl acrylates and hydroxy alkyl methacrylates having 1-4 carbon atoms in the alkyl groups such as hydroxy methyl acrylate, hydroxy methyl methacrylate, hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl methacrylate, hydroxy propyl acrylate, a o hydroxy butyl acrylate, hydroxy butyl methacrylate and the like.
The fluoroalkyl containing monomers are used in amounts of about 0.1-5.0% by weight, based on the weight of the acrylic polymer.
Useful fluorocarbon monomers are represented by the formula O
CH2=CR-~-p-(CHZ)n-Rf 2s where R is hydrogen or an alkyl group having 1-2 carbon atoms, n is an integer of 1-18 and Rfis a fluoroalkyl containing group having at least 4 carbon atoms and preferably a straight chain or branched chain ffuoroalkyl group having 4-20 carbon atoms which optionally can contain an oxygen atom.
s o Typically useful perfluoroalkyl containing monomers are perfluoro methyl ethyl methacrylate, pertluoro ethyl ethyl methacrylate, perfluoro butyl ethyl methacrylate, perfluoro pentyl ethyl methacrylate, perfluoro hexyl ethyl methacrylate, perfluoro octyl ethyl methacrylate, perfluoro decyl ethyl methacrylate, perfluoro lauryl ethyl methacrylate, 35 pertluoro stearyl ethyl methacrylate, perfluoro methyl ethyl acrylate, pertluoro ethyl ethyl acrylate, perfluoro butyl ethyl acrylate, perfluoro pentyl ethyl acrylate, perfluoro hexyl ethyl acrylate, perffuoro octyl ethyl acrylate, perfluoro decyt ethyl acrylate, perfluoro lauryl ethyl acrylate, perfluoro stearyl ethyl acrylate, and the like. Preferred are perffuoro alkyl ethyl methacrylates wherein the fluoroalkyl group contains 4-20 carbon atoms.
' s Other useful fluoroalkyl containing monomers are represented by the formula R~-S02 N-(CH2)~ O-~-CR=CH2 where R is as defined above, to Rl is a fluoroalkyl group having 4-12 carbon atoms, R2 is an alkyl group having 1-4 carbon atoms and n is an integer of 1-4.
Typical of these monomers are the following:
C8F~7S02N(CH2)2-O-~-CH=CHZ
CH3 ~ . CH3 C$F~7S02N(CH2)2-O-~-~-CH2 C$F~7S02N(Cti2)2-~-~-CH=CH2 CgF~7S02N(Cti2)2-O-C-C=CH2 C8F17S02N(CH2)i O-OC-CI-I-CH2 WO 97/14733 PC'r/L1S96/16289 Preferred acrylic polymers which form high quality coatings contain polymerized monomers of an alkyl methacrylate having 2-6 carbon atoms in the alkyl group, an alkyl acrylate having 2-8 carbon atoms in the alkyl group, a hydroxy alkyl acrylate having 2-4 carbon atoms in the alkyl s group, styrene and fluoroalkyl ethyl methacrylate having 4-20 carbon atoms in the alkyl group. One particularly preferred polymer contains butyl methacrylate, butyl acrylate, styrene, hydroxy propyl acrylate and the above fluoroalkyl containing monomer.
Another preferred acrylic polymer contains polymerized i o monomers of an alkyl methacrylate having 2-6 carbon atoms in the alkyl group, an alkyl acrylate having 2-8 carbon atoms in the alkyl group, styrene, an alkylene glycol methacrylate and a fluoroalkyl ethyl methacrylate having 4-20 carbon atoms in the alkyl group. One particularly preferred polymer contains butyl methacrylate, butyl acrylate, hydroxy propyl acrylate, i5 ethylene triglycol methacrylate and the above ffuoroalkyl ethyl methacrylate monomer.
The coating composition contains about 10-60% by weight of a fluorinated organic polyisocyanate crosslinking agent which is an adduct of a fluorinated monofunctional alcohol and a conventional organic ao polyisocyanate. About 0.1-33 mole percent of active isocysnate groups are reacted with the fluorinated monofnnctionai alcohol to form a fluorinated organic polyisocyanate. Typically, the constituents are reacted with a catalyst for about 0.1-4 hours at temperatures of about 50-120°C to form the adduct.
Any of the conventional aromatic, aliphatic, cycloaliphatic di and trifunctional polyisocyanates can be used. Typically useful diisocyanates are 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-biphenylene diisocyanate, toluene diisocyanate, bis cyclohexyl diisocyanate, tetramethylene xylene diisocyanate, ethyl ethylene so diisocyanate, 2,3-dimethyl ethylene diisocyanate, 1-methyltrimethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-phenylene diisocyanate, 1,5-naphthalene diisocyanate, bis-(4-isocyanatocyclohexyl)-methane, 4,4'-diisocyanatodiphenyl ether and the like.
35 Typical trifunctional isocyanates that can be used are triphenylmethane triisocyanate, 1,3,5-benzene triisocyanate, 2,4,5-toluene triisocyanate and the like. Oligomers of diisocyanates also can be used such as the trimer of hexamethylene diisocyanate which is sold under the tradename "Desmodur" N. One particularly preferred oligomer is "Desmodur" N-3390.
Typical fluorinated monofunctional alcohols used to form the isocyanate functional adducts are represented by the formula Ra I
Rf-(X)n (CHZCH-O)m H
where R f is as defined above, a fluoroalkyl containing group having at least 4 carbon atoms and preferably a straight chain or branched chain fluoroalkyl group having 4-20 carbon atoms which optionally can contain oxygen atoms as ether groups or can contain 1-5 chlorine atoms or i o I-S hydrogen atoms. Preferably, R f is a perfluoroalkyl group having 4-20 carbon atoms and most preferably, R f is a perfluoroalkyl group containing 6-12 carbon atoms. X is a divalent radical, preferably -CH2CH20-, -S02N(R4)CH2CH20-, -CH2-, -O-, -CH20- where R4 is an alkyl group preferably having 1-4. carbon atoms. R3 is H or an alkyl group having 1-4 is carbon atoms, H and methyl being preferred, n is 0-1 and m is 0-30, provided that if n is 0, then m must be greater than or equal to l, if m is 0, then n is 1; if X is -O-, m must be greater than or equal to 1; and m preferably 1-20.
The following are preferred fluorinated monofunctional a o alcohols:
Rf-~CH2--CHZ O ~H
where R f is a perfluoroalkyl group having 6-12 carbon atoms and n is 5-15;
H-ECF2CF2)n-CH20H
as where n is 1-6;
Rs I
CgF~7-SO2 N-(CHZ-CH2-O~H
where RS is an alkyl group having 1-4 carbon atoms and n is 1-30;
CF3-(-O-C-CF2 nO-ECH2-CH2 O- nH
F
so where n is 0-10 and m is 1-20; and Rp-CHZ--CH2--OH where R f is described above.
To improve weatherability of a clear coating composition about 0.1-10% by weight, based on the weight of the binder , of ultraviolet light stabilizers, screeners, quenchers and antioxidants usually are added.
Typical ultraviolet light screeners and stabilizers include the following:
Benzophenones such as hydroxy dodecyl oxy benzophenone, 2,4-dihydroxy benzophenone, hydroxy benzophenones containing sulfonic acid groups and the like.
io Benzoates such as dibenzoate of diphenylol propane, tertiary butyl benzoate of diphenylol propane and the like.
Triazines such as 3,5-dialkyl-4-hydroxy phenyl derivatives of triazine, sulfur containing derivatives of dialkyl-4-hydroxy phenyl triazine, hydroxy phenyl-1,3,5-triazine and the like.
15 Triazoles such as 2-phenyl-4-(2,2'-dihydroxybenzoyl)-triazole, substituted benzotriazoles such as hydroxy-phenyltaiazole and the like.
Hindered amines such as bis(1,2,2,6,6 pentamethyl-4-piperidinyl sebacate), di[4(2,2,6,6,tetramethyl piperidinyl)] sebacate and the 2 0 like and any mixtures of any of the above.
The coating composition contains a sufficient amount of a catalyst to cure the composition at ambient temperatures. Generally, about 0.01-2% by weight, based on the weight of the binder, of catalyst is used.
Typically useful catalysts are triethylene diamine and alkyl tin laurates such 2 s as dibutyl tin dilaurate, dibutyl tin diacetate, tertiary amines and the like.
Preferred is dibutyl tin dilaurate.
Generally, flow control agents are used in the composition in amounts of about 0.1-5% by weight, based on the weight of the binder, such as polyacrylic acid, polyalkylacrylates, polyether modified dimethyl s o polysiloxane copolymers and polyester modified polydimethyl siloxane.
When the coating composition is used as a clear coating composition usually over a pigmented base coat, it may be desirable to use pigments in the coating composition which have the same refractive index as the dried coating. Typically useful pigments have a particle size of about 35 0.015-50 micron and are used in a pigment to binder weight ratio of about 1:100 to 10:100 and are inorganic siliceous pigments such as silica pigment having a refractive index of about 1.4-1.6.
It is highly desirable to use at least some fluorinated organic polyisocyanate crosslinking agent, as described above, in the pigmented base coat over which the clear coat of this invention is applied to significantly reduce cratering of the base coat. Usually, about 10-40% by s weight, based on the weight of the binder, of the fluorinated polyisocyanate is used in the base coat.
When the coating composition is used as a clear coating on a vehicle such as a car, truck, bus, train, or on construction equipment, industrial equipment, structures such as tanks, bridges, exterior or interior i o of buildings, a basecoating which may be either a solvent based or waterbased composition is first applied and then the clear coating is applied usually by conventional means such as spraying or electrostatic spraying.
The clear coating is dried and cures at ambient temperatures but moderately high temperatures of up to about 90°C can be used to shorten drying time.
i5 The coating composition can be used as a conventional pigmented coating composition containing pigments in a pigment to binder weight ratio of about 0.1-100. The composition can be used to coat any of the aforementioned items and substrates and provides a finish that has good gloss and is weatherable, tough and hard.
2 o The following examples illustrate the invention. All parts and percentages are on a weight basis unless otherwise specified. Molecular weight was determined by gel permeation chromatography using polystyrene as the standard.
An acrylic polymer I solution was prepared in which the acrylic polymer has fluoroalkyl groups by charging the following constituents into a reactor equipped with a heat source, a thermometer and a stirrer:
Portion 1 Parts By Wei It Methyl amyl ketone 699.20 Portion 2 Butyl methacrylate monomer (BMA) 583.80 Styrene monomer (S) 307.28 Butyl acrylate monomer (BA) 343.20 Hydroxy propyl acrylate monomer (HPA)783.60 Methyl amyl ketone 4.72 Portion 3 Fluoroalkyl ethyl methacrylate monomer (FAMA) 30.73 -(fluoroalkyl group containing C-4. about 4%, C-6 about 30%, C-8 about 30%, C-10 about 20%, C-12 about 10% C-14 and above about 5%) Methyl amyl ketone 30.00 Portion 4 T-butyl peroxy acetate 69.01 Methyl amyl ketone 114.59 Portion 5 Methyl amyl ketone 33.28 Total 2999.99 Portion 1 was charged into the reaction vessel and blanketed with nitrogen and Portion 2 was premixed and added over a 360 minute period while holding the resulting mixture at its reflex temperature of about 150°C. Portion 3 was premixed and then added at one time to the reaction s mixture 350 minutes after the start of the addition of Portion 2. Portion 4 was premixed and added at the same time as Portion 2 to the reaction mixture over a 375 minute period and then Portion 5 was added and the reaction mixture was held at its reflex temperature for an additional 60 minutes. The resulting polymer solution was cooled to room temperature.
1 o The resulting acrylic polymer solution I had a weight solids content of about 70%, a polymer of BMA/SBAIHPA/FAMA in the following percentages 28.5%/15.0%/16.75%/38.25%/1.5% and the polymer had a weight average molecular weight of about 7,000.
Fluorinated polyisocyanate solution I was prepared by mixing is the following constituents in a reaction vessel equipped with a mechanical stirrer, condenser, nitrogen inlet and a thermocouple:
Portion 1 Parts by Weight Aliphatic isocyanate resin - trimer of hexamethylene 3000.00 diisocyanate (98.9% solids) Butyl acetate 275.00 Ethyl acetate 550.00 Ethylene glycol monobutyl ether acetate 175.00 Portion 2 Fluoroalkyl alcohol 27.20 [F(CF2)nCH2CH20(CH2CH20~H where n is an average of 6 and m is an average of 7.5]
Di-n-butyl tin dilaurate solution (2% solids in ethyl 0.50 acetate) Total 4027.70 Portions 1 and 2 were each added to the reaction vessel under ' a positive pressure of nitrogen and heated to about 75-80°C and held at this temperature for about 2 hours and allowed to cool overnight. The resulting fluorinated polyisocyanate solution I contained about 1% of the fluorinated s component.
Fluorinated polyisocyanate solution II was prepared as above except the amount of the fluorinating component was reduced by 50%
which resulted in a fluorinated polyisocyanate that contained 0.5% of the fluorinated component.
i o A clear acrylic composition I was prepared as follows:
Parts by Weight Portion 1 Methyl ethyl ketone 2.54 Toluene 2.67 Dibasic acid ester (ester mixture of adipic acid, glutaric1.79 acid and succinic acid) Butyl Cellosolve Acetate 4.96 Poz'tion 2 Acrylic polymer I solution (prepared above) 72.79 Portion 3 Resiflow S (Acrylic polymer flow additive) 0.35 "Tinuvin" 328 -. 2-(2-hydroxy-3,5-ditertiary amyl phenol)5.58 -2H-benzotriazole) "Tinuvin" 292 - (1,2,2,6,6-pentamethyl-4-piperidinyl) 0.87 sebacate Dibutyl tin dilaurate 0.92 PM acetate 7.38 Total 100.00 The constituents of Portion 1 were charged int o a mixing vessel in the order shown with continuous mixing. Portion 2 was added and mixed for 15 minutes. The constituents of Portion 3 were charged into the i5 mixing vessel in the order shown with constant mixing.
The resulting composition had a solids content of about 53.5%.
A clear coating composition I was prepared by mixing the above clear acrylic composition I with a the above prepared fluorinated polyisocyanate solution I in a 3/1 volume ratio. Clear coating composition II was prepared by mixing the above clear acrylic composition I with the s above prepared fluorinated polyisocyanate solution II in a 3/1 volume ratio.
A first set of two phosphated cold rolled steel panels that had.
been coated with a cured electrocoating composition of a polyepoxy hydroxy ether resin crosslinked with a polyisocyanate were spray coated with a white basecoat coating composition of an acrylic polymer containing io an organic polyisocyanate crosslinking agent to a dry film thickness of about 18-23 microns. The basecoat was allowed to stand for about 10 minutes to allow solvent to evaporate and then the above prepared clear coating composition I was spray applied. Two coats were applied with a solvent evaporation time of 2 minutes between the application of each coat.
i5 The resulting film was dried at about 83°C for about 30 minutes. The dry film thickness of the clear coat was about 44-56 microns. The resulting clear coat was smooth and essentially free of craters and had an excellent appearance.
A second set of two panels was prepared. Phosphated cold 2 o rolled steel panel electrocoated with the same above described electrocoating composition were coated with a black basecoat coating composition identical to the white basecoat coating composition except black pigmentation was used instead of white pigment and coated with the clear coating composition I as above and dried and cured as above. The a s resulting clear coat was smooth and essentially free of craters and had an excellent appearance. The following properties of the clear coated panel of 20° Gloss and Distinctness of Image (DOI) were measured and the results are shown in Table I.
A third and fourth set of panels were prepared identical to the 3 o above first and second set of panels except that clear coating composition II
was used in place of clear coating composition I. The results are shown in Table I.
Calculated ClearBase 20 PPM
Coat Coat oss OI Fluorine in Com osition I black 80.2 81.3 6500 I black 86.6 89.2 6500 I white 77.2 60.2 6500 I white 83.2 67.4 6500 II black 77.5 90.7 5600 II black 85.3 91.3 5600 II white 85.8 96.8 5600 II white 86.1 89.2 _ I ~ ~ I 5600 Fluorinated polyisocyanate solution III was prepared by s mixing the following constituents in a reaction vessel equipped with a mechanical stirrer, condenser, nitrogen inlet and a thermocouple:
Portion 1 Parts By Wei;~ht Aliphatic isocyanate resin (described in Example 1) 3,626.0 Butyl acetate 332.0 Ethyl acetate 665.0 Ethylene glycol monobutyl ether acetate 212.0 Portion 2 Fluoroalkyl alcohol 116.0 [F(CF2CF2)nCH2CH20H which is a blend of homologuous series where 1-2% n =2, 27-34% n = 3, 29-34% n = 4, 17-21% n = 5, 6-9% n = 6, 2-5% n = 7 and 1-2% n = 8]
Di-n-butyl tin dilaurate (2% solids in ethyl acetate) 0.5 Total 4951.5 Portions 1 and 2 were each added to the reaction vessel under a positive pressure of nitrogen and heated to about 75-85°C and held at this temperature for about 2 hours and allowed to cool overnight. The resulting to fluorinated polyisocyanate solution III contained about 2.5% of the fluorinated component.
A clear coating composition III was prepared by mixing the clear acrylic composition I, described in Example l, with the above fluorinated polyisocyanate solution III in a 3/1 volume ratio. Two phosphated cold rolled steel panels electrocoated as described in Example 1 were spray coated with a white base coat described in Example 1 and coated with the clear coating composition III and cured following the procedure of Example 1. The resulting clear coat was smooth and s essentially free of craters and had an excellent appearance.
EXAMP~,E 3 "
Fluorinated polyisocyanate solution IV was prepared by mixing the following constituents in a reaction vessel equipped with a io mechanical stirrer, condenser, nitrogen inlet and a thermocouple:
Portioxi 1 Parts Bv Weight Aliphatic isocyanate resin (described in Example 1) 3,064.0 Butyl acetate 281.0 Ethyl acetate 562.0 Ethylene glycol monobutyl ether acetate 179.0 Portion 2 Fluoroalkyl alcohol 27.8 [Rf CH2CH2-O-(CH2CH20)n-H where Rf is approximately 1% CF9, 50-60% C6F13, 20-40%
C8F17, 5-15% C10F21, 1-S% C12F25, n is 15-20]
Di-n-butyl tin dilaurate (2% solids in ethyl acetate) 0.5 Total 4114.3 Portions l and 2 were each added to the reaction vessel under a positive pressure of nitrogen and heated to about 75-85°C and held at this temperature for about 2 hours and allowed to cool overnight.
A clear coating composition IV was prepared by mixing the is clear acrylic composition I, described in Example 1, with the above fluorinated polyisocyanate solution IV in a 3/1 volume ratio. Two phosphated cold rolled steel panels electrocoated as described in Example 1 were spray coated with a white base coat described in Example 1 and coated with the clear coating composition IV and cured following the z o procedure of Example I. The resulting clear coat was smooth and essentially free of craters and had an excellent appearance.
Claims (11)
1. A coating composition containing about 45-80% by weight of a binder and 20-55% by weight of an organic liquid; wherein the binder comprises (A) about 40-90% by weight, based on the weight of the binder, of an acrylic polymer consisting essentially of about 20-45% by weight, based on the weight of the acrylic polymer, of polymerized hydroxyl containing monomers selected from the group consisting of hydroxy alkyl acrylate and hydroxy alkyl methacrylates having 1-4 carbon atoms in the alkyl groups, 50 - 79.9% by weight, based on the weight of the acrylic polymer, of polymerized monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates having 1 - 18 carbon atoms in the alkyl groups, styrene and any mixtures of the above and 0.1 - 5.0% by weight, based on the weight of the acrylic polymer, of polymerized fluoroalkyl containing monomer represented by the formula where R is selected from the group consisting of hydrogen or an alkyl group having 1 - 2 carbon atoms, n is an integer of 1-11 and R f is a ffuoroalkyl containing group having at least 4 carbon atoms and the acrylic polymer having a weight average molecular weight of about 2,000 - 20,000 determined by gel permeation chromatography, and (B) about 10-60% by weight, based on the weight of the binder, of a fluoripated organic polyisocyanate crosslinking agent consisting essentially of an adduct of a fluorinated monofunctional alcohol and an organic polyisocyanate where the fluorinated monofunctional alcohol is represented by the formula where R f is as defined above, X is a divalent radical, R3 is H or an alkyl group having 1-4 carbon atoms, n is 1 and m is 1-30 and where about 0.1-33 mole percent of active isocyanate groups are reacted with the fluorinated monofunctional alcohol.
2. The coating composition of Claim 1 in which R f of the fluoroalkyl monomer of the acrylic polymer and the fluorinated organic polyisocyanate is a straight chain or branched chain perfluoroalkyl group having 4-20 carbon atoms.
3. The coating compositions of Claim 2 in which the acrylic polymer consists essentially of polymerized monomers of an alkyl methacrylate having 2-carbon atoms in the alkyl groups, an alkyl acrylate having 2-8 carbon atoms in the alkyl group, a hydroxy alkyl acrylate having 2-4 carbon atoms in the alkyl group, styrene and a fluoroalkyl containing monomer wherein R is CH3 and n is 2.
4. The coating composition of Claim 3 in which the acrylic polyerm consists essentially of butyl methacrylate, butyl acrylate, styrene, hydroxy propyl acrylate and the perfluoroalkyl containing monomer.
5. The coating composition of Claim 3 in which the fluoroalkyl containing monomer of the acrylic polymer is represented by the formula where R is as defined in Claim 1, R1 is a perfluoroalkyl group having 4-12 carbon atoms, R2 is an alkyl group having 1-4 carbon atoms and n is an integer of 1-4.
6. The coating composition of Claim 1 in the fluorinated monofunctional alcohol X is -O-, -CH2O-, CH2CH2O-, -SO2N(R4)CH2CH2O-, CH2- where R4 is H or methyl.
7. The coating composition of Claim 1 in which the organic polyisocyanate is an aromatic diisocyanate, aliphatic diisocyanate, cycloaliphatic diisocyanate, aromatic triisocyanate, aliphatic triisocyanate, cycloaliphatic triisocyanate or an oligomer of a diisocyanate.
8. The coating composition of Claim 1 containing about 0.1-10% by weight, based on the weight of the binder, of ultraviolet light stabilizers or an antioxidant or mixtures thereof.
9. A substrate coated with a dried and cured layer of the composition of Claim 1.
10. A substrate coated with a pigmented base coat on which is coated a clear layer of the dried and cured composition of Claim 1.
11. The coated substrate of Claim 10 in which the pigmented base coat contains about 10-40% by weight, based on the weight of binder of the base coat, of a fluorinated polyisocyanate crosslinking agent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/543,721 US5597874A (en) | 1995-10-16 | 1995-10-16 | Coating compositions of an acrylic fluorocarbon polymer and a fluorinated polyisocyanate |
| US08/543,721 | 1995-10-16 | ||
| PCT/US1996/016289 WO1997014733A1 (en) | 1995-10-16 | 1996-10-11 | Coating compositions of an acrylic fluorocarbon polymer and a fluorinated polyisocyanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2234421A1 CA2234421A1 (en) | 1997-04-24 |
| CA2234421C true CA2234421C (en) | 2004-02-17 |
Family
ID=24169307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002234421A Expired - Fee Related CA2234421C (en) | 1995-10-16 | 1996-10-11 | Coating compositions of an acrylic fluorocarbon polymer and a fluorinated polyisocyanate |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US5597874A (en) |
| EP (1) | EP0856021B1 (en) |
| JP (1) | JP4074340B2 (en) |
| AU (1) | AU706335B2 (en) |
| BR (1) | BR9611102A (en) |
| CA (1) | CA2234421C (en) |
| DE (1) | DE69603195T2 (en) |
| NZ (1) | NZ321114A (en) |
| WO (1) | WO1997014733A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5914384A (en) * | 1997-11-21 | 1999-06-22 | E. I. Du Pont De Nemours And Company | Coating compositions containing a highly fluorinated hydroxyl containing additive |
| US6168866B1 (en) | 1998-08-19 | 2001-01-02 | 3M Innovative Properties Company | Abrasion and stain resistant curable fluorinated coating |
| US6586530B1 (en) | 2001-09-27 | 2003-07-01 | Ppg Industries Ohio, Inc. | Low surface tension (meth) acrylate containing block copolymer prepared by controlled radical polymerization |
| US6841641B2 (en) | 2001-09-27 | 2005-01-11 | Ppg Industries Ohio, Inc. | Copolymers comprising low surface tension (meth) acrylates |
| US6583223B2 (en) | 2001-09-27 | 2003-06-24 | Ppg Industries Ohio, Inc. | Coating compositions which contain a low surface tension (meth) acrylate containing block copolymer flow control agent |
| US6933005B2 (en) * | 2003-09-22 | 2005-08-23 | E. I. Du Pont De Nemours And Company | Method for achieving recoat adhesion over a fluorinated topcoat |
| US7348389B2 (en) * | 2003-09-22 | 2008-03-25 | E. I. Du Pont De Nemours And Company | Method for achieving recoat adhesion over a fluorinated topcoat |
| US7288282B2 (en) * | 2003-09-22 | 2007-10-30 | E. I. Du Pont De Nemours And Company | Coating compositions containing a fluorinated organosilane polymer |
| US8431216B2 (en) * | 2007-05-05 | 2013-04-30 | Lg Display Co., Ltd. | Optical film for a display device and method of fabricating the same |
| US9464160B2 (en) | 2010-08-27 | 2016-10-11 | The Chemours Company Fc, Llc | Fluorinated ethoxylated polyurethanes |
| WO2013081816A1 (en) | 2011-11-30 | 2013-06-06 | U.S. Coatings Ip Co. Llc | Clear coat coating composition |
| WO2013081815A1 (en) | 2011-11-30 | 2013-06-06 | U.S. Coatings Ip Co. Llc | Clear coat coating composition |
| EP2785758B1 (en) | 2011-11-30 | 2015-10-28 | Axalta Coating Systems IP Co. LLC | Clear coat coating composition |
| WO2013081892A1 (en) | 2011-11-30 | 2013-06-06 | U.S. Coatings Ip Co. Llc | Coating composition |
| RU2494875C1 (en) * | 2012-02-29 | 2013-10-10 | Закрытое акционерное общество по разработке и внедрению новых информационных материалов и технологий "БИТ" | Protective coating for power-saving films |
| US10040965B2 (en) | 2013-11-20 | 2018-08-07 | Osaka Organic Chemical Industry Ltd. | Clear coating composition |
| JP6157442B2 (en) * | 2013-12-25 | 2017-07-05 | 大阪有機化学工業株式会社 | Clear coat composition |
| PL3230335T3 (en) * | 2014-12-08 | 2019-07-31 | Basf Coatings Gmbh | Coating compositions and coatings prepared from these and their use |
| RU2670274C1 (en) * | 2014-12-08 | 2018-10-22 | БАСФ Коатингс ГмбХ | Non-aqueous coating compositions, coatings obtained from them and with improved adhesion and scrub resistance, and also their application |
| CN104710557A (en) * | 2014-12-31 | 2015-06-17 | 佛山市顺德区巴德富实业有限公司 | Fluorine-containing acrylate emulsion and preparation method thereof |
| WO2016176389A1 (en) | 2015-04-30 | 2016-11-03 | The Chemours Company Tt, Llc | Crosslinkable fluorinated urethane additives for durable exterior coatings |
| WO2017081126A1 (en) | 2015-11-11 | 2017-05-18 | Solvay Specialty Polymers Italy S.P.A. | Novel hydroxy-terminated (per)fluoropolyether-urethane polymers and their use in clear-coat compositions |
| CN109929066A (en) * | 2017-12-15 | 2019-06-25 | 上海飞凯光电材料股份有限公司 | A kind of UV-cured resin, preparation method, coating |
Family Cites Families (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2803615A (en) * | 1956-01-23 | 1957-08-20 | Minnesota Mining & Mfg | Fluorocarbon acrylate and methacrylate esters and polymers |
| US3255131A (en) * | 1961-05-10 | 1966-06-07 | Minnesota Mining & Mfg | Fluorochemical-containing varnishes |
| CH1121365D (en) * | 1964-08-14 | |||
| US3318852A (en) * | 1965-04-05 | 1967-05-09 | Minnesota Mining & Mfg | Fluorine-containing polymers |
| US3478116A (en) * | 1967-07-26 | 1969-11-11 | Du Pont | Fluorinated alcohols |
| US3972856A (en) * | 1969-03-10 | 1976-08-03 | Minnesota Mining And Manufacturing Company | Polyurethanes containing poly(perfluoroalkylene oxides) units |
| US3759874A (en) * | 1971-08-30 | 1973-09-18 | Fmc Corp | Fluorinated polyurethanes as soil release agents |
| FR2476097A1 (en) * | 1980-02-19 | 1981-08-21 | Ugine Kuhlmann | |
| US4396680A (en) * | 1981-03-04 | 1983-08-02 | E. I. Du Pont De Nemours And Co. | Substrate coated with crater resistant acrylic enamel |
| US4371657A (en) * | 1981-03-04 | 1983-02-01 | E. I. Du Pont De Nemours And Company | Crater resistant acrylic enamel |
| JPS5834866A (en) * | 1981-08-27 | 1983-03-01 | Dainippon Ink & Chem Inc | Composition for urethane coating |
| FR2540131B1 (en) * | 1983-01-28 | 1986-04-04 | Atochem | COMPOSITIONS AND METHOD FOR OLEOPHOBIC AND HYDROPHOBIC TREATMENT OF CONSTRUCTION MATERIALS |
| JPS60184513A (en) * | 1984-03-02 | 1985-09-20 | Showa Denko Kk | Production of graft polymer |
| JPS6114267A (en) * | 1984-06-29 | 1986-01-22 | Showa Denko Kk | Water-and oil-repellent paint |
| JPS6123657A (en) * | 1984-07-11 | 1986-02-01 | Kansai Paint Co Ltd | Anti-icing organic resin coating composition |
| JPS6123656A (en) * | 1984-07-11 | 1986-02-01 | Kansai Paint Co Ltd | Anti-icing organic coating composition |
| JPS6163646A (en) * | 1984-09-04 | 1986-04-01 | Sannopuko Kk | Fluorine-containing isocyanate compound and surface treatment using same |
| JPS6195078A (en) * | 1984-10-15 | 1986-05-13 | Kansai Paint Co Ltd | Anti-icing organic resin coating composition |
| IT1183345B (en) * | 1985-02-13 | 1987-10-22 | Montefluos Spa | FLUORINATED POLYURETHANE CONTAINING POLYOSIPERFLUOROALKYLENE BLOCKS OF IMPROVED MECHANICAL CHARACTERISTICS |
| JPS6226736A (en) * | 1985-07-26 | 1987-02-04 | Hitachi Ltd | Metalizing method for x-ray target |
| US5159017A (en) * | 1986-01-17 | 1992-10-27 | Nippon Paint Co., Ltd. | Crosslinked polymer microparticles and coating composition containing the same |
| JPS62267376A (en) * | 1986-05-15 | 1987-11-20 | Atom Kagaku Toryo Kk | Paint composition |
| US4812337A (en) * | 1986-11-25 | 1989-03-14 | Kansai Paint Company, Limited | Metallic coating method |
| US4722545A (en) * | 1987-05-04 | 1988-02-02 | Ford Motor Company | Method and apparatus for determining the center position of a vehicular steering system |
| JP2508760B2 (en) * | 1987-10-20 | 1996-06-19 | 旭硝子株式会社 | Water and oil repellent with dirt removability |
| US4791166A (en) * | 1988-03-23 | 1988-12-13 | Hoechst Celanese Corporation | Fluorocarbon polymer compositions and methods |
| US4841007A (en) * | 1988-03-28 | 1989-06-20 | Becton Dickinson And Company | Fluorinated polyetherurethanes and medical devices therefrom |
| JP2628373B2 (en) * | 1989-04-28 | 1997-07-09 | 大日精化工業株式会社 | Paint composition |
| JPH0312269A (en) * | 1989-06-12 | 1991-01-21 | Mitsubishi Rayon Co Ltd | Film forming method |
| DE3943127A1 (en) * | 1989-12-28 | 1991-07-04 | Hoechst Ag | URETHANES AS ALIPHATIC FLUORO ALCOHOL, ISOCYANATES AND CARBONIC ACIDS, PROCESS FOR THEIR PREPARATION AND THEIR USE |
| US5206286A (en) * | 1990-04-02 | 1993-04-27 | Ppg Industries, Inc. | Aqueous emulsion polymers prepared with crosslinkable non-ionic surfactants |
| JPH03287615A (en) * | 1990-04-05 | 1991-12-18 | Showa Denko Kk | Water-and oil-repellent composition |
| DE4027594A1 (en) * | 1990-08-31 | 1992-03-05 | Herberts Gmbh | WATER-DUMBABLE COPOLYMER, THEIR PRODUCTION AND USE, AND AQUEOUS COATING AGENTS |
| GB9026687D0 (en) * | 1990-12-07 | 1991-01-23 | Vascutek Ltd | Process for providing a low-energy surface on a polymer |
| DE4143390A1 (en) * | 1991-04-26 | 1993-04-01 | Fluorine contg. (co)polymers, useful for water- and oil repellent treatment of substrates | |
| DE4136768A1 (en) * | 1991-11-08 | 1993-05-13 | Bayer Ag | THE USE OF POLYISOCYANATE SOLUTIONS FOR IMPREGNATING MINERAL SUBSTANCES |
| US5250698A (en) * | 1992-08-05 | 1993-10-05 | Ciba-Geigy Corporation | 2-(2-hydroxy-3-perfluoroalkyl thiomethyl-5-alkylphenyl)2H-benzotriazoles and stabilized compositions thereof |
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1995
- 1995-10-16 US US08/543,721 patent/US5597874A/en not_active Expired - Lifetime
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1996
- 1996-10-11 NZ NZ321114A patent/NZ321114A/en unknown
- 1996-10-11 EP EP96936367A patent/EP0856021B1/en not_active Expired - Lifetime
- 1996-10-11 JP JP51588497A patent/JP4074340B2/en not_active Expired - Fee Related
- 1996-10-11 AU AU74392/96A patent/AU706335B2/en not_active Ceased
- 1996-10-11 DE DE69603195T patent/DE69603195T2/en not_active Expired - Fee Related
- 1996-10-11 WO PCT/US1996/016289 patent/WO1997014733A1/en active IP Right Grant
- 1996-10-11 CA CA002234421A patent/CA2234421C/en not_active Expired - Fee Related
- 1996-10-11 BR BR9611102A patent/BR9611102A/en not_active IP Right Cessation
- 1996-10-28 US US08/698,983 patent/US5705276A/en not_active Expired - Fee Related
Also Published As
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|---|---|
| NZ321114A (en) | 1999-08-30 |
| DE69603195D1 (en) | 1999-08-12 |
| BR9611102A (en) | 1999-07-13 |
| US5597874A (en) | 1997-01-28 |
| CA2234421A1 (en) | 1997-04-24 |
| DE69603195T2 (en) | 1999-11-18 |
| JPH11513735A (en) | 1999-11-24 |
| JP4074340B2 (en) | 2008-04-09 |
| EP0856021A1 (en) | 1998-08-05 |
| AU7439296A (en) | 1997-05-07 |
| WO1997014733A1 (en) | 1997-04-24 |
| US5705276A (en) | 1998-01-06 |
| EP0856021B1 (en) | 1999-07-07 |
| AU706335B2 (en) | 1999-06-17 |
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