CA1250986A - Acrylic polyurethane coating composition - Google Patents
Acrylic polyurethane coating compositionInfo
- Publication number
- CA1250986A CA1250986A CA000475436A CA475436A CA1250986A CA 1250986 A CA1250986 A CA 1250986A CA 000475436 A CA000475436 A CA 000475436A CA 475436 A CA475436 A CA 475436A CA 1250986 A CA1250986 A CA 1250986A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- coating composition
- binder
- addition
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6258—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids the acid groups being esterified with polyhydroxy compounds or epoxy compounds during or after polymerization
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
-
- 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
Abstract
TITLE
Acrylic Polyurethane Coating Composition ABSTRACT
A coating composition in which the binder contains the following:
(1) an acrylic polymer having pendent hydroxyl containing ester groups of ester group A of the formula and ester group (B) which is either wherein R1 is a saturated hydrocarbon group having 2-4 carbon atoms, R2 is a tertiary hydrocarbon group having 8 through 10 carbon atoms and (2) an aliphatic, aromatic or cycloaliphatic polyisocyanate:
The composition can be used as an unpigmented clear finish or can contain convention pigments and be used as a colored finish. The composition is useful for refinishing trucks and automobiles and as an original finish for trucks, automobiles, boats, outdoor equipment and the like since the resulting finish in glossy, durable and weatherable.
Acrylic Polyurethane Coating Composition ABSTRACT
A coating composition in which the binder contains the following:
(1) an acrylic polymer having pendent hydroxyl containing ester groups of ester group A of the formula and ester group (B) which is either wherein R1 is a saturated hydrocarbon group having 2-4 carbon atoms, R2 is a tertiary hydrocarbon group having 8 through 10 carbon atoms and (2) an aliphatic, aromatic or cycloaliphatic polyisocyanate:
The composition can be used as an unpigmented clear finish or can contain convention pigments and be used as a colored finish. The composition is useful for refinishing trucks and automobiles and as an original finish for trucks, automobiles, boats, outdoor equipment and the like since the resulting finish in glossy, durable and weatherable.
Description
TITLE
Acrylic Polyurethane Coating Composi~ion BACKGROUND OF THE INVENTION
This invention i5 directed to a polyurethane coating composition and in particular to an improved acrylic polyurethane coating composition.
~ crylic polyurethane coating composition~
are well known and ha~e been widely used to finish and repair finishes on automobil~s and trucks. One particular high quality acrylic polyurethane coa.ting co~.position describad in Vasta U.S. 3,55~,564 issued January 26, 1971 has bean widely used for finishing, refinishing and repairing automobiles anZ trucks.
Another high quality polyurethane finish containing metallic flake pigments that provides excellent glamour and a high qualit~ appearance and is used to finish automobiles and trucks is described in Crawley et al. U.S. Patent 4,1~1,571 issued December 26, 1978. However, there is a need to improve long term 0 weatherability of finishes of these compositions.
SUM~IARY OF THE I~ENTICN
The coating COMpOSitiOn has a binder solids content cf 5-75% by ~eight and contains 95-25% by weight of an organic liquid: the solids consi6 essentially of about ~1) 50--95% by weight of an acrylic polymer having a bac~bone of polymecized ~onomers of the group of styrene, alkyl methacrylate, alkyl acrylate or mixtures thereof, each having 1-12 carbon atoms in the alkyl groups alld having polvmeciæed ethylenically unsatuIated ester units that form ester groups pending from -tha carbon atoms of the bac~bone that comprise about 10 to 75%
of the totai weight of ~he polymer and are of ester group (A) --C 0- Rl - OH
and ester group (B) which is either O OH
"
- C - O - CH2 - C- H ,, 2 CH~ - O ~C ~ R
O H OH
,. -or a mixture of these groups;
wherein Rl is a sa~urated hydrocarbon radical having 2-4 carbon atoms, R2 is a tertiary hydrocarbon group having 8-10 carbon atoms; and
Acrylic Polyurethane Coating Composi~ion BACKGROUND OF THE INVENTION
This invention i5 directed to a polyurethane coating composition and in particular to an improved acrylic polyurethane coating composition.
~ crylic polyurethane coating composition~
are well known and ha~e been widely used to finish and repair finishes on automobil~s and trucks. One particular high quality acrylic polyurethane coa.ting co~.position describad in Vasta U.S. 3,55~,564 issued January 26, 1971 has bean widely used for finishing, refinishing and repairing automobiles anZ trucks.
Another high quality polyurethane finish containing metallic flake pigments that provides excellent glamour and a high qualit~ appearance and is used to finish automobiles and trucks is described in Crawley et al. U.S. Patent 4,1~1,571 issued December 26, 1978. However, there is a need to improve long term 0 weatherability of finishes of these compositions.
SUM~IARY OF THE I~ENTICN
The coating COMpOSitiOn has a binder solids content cf 5-75% by ~eight and contains 95-25% by weight of an organic liquid: the solids consi6 essentially of about ~1) 50--95% by weight of an acrylic polymer having a bac~bone of polymecized ~onomers of the group of styrene, alkyl methacrylate, alkyl acrylate or mixtures thereof, each having 1-12 carbon atoms in the alkyl groups alld having polvmeciæed ethylenically unsatuIated ester units that form ester groups pending from -tha carbon atoms of the bac~bone that comprise about 10 to 75%
of the totai weight of ~he polymer and are of ester group (A) --C 0- Rl - OH
and ester group (B) which is either O OH
"
- C - O - CH2 - C- H ,, 2 CH~ - O ~C ~ R
O H OH
,. -or a mixture of these groups;
wherein Rl is a sa~urated hydrocarbon radical having 2-4 carbon atoms, R2 is a tertiary hydrocarbon group having 8-10 carbon atoms; and
(2) 5-50% by weight of an aliphatic, aromatic or cycloaliphatic polyisocyanate.
DFSCRIPTTON OF rrHE INVF~NTION
The composition contains about 5-75% by weight of binder solids and about 95-25% by weight of an organic li~uid. The binder solids of the composition are o~ about 50-~5% by weigh~ of an acrylic polymer and 5-50% by weight of a polyisocyanate.
lrhe accylic polymec is prepared charging the monomers that for~ the backbone of the polymer along 5 with solvents and polymerization ca~alyst into. a ~25~6 polymerization vessel and reacting about 80-200C for about 1-5 hours to form a polymer having pendent carboxyl groups. Then glycidyl ester tha~ forms es~er group (B) by reacting with carboxyl group is added with solvent an esterification catalyst and heated to reflux temperature of about 80-200C for about 1-4 hours.
Typical monomers used to form the backbone are as follows: styrene, alkyl methacLy1ate having 1-12 carbon atoms such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, ethyl hexyl methacrylate, nonyl me~hacrylate, decyl methacrylate lauryl methacrylate, alkyl acrylates having 1-12 carbon atoms in the alkyl group such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, ethyl hexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate. ~ydroxy alkyl acrylates and methacrylates are used to provide ester group (A) and typically are hydroxy et~yl acrylate, hydroxy propyl acrylate, hydroxybutyl acrylate, hydroxy ethyl methacrvlate, hydroxy propyl methacrylate and hydroxy butyl methacrylate. About 1-5% by weight of an ethylenically unsaturated carboxylic acid is also used to provide an esterîfication site for glycidyl ester which forms estar group (B). Typical acids are me~hacrylic acid and acrylic acid. ~i.carboxylic acids such as itaconic acid can be used.
~2~
The glycidyl ester used to form este~ group (B) of the polymer has the formula ~ 0 where R2 is a tertiary aliphatic hydrocarbon of 8-10 carbon atom~ and is described in U.S. Patent 3,275,583 issued September 27, 1966.
The acrylic polymer has a weight average molecular weight o~ about 5,000-60,000 determined by gel permeation chromatography using polymethylmethacrylate as a standard. Preferably, the polymer has a weight average ¢.olecular weight of about 20,000-40,000.
Suitable eolymerization catalysts that are used in ~he pLocess to prepare the acrylic polymer are tertiary butyl peroxide, cumen hydroperoxide, azobisisobutyronitrile and the like. To prepare the ester group (B) esterification ca~alyst, such as quaternary bases or salts as benzyltrimethylammonium hydroxide, benzyltrimetnylammonium cnloride, octadecyltrimethylammonium chloride, or an amine, such a trie~hylamine, are used.
Suitable solvents which are used to prepare the acrylic polymer ar~ toluene, xylene, butyl acetate, acetone, methylisobutyl ketone, methylethyl ketone, and other aliphatic esters, ethers, ketones and other solvents which are nonreactive with the monomers used to ~orm the aceylic polymer.
one pre~erred acrylic ~olymer contains 20-40% by weight styrene, 10-30% by weight methyl methacrylate, 5-25% hydro~y e~hyl me~hacrylate and ~2~
5-15% by weight methacrylic acid which has been esterified with the aformentioned glycidyl ester to provide about 15-65% by weight o~ ester group (B).
Preferably, the acrylic polymer contains a molar ratio of ester group (A) to ester group (B) of about 1:1 to 1:2.5.
~n advantage of the acrylic polyme~ used in the composition of this invention is that it is prepared without an acid anhydride constituent as is the acrylic polymer of the aforementioned Vasta '564 patent and is not adversely af~ected by contamination of a slight amount of water in the polymerization process. Finishes formed from the coating composition of this invention are less susceptible to hydrolysis and deg~adation by ultraviolet light than finishes formed with prior art acrylic polyurethane compositions and have excellent weatherability.
Typical polyisocyanates that can be used to form the coating composition are aliphatic, aromatic or cycloaliphatic polyisocyanates. Typical polyisocyanates a~e as follows:
diphenylmethane-~,4'-diisocyanate, diphenylene-4-4'-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diiocyanate,
DFSCRIPTTON OF rrHE INVF~NTION
The composition contains about 5-75% by weight of binder solids and about 95-25% by weight of an organic li~uid. The binder solids of the composition are o~ about 50-~5% by weigh~ of an acrylic polymer and 5-50% by weight of a polyisocyanate.
lrhe accylic polymec is prepared charging the monomers that for~ the backbone of the polymer along 5 with solvents and polymerization ca~alyst into. a ~25~6 polymerization vessel and reacting about 80-200C for about 1-5 hours to form a polymer having pendent carboxyl groups. Then glycidyl ester tha~ forms es~er group (B) by reacting with carboxyl group is added with solvent an esterification catalyst and heated to reflux temperature of about 80-200C for about 1-4 hours.
Typical monomers used to form the backbone are as follows: styrene, alkyl methacLy1ate having 1-12 carbon atoms such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, ethyl hexyl methacrylate, nonyl me~hacrylate, decyl methacrylate lauryl methacrylate, alkyl acrylates having 1-12 carbon atoms in the alkyl group such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, ethyl hexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate. ~ydroxy alkyl acrylates and methacrylates are used to provide ester group (A) and typically are hydroxy et~yl acrylate, hydroxy propyl acrylate, hydroxybutyl acrylate, hydroxy ethyl methacrvlate, hydroxy propyl methacrylate and hydroxy butyl methacrylate. About 1-5% by weight of an ethylenically unsaturated carboxylic acid is also used to provide an esterîfication site for glycidyl ester which forms estar group (B). Typical acids are me~hacrylic acid and acrylic acid. ~i.carboxylic acids such as itaconic acid can be used.
~2~
The glycidyl ester used to form este~ group (B) of the polymer has the formula ~ 0 where R2 is a tertiary aliphatic hydrocarbon of 8-10 carbon atom~ and is described in U.S. Patent 3,275,583 issued September 27, 1966.
The acrylic polymer has a weight average molecular weight o~ about 5,000-60,000 determined by gel permeation chromatography using polymethylmethacrylate as a standard. Preferably, the polymer has a weight average ¢.olecular weight of about 20,000-40,000.
Suitable eolymerization catalysts that are used in ~he pLocess to prepare the acrylic polymer are tertiary butyl peroxide, cumen hydroperoxide, azobisisobutyronitrile and the like. To prepare the ester group (B) esterification ca~alyst, such as quaternary bases or salts as benzyltrimethylammonium hydroxide, benzyltrimetnylammonium cnloride, octadecyltrimethylammonium chloride, or an amine, such a trie~hylamine, are used.
Suitable solvents which are used to prepare the acrylic polymer ar~ toluene, xylene, butyl acetate, acetone, methylisobutyl ketone, methylethyl ketone, and other aliphatic esters, ethers, ketones and other solvents which are nonreactive with the monomers used to ~orm the aceylic polymer.
one pre~erred acrylic ~olymer contains 20-40% by weight styrene, 10-30% by weight methyl methacrylate, 5-25% hydro~y e~hyl me~hacrylate and ~2~
5-15% by weight methacrylic acid which has been esterified with the aformentioned glycidyl ester to provide about 15-65% by weight o~ ester group (B).
Preferably, the acrylic polymer contains a molar ratio of ester group (A) to ester group (B) of about 1:1 to 1:2.5.
~n advantage of the acrylic polyme~ used in the composition of this invention is that it is prepared without an acid anhydride constituent as is the acrylic polymer of the aforementioned Vasta '564 patent and is not adversely af~ected by contamination of a slight amount of water in the polymerization process. Finishes formed from the coating composition of this invention are less susceptible to hydrolysis and deg~adation by ultraviolet light than finishes formed with prior art acrylic polyurethane compositions and have excellent weatherability.
Typical polyisocyanates that can be used to form the coating composition are aliphatic, aromatic or cycloaliphatic polyisocyanates. Typical polyisocyanates a~e as follows:
diphenylmethane-~,4'-diisocyanate, diphenylene-4-4'-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diiocyanate,
3,3'-dimethoxy-~-4'-diphenylene diisocyanate methylene-bi~-(4-cyclohexylisocyanate) tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene dii60cyanate, ethylene diisocyanate, ethylidene diisocyanate, propylene-1,2-diisocyanâte, cyclohexylene-1,2-diisocyanate, m-phenylene diisocyanate, ~2~86 p-phenylene diisocyanate 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'~dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-diphenyl-4,4'-biphenylene diisocyanate,
4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, furfurylidene diisocyanate, bis-(Z-isocyanatoethyl)fumarate, 1,3,5-benzene triisocyanate, para,para',para''-triehenylmethane triisocyanate, 3,3'-diisocyanatodiphropy ether, xylylene diisocyanate, , ~diphenyl propane-4,4'-diisocyanate.
The product of one of the above isocyanates with a deficien~ amount of a low moleculaL weight alcohol, such as, 1,4-butane diol, glycerine, trimethylolpropane, hexane diol or a triol may be used as a polyisocyanate in the coating composition of this invention. These polyisocyanates can be made according to Bunge et al. U.S. 2,855,421, issued October 7, 1958.
Another preferred polvisocyanate is a biuret of the formula:
O
/ C - NH(R3)NCo OCN(R3)N
\ C-~NH~R3)NCo o wherein R3 is an ali~hat.ic hydrocarbon group having 1--12 carbo~ atoms. one ~articularly pceferred biuret is the biuret of hexamethylene diisocyanate. These biurets ean be made aceording to Mayer et al. U.S. 3,245,941, issued ~pril 12, 1966.
one particularly preferred polyisocyanate that forms a high quality durable and weatherable produc~ is 4 (R )-NC0 N
C~C/ \C ~
Il o where R4 is a hydrocarbon group having 6 carbon atoms. The above polyisocyanate is 1,3,5-tri6(6-isocyanatohexyl)1,3,5-triazine 2,4,6(lH,3H,5H)trione. Commereially available poly;soeyanate eompositions eontain the above polyisoeyanate and small amounts of higher molecular weight moieties sueh as dimers, trimers and hexamers of the above polyisocyanate.
The eomposition ean be used as a clear coat whieh is unpigmented or ean contain relatively small amounts of pigment having the same refraetive index as the resulting finish sueh as siliea, These elear coats are generally used over a base coat. Usually the clear coat is applied ovec the base coat while the base eoat is still wet and then both coats are cured.
The composition can be pigmented in a pigment to binder weight catio of about 0,1/100 to ~5 100/100. Conventional pigments can be used in the ~.25~
composi~ion such as metallic oxides, pr~ferably titanium dioxide, zinc oxide, iron oxide, and the like, metallic powders, metallic hydroxides, phthalocyanine pigments such as copper phthalocyanine blue or green, quinacridones, sulfates, carbonates, carbon blacks, silica, and other pigments, organic dyes, lakes, and the like.
Metallic flake pigments used in the composition are any of those pigments that provide a finish with metallic glamour. These pigments include any of the conventional metallic flake pigments, ~uch as aluminum flake, nickel flake, nickel-chrome flake, b~lt also includes Fire Frost* flake which is a polyestec flake coated with a layer of vapor-deposited aluminum and ~~1air* pigments which are mica flakes coated with titanium dioxide.
Generally, when metallic flake pigments are used in the composition, about 1-15% by weight, based on the weight of the binder, of cellulose ace~ate butyrate is used in addition to the above binder constituents. The cellulose acetate butyrate used in the composition has a butyryl conten~ of about 50-60% by weight, a hydroxyl content of 1.0-3.0~ by weight and has a viscosity of about 0.02-5.0 seconds 25 measured at 25C according to ASTM D-1343-56. One preferred cellulose acetate butyrate that ~orms a high glamour finish has a buty~yl content of 53-55%
by weisht and a viscosity of about o.l-O.~ seconds and a hyd.oxyl content of 1.5-2.5% by weight.
The composition also can ccntain in addition to the binder about 0.05-1.0% by weight, based on the weight Or the binder, of an alkyl acid phosphate having 1-~2 carbon atoms in the alkyl group.- Typical alkyl acid phosphates are monoalkyl acid phosphates * denotes trade mark ~2~
or mixtures thereo~ and have an acid No. of about 4-250 and are as follows:
methyl acid phosphate ethyl acid phosphate propyl acid phosphate isopropyl acid pho~phate pentyl acid phosphate hexyl acid phosphate 2-ethylhexyl acid phosphate octyl acid phosphate nonyl acid phospha~e decyl acid phosphate and - lauryl acid phosphate.
Butyl acid phosphate is one pre.erred compound that provides a proper curing composition.
One technique for preparing this butyl phosphate is to react phosphorus pentoxide with butanol giving a product tha~ has an acid number of about 100-150.
The coating composition can contain in addition to the above components about 0.1-5% by weight, based on the weight o~ the binder, o~
ultra~iolet light stabilizers. Preferably a blend of a benzotriazole and a hindered amine light stabilizer is used.
Typical ultraviolet light s~abilizers ~hat are usef~l are as follows:
Benzophenones such as hydroxydodecyl benzophenone, 2,4-dihydroxybenzophenone, hydroxy-benzophencnes containing sulfonic acid groups, 2,4-dihydroxy-3',5'-di-t-butylbenzophenone, 2,2',4'-trihydroxybenzophenone esters of dicarboxylic acids, 2-hydroxy-4-aceyloxyethoxybenzophenone, aliphatic mono--esteLs of 2,2',4-trihydroxy-4'-alkoxybenzophenone, 2-hydroxy-4-methoxy-2l-carboxyben%ophenone;
~ 25(~6 triazoles such as 2-phenyl-4-(2'-4'-dihydroxy-benzoyl)triazoles, substituted benzotriazoles such as hydroxyphenyltriazoles such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-octylph~nyl)naphthotriazole;
Triazines such as 3,5-dialkyl-4-hydroxyphenyl derivatives of triazine, sulfur-containing derivatives of dialkyl-4-hydroxyphenyltriazines, hydroxyphenyl-1,3,5-triazines and such triazines containing sulfonic acid groups, aryl-1,35-triazines, orthohydroxyaryl-s-triazine;
Benzoates such as dibenzoate of diphenylolpropane, t-butyl benzoate of diphenylolpropane, nonyl phenyl benzoate, octyl phenyl benzoate, r~sorcinol dibenæoate.
Other ultraviolet light stabilizers that can be used include lower alkyl thiomethylene-containing phenols, substituted benzenes such as 1,3-3-bis(2'-hydroxyben20yl)benzene, metal derivatives of 3,5,-di-t-butyl-4-hydroxyphenyl propionic acid, asymmetrical oxalic acid diarylamides, alkylhydroxyphenylthioalkanoic acid esters, dialkylhydroxyphenylalkanoic acid esters of di- and tri-pentaerythritol, phenyl- and naphthlene-substituted oxalic acid diamides, methyl-b-(3,5-di-t butyl-4-hydroxyphenyl)propionate, a . a ' -bis(2-hydroxy-phenyl3diisopropylbenzene, 3,5'-dibromo-2'-hydroxy-acetophenone, ester derivatives of 4,4-bis(4'-hydroxyphenyl)pentanoic acid wherein there is at least one unsubstituted position ortho to the aromatic hydroxyl groups, organophosph~rus sulfides such as ~2~
bis(diphenyl-phosphinothioyl)monosulfide and bis(diphenylphosphino-thioyl)disulfide, 4-benzoyl-6-(dialkylhydroxybenzyl) resorcinol, bis(3-hydroxy-4-benzoylphenoxy)diphenylsilane, bis(3-hydroxy-4-benzoylphenoxy)dialkylsilane~
1,8-naphthalimides, -cyano- B,~-diphenylacrylic acid derivatives, bist2-benzoxazolyl)alkanes, bis(2-naphthoxa-zolyl)alkanes, methylene malonitriles con~aining aryl and heterocyclic substitutes, alkylenebis(dithio)carbamate, 4-benzoyl-3-hydroxyphenoxyethyl acrylate, 4-benzoyl-3-hydroxyphenoxyethyl methaceyla~e, aryl-or alkyl-substituted acrylonitriles, 3-methyl-5-isopropyl-phenyl-6-hydroxycoumarone.
Particularly useful ultraviolet light stabilizers that can be.used are hindered amines of piperidyl derivati~es such as those disclosed in ~urayama et al., U.S. Patent 4,061,616, issued December 6, 1977, column 2, line 65, through column 4, line 2, and nickel compounds such as [l-phenyl-3-methyl-4-decanoylpyrazolate(5)]-Ni, bis~phenyldithiocarbamato]-Ni(II), and others listed in the above patent, column 8, line 44 through line 55.
The following ulteaviolet light stabilizers are particularly pre~erred:
bis(l,2,2,6,6-pentamethyl-4-piperidinyl)decanedioate, a blend of 2-[2~-hydroxy-3~,5~-1(1-l-dimethyl-propyl)phenyl]benzo-tria~ole and bis-~4-(1,2,2,6,6-eenta~ethylpiperidyl)]2-butyl-2-[(3,5 -t-butyl-4-hvdroxyphenyl)methyl]-propanedioate. The stabilizers can be used in any ratio however, a 1:1 ratio of benzotriazole to propanedioate is pre~erred.
3L~50~
The coating composition can contain in addition to the above components about 0.01 0.10% by weight, based on the weight of the binder~ of an organo metal catalyst and~or an amine catalyst such S as 1,4 diaza-bicyclo (2,2,2) octane. Typical organo metal catalyst aee stannous dioctoate and alkyl metal laurates, such as alkyl tin laurate, alkyl cobalt laurate, alkyl manganese laurate, alkyl zirconium laurate, alkyl nickel laurate. The alkyl group can have from 1-12 carbon atoms. Particularly useful catalysts are dibutyl tin dilaurate and stannous dioctoate.
- The coating composition also can contain in addition to the above components about 0.05-2% by weight, based on the weight of the binder, of poly 2-ethylhexyl acrylate. ~nother component that can be used in the coating composition is about 0.05-2% by weight, based on the weight of the binder, of polydimethyl siloxane. Both of these compounds are used to reduce surface imperfections in the dried and cured pair.t film.
A~y of the aforementioned solventO can be used to ~orm the composition and can be used to reduce the composition to an application viscosity.
The coating composition is applied by conventional techniques such as brushing, spraying, dipping, flow coating and th.e like, and either dried at ambient temperatures or a elevated temperatures of 50-100C for 2-30 minutes. The resulting layer o~
coating is about 0.1-5 mils thick. Usually, about a L-3 mil thick layer is applied.
Tlle composition can be ap?lied over a wide variety of substrates such as metal, wood, glass, plastics, primed metals, or previous coated or 5 painted me~als. If used to repair an existing finish, the composition is usually applied over an acrylic primer surfacer. The composition can be applied directly to an acrylic lacquer or enamel finish that has been sanded and cleaned with ~olvent. The composition can be applied as an original finish over an epoxy primer or other conventional ~rimers or can be ap~lied directly to bare metal. It is preferred to have the metal surface treated with a phosphate.
The following Examples illus~rate the invention. The parts and percentages are by weigh~
unless otherwise specified.
EXAMPLE
An acrylic resin solution is prepared by charging the following constituents into a polymerization vessel containing a mixer, a thermometer and a heat source:
Parts by Portion l Weiqht 20 Styrene monomer 94.7 Methyl methacrylate monomer 97.0 Hydroxyethyl methacrylate monomer 36.2 Methacrylic acid 12.4 Ethylene glycol monoethyl ether765.5 acetate Portion 2 Ethylene glycol monoethyl ether23.2 acetate t-Butyl peracetate l.5 30 _rtio~ 3 Styrene monomer 482.8 Methyl methacrylate monolner257.2 ~Iydroxy ethyl methacrylate monomer l.99.8 ~ethacrylic acid 170.0 ~ :25~8~
Portion 4 Ethylene glycol mono ethyl ether 210.0 acetate Toluene 73.6
The product of one of the above isocyanates with a deficien~ amount of a low moleculaL weight alcohol, such as, 1,4-butane diol, glycerine, trimethylolpropane, hexane diol or a triol may be used as a polyisocyanate in the coating composition of this invention. These polyisocyanates can be made according to Bunge et al. U.S. 2,855,421, issued October 7, 1958.
Another preferred polvisocyanate is a biuret of the formula:
O
/ C - NH(R3)NCo OCN(R3)N
\ C-~NH~R3)NCo o wherein R3 is an ali~hat.ic hydrocarbon group having 1--12 carbo~ atoms. one ~articularly pceferred biuret is the biuret of hexamethylene diisocyanate. These biurets ean be made aceording to Mayer et al. U.S. 3,245,941, issued ~pril 12, 1966.
one particularly preferred polyisocyanate that forms a high quality durable and weatherable produc~ is 4 (R )-NC0 N
C~C/ \C ~
Il o where R4 is a hydrocarbon group having 6 carbon atoms. The above polyisocyanate is 1,3,5-tri6(6-isocyanatohexyl)1,3,5-triazine 2,4,6(lH,3H,5H)trione. Commereially available poly;soeyanate eompositions eontain the above polyisoeyanate and small amounts of higher molecular weight moieties sueh as dimers, trimers and hexamers of the above polyisocyanate.
The eomposition ean be used as a clear coat whieh is unpigmented or ean contain relatively small amounts of pigment having the same refraetive index as the resulting finish sueh as siliea, These elear coats are generally used over a base coat. Usually the clear coat is applied ovec the base coat while the base eoat is still wet and then both coats are cured.
The composition can be pigmented in a pigment to binder weight catio of about 0,1/100 to ~5 100/100. Conventional pigments can be used in the ~.25~
composi~ion such as metallic oxides, pr~ferably titanium dioxide, zinc oxide, iron oxide, and the like, metallic powders, metallic hydroxides, phthalocyanine pigments such as copper phthalocyanine blue or green, quinacridones, sulfates, carbonates, carbon blacks, silica, and other pigments, organic dyes, lakes, and the like.
Metallic flake pigments used in the composition are any of those pigments that provide a finish with metallic glamour. These pigments include any of the conventional metallic flake pigments, ~uch as aluminum flake, nickel flake, nickel-chrome flake, b~lt also includes Fire Frost* flake which is a polyestec flake coated with a layer of vapor-deposited aluminum and ~~1air* pigments which are mica flakes coated with titanium dioxide.
Generally, when metallic flake pigments are used in the composition, about 1-15% by weight, based on the weight of the binder, of cellulose ace~ate butyrate is used in addition to the above binder constituents. The cellulose acetate butyrate used in the composition has a butyryl conten~ of about 50-60% by weight, a hydroxyl content of 1.0-3.0~ by weight and has a viscosity of about 0.02-5.0 seconds 25 measured at 25C according to ASTM D-1343-56. One preferred cellulose acetate butyrate that ~orms a high glamour finish has a buty~yl content of 53-55%
by weisht and a viscosity of about o.l-O.~ seconds and a hyd.oxyl content of 1.5-2.5% by weight.
The composition also can ccntain in addition to the binder about 0.05-1.0% by weight, based on the weight Or the binder, of an alkyl acid phosphate having 1-~2 carbon atoms in the alkyl group.- Typical alkyl acid phosphates are monoalkyl acid phosphates * denotes trade mark ~2~
or mixtures thereo~ and have an acid No. of about 4-250 and are as follows:
methyl acid phosphate ethyl acid phosphate propyl acid phosphate isopropyl acid pho~phate pentyl acid phosphate hexyl acid phosphate 2-ethylhexyl acid phosphate octyl acid phosphate nonyl acid phospha~e decyl acid phosphate and - lauryl acid phosphate.
Butyl acid phosphate is one pre.erred compound that provides a proper curing composition.
One technique for preparing this butyl phosphate is to react phosphorus pentoxide with butanol giving a product tha~ has an acid number of about 100-150.
The coating composition can contain in addition to the above components about 0.1-5% by weight, based on the weight o~ the binder, o~
ultra~iolet light stabilizers. Preferably a blend of a benzotriazole and a hindered amine light stabilizer is used.
Typical ultraviolet light s~abilizers ~hat are usef~l are as follows:
Benzophenones such as hydroxydodecyl benzophenone, 2,4-dihydroxybenzophenone, hydroxy-benzophencnes containing sulfonic acid groups, 2,4-dihydroxy-3',5'-di-t-butylbenzophenone, 2,2',4'-trihydroxybenzophenone esters of dicarboxylic acids, 2-hydroxy-4-aceyloxyethoxybenzophenone, aliphatic mono--esteLs of 2,2',4-trihydroxy-4'-alkoxybenzophenone, 2-hydroxy-4-methoxy-2l-carboxyben%ophenone;
~ 25(~6 triazoles such as 2-phenyl-4-(2'-4'-dihydroxy-benzoyl)triazoles, substituted benzotriazoles such as hydroxyphenyltriazoles such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-octylph~nyl)naphthotriazole;
Triazines such as 3,5-dialkyl-4-hydroxyphenyl derivatives of triazine, sulfur-containing derivatives of dialkyl-4-hydroxyphenyltriazines, hydroxyphenyl-1,3,5-triazines and such triazines containing sulfonic acid groups, aryl-1,35-triazines, orthohydroxyaryl-s-triazine;
Benzoates such as dibenzoate of diphenylolpropane, t-butyl benzoate of diphenylolpropane, nonyl phenyl benzoate, octyl phenyl benzoate, r~sorcinol dibenæoate.
Other ultraviolet light stabilizers that can be used include lower alkyl thiomethylene-containing phenols, substituted benzenes such as 1,3-3-bis(2'-hydroxyben20yl)benzene, metal derivatives of 3,5,-di-t-butyl-4-hydroxyphenyl propionic acid, asymmetrical oxalic acid diarylamides, alkylhydroxyphenylthioalkanoic acid esters, dialkylhydroxyphenylalkanoic acid esters of di- and tri-pentaerythritol, phenyl- and naphthlene-substituted oxalic acid diamides, methyl-b-(3,5-di-t butyl-4-hydroxyphenyl)propionate, a . a ' -bis(2-hydroxy-phenyl3diisopropylbenzene, 3,5'-dibromo-2'-hydroxy-acetophenone, ester derivatives of 4,4-bis(4'-hydroxyphenyl)pentanoic acid wherein there is at least one unsubstituted position ortho to the aromatic hydroxyl groups, organophosph~rus sulfides such as ~2~
bis(diphenyl-phosphinothioyl)monosulfide and bis(diphenylphosphino-thioyl)disulfide, 4-benzoyl-6-(dialkylhydroxybenzyl) resorcinol, bis(3-hydroxy-4-benzoylphenoxy)diphenylsilane, bis(3-hydroxy-4-benzoylphenoxy)dialkylsilane~
1,8-naphthalimides, -cyano- B,~-diphenylacrylic acid derivatives, bist2-benzoxazolyl)alkanes, bis(2-naphthoxa-zolyl)alkanes, methylene malonitriles con~aining aryl and heterocyclic substitutes, alkylenebis(dithio)carbamate, 4-benzoyl-3-hydroxyphenoxyethyl acrylate, 4-benzoyl-3-hydroxyphenoxyethyl methaceyla~e, aryl-or alkyl-substituted acrylonitriles, 3-methyl-5-isopropyl-phenyl-6-hydroxycoumarone.
Particularly useful ultraviolet light stabilizers that can be.used are hindered amines of piperidyl derivati~es such as those disclosed in ~urayama et al., U.S. Patent 4,061,616, issued December 6, 1977, column 2, line 65, through column 4, line 2, and nickel compounds such as [l-phenyl-3-methyl-4-decanoylpyrazolate(5)]-Ni, bis~phenyldithiocarbamato]-Ni(II), and others listed in the above patent, column 8, line 44 through line 55.
The following ulteaviolet light stabilizers are particularly pre~erred:
bis(l,2,2,6,6-pentamethyl-4-piperidinyl)decanedioate, a blend of 2-[2~-hydroxy-3~,5~-1(1-l-dimethyl-propyl)phenyl]benzo-tria~ole and bis-~4-(1,2,2,6,6-eenta~ethylpiperidyl)]2-butyl-2-[(3,5 -t-butyl-4-hvdroxyphenyl)methyl]-propanedioate. The stabilizers can be used in any ratio however, a 1:1 ratio of benzotriazole to propanedioate is pre~erred.
3L~50~
The coating composition can contain in addition to the above components about 0.01 0.10% by weight, based on the weight of the binder~ of an organo metal catalyst and~or an amine catalyst such S as 1,4 diaza-bicyclo (2,2,2) octane. Typical organo metal catalyst aee stannous dioctoate and alkyl metal laurates, such as alkyl tin laurate, alkyl cobalt laurate, alkyl manganese laurate, alkyl zirconium laurate, alkyl nickel laurate. The alkyl group can have from 1-12 carbon atoms. Particularly useful catalysts are dibutyl tin dilaurate and stannous dioctoate.
- The coating composition also can contain in addition to the above components about 0.05-2% by weight, based on the weight of the binder, of poly 2-ethylhexyl acrylate. ~nother component that can be used in the coating composition is about 0.05-2% by weight, based on the weight of the binder, of polydimethyl siloxane. Both of these compounds are used to reduce surface imperfections in the dried and cured pair.t film.
A~y of the aforementioned solventO can be used to ~orm the composition and can be used to reduce the composition to an application viscosity.
The coating composition is applied by conventional techniques such as brushing, spraying, dipping, flow coating and th.e like, and either dried at ambient temperatures or a elevated temperatures of 50-100C for 2-30 minutes. The resulting layer o~
coating is about 0.1-5 mils thick. Usually, about a L-3 mil thick layer is applied.
Tlle composition can be ap?lied over a wide variety of substrates such as metal, wood, glass, plastics, primed metals, or previous coated or 5 painted me~als. If used to repair an existing finish, the composition is usually applied over an acrylic primer surfacer. The composition can be applied directly to an acrylic lacquer or enamel finish that has been sanded and cleaned with ~olvent. The composition can be applied as an original finish over an epoxy primer or other conventional ~rimers or can be ap~lied directly to bare metal. It is preferred to have the metal surface treated with a phosphate.
The following Examples illus~rate the invention. The parts and percentages are by weigh~
unless otherwise specified.
EXAMPLE
An acrylic resin solution is prepared by charging the following constituents into a polymerization vessel containing a mixer, a thermometer and a heat source:
Parts by Portion l Weiqht 20 Styrene monomer 94.7 Methyl methacrylate monomer 97.0 Hydroxyethyl methacrylate monomer 36.2 Methacrylic acid 12.4 Ethylene glycol monoethyl ether765.5 acetate Portion 2 Ethylene glycol monoethyl ether23.2 acetate t-Butyl peracetate l.5 30 _rtio~ 3 Styrene monomer 482.8 Methyl methacrylate monolner257.2 ~Iydroxy ethyl methacrylate monomer l.99.8 ~ethacrylic acid 170.0 ~ :25~8~
Portion 4 Ethylene glycol mono ethyl ether 210.0 acetate Toluene 73.6
5 t-Butyl peracetate 28.4 Portion 5 Cardura* E ester(a mixed glycidyl ester of a synthetic tertiary carboxylic acid of the formula /o\
CH2 - CH CH2 - o - C - R2 where R2 is a tertiary aliphatic hydrocarbon group of 10 carbon atoms.) Benzyltrimethyl ammonium hydroxide 0.6 Portion 6 Ethylene glycol monoethylether363.3 acetate Toluene 111.5 Total3504.7 Portion 1 was charged into the polymerization vessel and mixed and heate2 to its reflux temperature of about 138C. Portion 2 was pcemixed and added o~er 30 seconds to initiate the ~olymerization reaction. Portion 3 was premixed and added at a unifocm rate over 90 minutes while maintaining the resulting reaction mixture at its reflux tem~erature. Portion 4 was premixed and 75% of Por~ion 4 WdS added with Portion 3 above. The remaining 25% of Portion 4 was added at a uniform rate over a 50 minute period while maintaining the reaction mixture at its reflux temperature and the reaction mixture was held at this temperature lor an additional 10 minutes. Poction 5 was premixed and added and the reaction mixture was held at its re~lux temperature of about 155~C. The reaction was continued ~or about 4-5 houcs until the acid number * denotes trade mark ~2~
1~
of the resulting polymer was about 2-~. Pottion 6 was added and the resulting polymer solution was allowed to cool to an ambient temperature The resulting acrylic polymer solution had a 55% polymer solids content, a Gardner Holdt viscosity measured at 25C of about ~ and a relative viscosity measured at 25C of about 1.077. The polymer had the following composition 30% sytrene, 18.4% methyl methacrylate, 12.3~ hydroxyethyl methacrylate, 9.3%
methacrylic acid and 30% ~Cardura~ E ester and has an acid No. of 3 and a weight average molecular weight of about 48, 000 measured by gel permeation chromatography using polymethyl methacrylate as a standard.
Acrylic polymer solution 1 was prepared by blending the lollowing constituents:
Parts by Weiqht Acrylic polymee solution(prepared56.24 above) Ethylene glycol monoethyl ether 21.50 acetate Toluene 5 4z Ethyl acetate 13.46 Bis-~4-(1,2,2,6,6-pentamethyl 0.31 piperidyl)]-2-butyl-2-~(3,5-t-Dutyl-4-hydroxyphenyl) methyl]-propalledioate 2-~2'-hydroxy-3',5'~ dimethyl G.31 3Q propyl)phenyl]benzotriazole Dibutyltindilau ate solu~ion (0.2%1.~3 solids in ethyl acetate) Modaflow* solution (10% solids o~0.31 poly 2-ethylhexyl acrylate in organic solvent) * denotes trade mark ~ 25~386 Polydimethyl siloxane solution 0.62 (5% solids in xylene) Total 100.~0 ~ polyisocyanate solu~ion was prepared by blending together the following constituents:
Parts by Weiaht Desmodur* N3390~polyisocyanate 42.4 '4 having the structure described previously and is 1,3,5-tris(6-isocyanatohexyl)l,3,5-triazine 2,4,6(1H, 3H, 5H) trione and small amounts of higher molecular weight moieties) Ethyl acetate 57.6 Total lQ0.0 Clear paint l was formulated by blending the following:
Parts by Weiqht Acrylic polymer solution l80.2 (prepared above) Polyisocyanate solution 1 19.8 ~prepared above) Total lOG.0 The above clear paint l was sprayed on a steel panel coated with a pigmented acrylic lacquer base coat. The resulting coated panel was dried at ambient tempera~ures. The resulting coating had an outstandin~ appearance, excellent gloss measu_ed at 20C and 60~ and excellent distinctness of image.
Flexibility,adhesion, chip resis~ance, recoat properties, chemical resistance. humidity resistance and durability were measured and were at a le~el acceptable for commercial clear paint.
* denotes trade mark ~crylic polymer solution 2 was prepared by blending the following con~tituents:
Parts.by Weiqht S ~crylic polymer solution(prepared 48.75 above~
Ethylene glycol monoethyl ether 21.52 acetate Toluene 5.42 10 Ethyl acetate 13.48 Xylene 7.89 Bis-~4-(1,2,2,6,6-pentamethyl 0.27 piperidyl)]-2-butyl-2-[(3,5-t-butyl-4-hydLoxyphenyl) methyl]-propanedioate 2-[2'-hydroxy-3',5'-1(1-1-dimethyl0.27 propyl)phenyl]benzotriazole Dibutyltindilaurate solution(o.2% solids 1.59 in ethyl acetate) 20 "Modaflow" solution(described above) 0.27 Polymethyl s;loxane solu~ion0.54 (described above) Total 100.00 A polyisocyanate solution 2 was prepared by blending the following constituents:
Parts by _Weiqht "Desmodur" N 3390 (described above) 64.7 Ethyl acetate 35.3 Total 100.0 Clear paint 2 was formulated by blending ~he following constituents:
Parts by.
Wei~ht 5 ~crylic polymer solution 2 88.3 ~prepared above) Polyisocyanate solution 2 11.7 ~prepared above) Total 100.0 The above clear paint 2 was sprayed on a steel panel coated with a pigmented acrylic lacquer - base coat. The resulting coated panel was dried at ambient temperatures. The resulting coating had an outstanding apeearance, excellent gloss measured at 20 and 60, excellent distinctness of image. Flexibility, adhesion, chip resistance, recoat properties, chemical resistance, humidity resistance and durability were measured and were at a level acceptable for a commercial clear paint.
A white pigmented acrylic polymer 20 composition was prepared as follows:
Parts by Portion 1 Weinht _ _ ~ccylic polymer solution a . 80 (2repared above) 25 Titanium dioxide pigment 26.40 Ethylene glycol monoether ~.76 ether acetate Fumed silica O.o~
Portion II
Acrylic polymer solution 41.10 (prepared above) "Moda~low" solution (described 0.25 (above) 38~
Polymethyl siloxane solution 0.50 ~described above) Ethyl aceta~e 12.60 Dibutyltindilaurate solution 1.55 (described above) Total100.00 Portion 1 is premixed and charged into a conventional sand mill and ground to fineness o~ 0.1 microns. Portion 2 is premixed and then portion 1 is added to portion 2 wi~h mixing to form a white pigmented composition.
Polyisocyanate ~olution 3 was formulated by blending the following constituents:
Parts by Weiqht "Desmodur" N 3390(described 82.6 above) ~u~yl acetate ~.7 Solvesso* 100 (hydrocarbon 8.7 solvent) Total 100.0 ~ white paint was prepared by thoroughly blending the following:
Parts by Weiqht White pigmented acrylic polymer 89.8 compcsition (prepared above) Polyisocyanate solution 3 10.2 Total100.0 30 The white paint was reduced to a spray viscosity with conventional solven~s and sprayed onto steel panels pcimed with a pigmented alkyd cesin prime~ and dried at ambient temperatures. The resulting coating was about 2-3 mils thick. The resulting coating had an outstanding appearance, * denotes trade mark ~s~
2~
e.xcellent gloss and distinctness of image and commercially acceptable chip resistance, humidity resistance, chemical resistance and durability.
A second white paint was formulated using ;he indentical ingredients as above except the biuret of hexamethylene diisocyanate was substituted for the "Desmodur" N 3390 and the resulting paint was reduced to a spray viscosity and applied to s~eel panels having the same alkyd resin primer as above. The resulting coating was dried at ambient temperatures and the dried coating was about 2-3 mils in thickness.
The coa~ing had a good appearance, good gloss and distinctness of image and acceptable chip resistance, humidity resistance, chemical resistance and durability.
CH2 - CH CH2 - o - C - R2 where R2 is a tertiary aliphatic hydrocarbon group of 10 carbon atoms.) Benzyltrimethyl ammonium hydroxide 0.6 Portion 6 Ethylene glycol monoethylether363.3 acetate Toluene 111.5 Total3504.7 Portion 1 was charged into the polymerization vessel and mixed and heate2 to its reflux temperature of about 138C. Portion 2 was pcemixed and added o~er 30 seconds to initiate the ~olymerization reaction. Portion 3 was premixed and added at a unifocm rate over 90 minutes while maintaining the resulting reaction mixture at its reflux tem~erature. Portion 4 was premixed and 75% of Por~ion 4 WdS added with Portion 3 above. The remaining 25% of Portion 4 was added at a uniform rate over a 50 minute period while maintaining the reaction mixture at its reflux temperature and the reaction mixture was held at this temperature lor an additional 10 minutes. Poction 5 was premixed and added and the reaction mixture was held at its re~lux temperature of about 155~C. The reaction was continued ~or about 4-5 houcs until the acid number * denotes trade mark ~2~
1~
of the resulting polymer was about 2-~. Pottion 6 was added and the resulting polymer solution was allowed to cool to an ambient temperature The resulting acrylic polymer solution had a 55% polymer solids content, a Gardner Holdt viscosity measured at 25C of about ~ and a relative viscosity measured at 25C of about 1.077. The polymer had the following composition 30% sytrene, 18.4% methyl methacrylate, 12.3~ hydroxyethyl methacrylate, 9.3%
methacrylic acid and 30% ~Cardura~ E ester and has an acid No. of 3 and a weight average molecular weight of about 48, 000 measured by gel permeation chromatography using polymethyl methacrylate as a standard.
Acrylic polymer solution 1 was prepared by blending the lollowing constituents:
Parts by Weiqht Acrylic polymee solution(prepared56.24 above) Ethylene glycol monoethyl ether 21.50 acetate Toluene 5 4z Ethyl acetate 13.46 Bis-~4-(1,2,2,6,6-pentamethyl 0.31 piperidyl)]-2-butyl-2-~(3,5-t-Dutyl-4-hydroxyphenyl) methyl]-propalledioate 2-~2'-hydroxy-3',5'~ dimethyl G.31 3Q propyl)phenyl]benzotriazole Dibutyltindilau ate solu~ion (0.2%1.~3 solids in ethyl acetate) Modaflow* solution (10% solids o~0.31 poly 2-ethylhexyl acrylate in organic solvent) * denotes trade mark ~ 25~386 Polydimethyl siloxane solution 0.62 (5% solids in xylene) Total 100.~0 ~ polyisocyanate solu~ion was prepared by blending together the following constituents:
Parts by Weiaht Desmodur* N3390~polyisocyanate 42.4 '4 having the structure described previously and is 1,3,5-tris(6-isocyanatohexyl)l,3,5-triazine 2,4,6(1H, 3H, 5H) trione and small amounts of higher molecular weight moieties) Ethyl acetate 57.6 Total lQ0.0 Clear paint l was formulated by blending the following:
Parts by Weiqht Acrylic polymer solution l80.2 (prepared above) Polyisocyanate solution 1 19.8 ~prepared above) Total lOG.0 The above clear paint l was sprayed on a steel panel coated with a pigmented acrylic lacquer base coat. The resulting coated panel was dried at ambient tempera~ures. The resulting coating had an outstandin~ appearance, excellent gloss measu_ed at 20C and 60~ and excellent distinctness of image.
Flexibility,adhesion, chip resis~ance, recoat properties, chemical resistance. humidity resistance and durability were measured and were at a le~el acceptable for commercial clear paint.
* denotes trade mark ~crylic polymer solution 2 was prepared by blending the following con~tituents:
Parts.by Weiqht S ~crylic polymer solution(prepared 48.75 above~
Ethylene glycol monoethyl ether 21.52 acetate Toluene 5.42 10 Ethyl acetate 13.48 Xylene 7.89 Bis-~4-(1,2,2,6,6-pentamethyl 0.27 piperidyl)]-2-butyl-2-[(3,5-t-butyl-4-hydLoxyphenyl) methyl]-propanedioate 2-[2'-hydroxy-3',5'-1(1-1-dimethyl0.27 propyl)phenyl]benzotriazole Dibutyltindilaurate solution(o.2% solids 1.59 in ethyl acetate) 20 "Modaflow" solution(described above) 0.27 Polymethyl s;loxane solu~ion0.54 (described above) Total 100.00 A polyisocyanate solution 2 was prepared by blending the following constituents:
Parts by _Weiqht "Desmodur" N 3390 (described above) 64.7 Ethyl acetate 35.3 Total 100.0 Clear paint 2 was formulated by blending ~he following constituents:
Parts by.
Wei~ht 5 ~crylic polymer solution 2 88.3 ~prepared above) Polyisocyanate solution 2 11.7 ~prepared above) Total 100.0 The above clear paint 2 was sprayed on a steel panel coated with a pigmented acrylic lacquer - base coat. The resulting coated panel was dried at ambient temperatures. The resulting coating had an outstanding apeearance, excellent gloss measured at 20 and 60, excellent distinctness of image. Flexibility, adhesion, chip resistance, recoat properties, chemical resistance, humidity resistance and durability were measured and were at a level acceptable for a commercial clear paint.
A white pigmented acrylic polymer 20 composition was prepared as follows:
Parts by Portion 1 Weinht _ _ ~ccylic polymer solution a . 80 (2repared above) 25 Titanium dioxide pigment 26.40 Ethylene glycol monoether ~.76 ether acetate Fumed silica O.o~
Portion II
Acrylic polymer solution 41.10 (prepared above) "Moda~low" solution (described 0.25 (above) 38~
Polymethyl siloxane solution 0.50 ~described above) Ethyl aceta~e 12.60 Dibutyltindilaurate solution 1.55 (described above) Total100.00 Portion 1 is premixed and charged into a conventional sand mill and ground to fineness o~ 0.1 microns. Portion 2 is premixed and then portion 1 is added to portion 2 wi~h mixing to form a white pigmented composition.
Polyisocyanate ~olution 3 was formulated by blending the following constituents:
Parts by Weiqht "Desmodur" N 3390(described 82.6 above) ~u~yl acetate ~.7 Solvesso* 100 (hydrocarbon 8.7 solvent) Total 100.0 ~ white paint was prepared by thoroughly blending the following:
Parts by Weiqht White pigmented acrylic polymer 89.8 compcsition (prepared above) Polyisocyanate solution 3 10.2 Total100.0 30 The white paint was reduced to a spray viscosity with conventional solven~s and sprayed onto steel panels pcimed with a pigmented alkyd cesin prime~ and dried at ambient temperatures. The resulting coating was about 2-3 mils thick. The resulting coating had an outstanding appearance, * denotes trade mark ~s~
2~
e.xcellent gloss and distinctness of image and commercially acceptable chip resistance, humidity resistance, chemical resistance and durability.
A second white paint was formulated using ;he indentical ingredients as above except the biuret of hexamethylene diisocyanate was substituted for the "Desmodur" N 3390 and the resulting paint was reduced to a spray viscosity and applied to s~eel panels having the same alkyd resin primer as above. The resulting coating was dried at ambient temperatures and the dried coating was about 2-3 mils in thickness.
The coa~ing had a good appearance, good gloss and distinctness of image and acceptable chip resistance, humidity resistance, chemical resistance and durability.
Claims (23)
1. A coating composition having a binder solids content of 5-75% by weight and 95-25% by weight in an organic liquid; wherein the binder consists essentially of about (1) 50-95% by weight of an acrylic polymer having a backbone consisting essentially of polymerized monomers selected from the group consisting of alkyl methacrylate, alkyl acrylate each having 1-12 carbon atoms in the alkyl group, styrene or mixtures thereof and polymerized ethylenically unsaturated ester monomers that form ester groups pending from the carbon atoms of the polymer backbone and comprise about 10 to 75% of the total weight of the polymer and consisting essentially of ester group (A) and ester group (B) selected from the group consisting of or mixtures thereof.
wherein R1 is a saturated hydrocarbon group having 2-4 carbon atoms, R2 is a tertiary hydrocarbon group having 8 throught 10 carbon atoms; and (2) 5-50% by weight of an aliphatic, aromatic or cycloaliphatic polyisocyanate.
wherein R1 is a saturated hydrocarbon group having 2-4 carbon atoms, R2 is a tertiary hydrocarbon group having 8 throught 10 carbon atoms; and (2) 5-50% by weight of an aliphatic, aromatic or cycloaliphatic polyisocyanate.
2. The coating composition of claim l in which the polyisocyanate has the formula where R4 is a hydrocarbon group having 6 carbon atoms.
3. The coating composition of claim 1 in which the polyisocyanate is the biuret of hexamethylene diisocyanate.
4. The coating composition of Claim 1 in which the molar ratio of ester group (A) to ester group (B) is about 1:1 to 1:25.
5. The coating composition of claim 4 in which the acrylic polymer consists essentially of 20-40% by weight styrene, 10-30% by weight methyl methacrylate, 5-25% by weight of hydroxy ethyl methacrylate and 15-65% by weight of ester group (B).
6. The coating composition of claim 1 containing in addition about 0.05-1.0% by weight, based on the weight of the binder, of an alkyl acid phosphate.
7. The coating composition of claim 6 in which the alkyl acid phosphate is butyl acid phospate.
8. The coating composition of claim 1 containing in addition about 0.01-0.10% by weight, based on the weight of the binder, of an organo metal catalyst.
9. The coating composition of claim 8 in which the catalyst is dibutyltin dilaurate.
10. The coating composition of claim 1 containing in addition about 0.5-5% by weight, based on the weight of the binder, of ultraviolet light stabilizer.
11. The coating composition of claim 10 in which the ultraviolet light stabilizer is a blend of a benzotriazole and a hindered amine light stabilizer.
12. The coating composition of claim 1 containing in addition pigment in a pigment to binder ratio of about 0.1/100 to 100/100.
13. The coating composition of claim 12 in which the pigment contains metallic flake pigments.
14. The coating composition of claim 13 containing in addition 1-15% by weight, based on the weight of the binder, of cellulose acetate butyrate having a butyryl content of about 50-60% by weight, a hydroxyl content of about 1.0-3.0% by weight, and a viscosity of 0.02-5.0 seconds measured at 25°C.
according to ASTM D-1343-56.
according to ASTM D-1343-56.
15 . The coating composition of claim 1 containing in addition about 0.05-1.0% by weight, based on the weight of the binder, of an alkyl acid phosphate, 0.5-5% by weight, based on the weight of the binder, of a blend of ultraviolet light stabilizer of a benzotriazole and a hindered amine light stabilizer and 0.01-0.10% by weight, based on the weight of the binder, of an alkyl tin laurate catalyst.
16. The coating composition of claim 1 wherein (1) the acrylic polymer has a backbone of styrene and methyl methacrylate and ester group A is from hydroxy ethyl acrylate and ester group B is the esterification of methacrylic acid of the backbone with glycidyl ester of a tertiary carboxylic acid and wherein R1 is (CH2)2, and R2 is a tertiary hydrocarbon group having 8 through 10 carbon atoms; and (2) the polyisocyanate is 1,3,5-tris(6-isocyanatohexyl)1,3,5-triazine 2,4,6(1H,3H,5H)trione.
17. The coating composition of claim 16 containing in addition 0.5-5% by weight, based on the weight of the binder, of a blend of ultraviolet light stabilizers consisting of 2-[2-hydroxy-3, 5-1(1-1-dimethylpropyl)phenyl]benzotxiazole and bis-[4-(1,2,2,6,6-pentamethylpiperidyl)]2-butyl-2-[(3,5,-t-butyl-4-hydroxyphenyl)methyl]-propanedioate.
18. The coating composition of claim 17 containing in addition about 0.05-2% by weight, based on the weight of the binder, of polydimethyl siloxane.
19. The coating composition of claim 18 containing in addition about 0.05-2% by weight, based on the weight of the binder of poly 2-ethyl hexyl acrylate.
20. The coating composition of claim 16 containing in addition 0.1-5% by weight, based on the weight of the binder, of an ultraviolet light stabilizer consisting of bis(1,2,2,6,6-pentamethyl-4-piperidinyl)decane dioate.
21. The coating composition of claim 16 containing in addition pigment in a pigment to binder ratio of about 0.1/100 to 100/100.
22. A substrate coated with a layer of the composition of claim 1 containing pigment in a pigment to binder ratio of about 0.1/100 to 100/100 and having superimposed thereon a layer of a clear composition of claim 1.
23. A substrate coated with a layer of the composition of claim 1 containing pigment in a pigment to binder ratio of about 0.1/100 to 100/100 and having super imposed thereon a layer of a clear composition of claim 1 containing a blend of ultraviolet light stabilizers of a benzotriazole and a hindered amine light stabilizer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US587,062 | 1984-03-07 | ||
| US06/587,062 US4555535A (en) | 1984-03-07 | 1984-03-07 | Acrylic polyurethane coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1250986A true CA1250986A (en) | 1989-03-07 |
Family
ID=24348185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000475436A Expired CA1250986A (en) | 1984-03-07 | 1985-02-28 | Acrylic polyurethane coating composition |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4555535A (en) |
| CA (1) | CA1250986A (en) |
Families Citing this family (40)
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|---|---|---|---|---|
| EP0175344B1 (en) * | 1984-09-18 | 1990-05-02 | Dainippon Ink And Chemicals, Inc. | Process for producing polyisocyanate and resin composition comprising said polyisocyanate for use in paints |
| JPH064692B2 (en) * | 1984-11-02 | 1994-01-19 | 武田薬品工業株式会社 | Urethane resin composition |
| US4760167A (en) * | 1986-02-03 | 1988-07-26 | E. I. Du Pont De Nemours And Company | Coating composition of an amine polymer and a blocked polyisocyanate |
| US4659770A (en) * | 1986-02-03 | 1987-04-21 | E.I. Du Pont De Nemours And Company | Coating composition of an amine polymer and a blocked polyisocyanate |
| US4727100A (en) * | 1986-08-15 | 1988-02-23 | E. I. Du Pont De Nemours And Company | Coating composition containing a reactive urethane component an acrylic fatty acid drying oil resin and a metallic alkylate |
| US4727099A (en) * | 1986-08-15 | 1988-02-23 | E. I. Du Pont De Nemours And Company | Coating composition containing a reactive urethane component, a hydroxyl containing acrylic polymer having pendent ester groups and a metallic alkylate catalyst |
| US4988766A (en) * | 1987-05-13 | 1991-01-29 | Ppg Industries, Inc. | Polymers prepared by polymerizing alpha, beta-ethylenically unsaturated acids and epoxy compounds and crosslinked products therefrom |
| US4923915A (en) * | 1988-05-18 | 1990-05-08 | Corning Incorporated | Thermally stabilized resin coatings for optical fibers |
| US5234496A (en) * | 1991-07-30 | 1993-08-10 | E. I. Du Pont De Nemours And Company | Mica based pigments coated with alkylene glycol alkyl ether |
| US5380787A (en) * | 1992-08-24 | 1995-01-10 | Padico Co., Ltd. | Paint resembling stained glass |
| DE4317784A1 (en) * | 1993-05-28 | 1994-12-01 | Basf Lacke & Farben | Process for the production of structured coatings on plastic surfaces |
| DE4317861C1 (en) * | 1993-05-28 | 1994-11-24 | Herberts Gmbh | Process for multi-layer coating of substrates and application of the process |
| US5807494A (en) * | 1994-12-15 | 1998-09-15 | Boes; Ralph Ulrich | Gel compositions comprising silica and functionalized carbon products |
| IL116379A (en) * | 1994-12-15 | 2003-12-10 | Cabot Corp | Aqueous inks and coatings containing modified carbon products |
| US5554739A (en) * | 1994-12-15 | 1996-09-10 | Cabot Corporation | Process for preparing carbon materials with diazonium salts and resultant carbon products |
| US5575845A (en) * | 1994-12-15 | 1996-11-19 | Cabot Corporation | Carbon black products for coloring mineral binders |
| IL116378A (en) * | 1994-12-15 | 2003-05-29 | Cabot Corp | Non-aqueous coating or ink composition with improved optical properties containing modified carbon product and method of preparation of the composition |
| US5559169A (en) * | 1994-12-15 | 1996-09-24 | Cabot Corporation | EPDM, HNBR and Butyl rubber compositions containing carbon black products |
| US5571311A (en) * | 1994-12-15 | 1996-11-05 | Cabot Corporation | Ink jet ink formulations containing carbon black products |
| IL116376A (en) * | 1994-12-15 | 2001-03-19 | Cabot Corp | Aqueous ink jet ink compositions containing modified carbon products |
| IL116377A (en) | 1994-12-15 | 2003-05-29 | Cabot Corp | Reaction of carbon black with diazonium salts, resultant carbon black products and their uses |
| US6359059B1 (en) * | 1995-02-02 | 2002-03-19 | Basf Corporation | Paint compositions containing reactive urea/urethanes |
| US5977245A (en) * | 1995-02-02 | 1999-11-02 | Basf Corporation | Automotive undercoat coating compositions containing reactive urea/urethane compounds |
| US6028137A (en) * | 1995-05-22 | 2000-02-22 | Cabot Corporation | Elastomeric compounds incorporating silicon-treated carbon blacks |
| US5622557A (en) * | 1995-05-22 | 1997-04-22 | Cabot Corporation | Mineral binders colored with silicon-containing carbon black |
| HUP9802554A3 (en) * | 1995-05-22 | 1999-04-28 | Cabot Corp | Elastomeric compounds incorporating partially coated carbon blacks |
| US6323273B1 (en) | 1995-05-22 | 2001-11-27 | Cabot Corporation | Elastomeric compounds incorporating silicon-treated carbon blacks |
| US5958999A (en) * | 1996-04-05 | 1999-09-28 | Cabot Corporation | Ink compositions and method for generating images produced therefrom |
| US5698016A (en) * | 1996-06-14 | 1997-12-16 | Cabot Corporation | Compositions of modified carbon products and amphiphilic ions and methods of using the same |
| US5707432A (en) * | 1996-06-14 | 1998-01-13 | Cabot Corporation | Modified carbon products and inks and coatings containing modified carbon products |
| WO1997047382A1 (en) | 1996-06-14 | 1997-12-18 | Cabot Corporation | Modified carbon adsorbents and processes for adsorption using the same |
| US5747562A (en) * | 1996-06-14 | 1998-05-05 | Cabot Corporation | Ink and coating compositions containing silicon-treated carbon black |
| DE19652145A1 (en) * | 1996-12-14 | 1998-06-18 | Herberts Gmbh | Binder composition, coating compositions containing it, their production and use |
| US5919855A (en) * | 1997-02-11 | 1999-07-06 | Cabot Corporation | Use of modified carbon black in gas-phase polymerizations |
| US6187376B1 (en) * | 1998-10-01 | 2001-02-13 | Basf Corporation | Method for improving the adhesion of a repair coating to a previously coated substrate |
| EP1125644A1 (en) * | 2000-02-16 | 2001-08-22 | Kansai Paint Co., Ltd. | Method for repair coating |
| US7390858B2 (en) * | 2005-10-18 | 2008-06-24 | Valspar Sourcing, Inc. | Coating compositions and methods |
| JP5059559B2 (en) * | 2006-12-05 | 2012-10-24 | リンテック株式会社 | Laser dicing sheet and chip body manufacturing method |
| US8114520B2 (en) * | 2006-12-05 | 2012-02-14 | Lintec Corporation | Laser dicing sheet and process for producing chip body |
| DE102012020742A1 (en) * | 2012-10-23 | 2014-04-24 | Oerlikon Trading Ag, Trübbach | Plastic part coated with an embedded PVD layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2855421A (en) * | 1952-07-03 | 1958-10-07 | Bayer Ag | Polyisocyanates and method of preparing polyisocyanates |
| NL103396C (en) * | 1959-05-19 | |||
| BE629937A (en) * | 1962-03-24 | |||
| US3330814A (en) * | 1963-05-27 | 1967-07-11 | Du Pont | Hydroxyl-containing copolymers |
| US3558564A (en) * | 1969-03-27 | 1971-01-26 | Du Pont | Thermosetting coating composition of an organic polyisocyanate and a polymer having pendant hydroxyl containing ester groups |
| US4020216A (en) * | 1975-06-03 | 1977-04-26 | E. I. Du Pont De Nemours And Company | Coating composition for flexible substrates |
| CA1090025A (en) * | 1975-12-29 | 1980-11-18 | Keenan L. Crawley | Polyurethane metallic enamel |
| DE2618809C2 (en) * | 1976-04-29 | 1983-06-30 | Hoechst Ag, 6230 Frankfurt | Process for the production of copolymers which are soluble in organic solvents and their use in reactive lacquers |
| US4215023A (en) * | 1978-11-13 | 1980-07-29 | E. I. Du Pont De Nemours And Company | Urethane enamel coating composition |
-
1984
- 1984-03-07 US US06/587,062 patent/US4555535A/en not_active Expired - Lifetime
-
1985
- 1985-02-28 CA CA000475436A patent/CA1250986A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US4555535A (en) | 1985-11-26 |
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