WO1996023034A1 - Vehicule polymere pour revetements a haute teneur en matieres solides - Google Patents

Vehicule polymere pour revetements a haute teneur en matieres solides Download PDF

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Publication number
WO1996023034A1
WO1996023034A1 PCT/US1996/000982 US9600982W WO9623034A1 WO 1996023034 A1 WO1996023034 A1 WO 1996023034A1 US 9600982 W US9600982 W US 9600982W WO 9623034 A1 WO9623034 A1 WO 9623034A1
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WIPO (PCT)
Prior art keywords
group
polyol
recited
polymeric vehicle
hardener
Prior art date
Application number
PCT/US1996/000982
Other languages
English (en)
Inventor
Frank Jones
Shou-Kuan Fu
Xiaoying Yuan
Jun Hua
Original Assignee
Eastern Michigan University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from PCT/US1995/001058 external-priority patent/WO1995020004A1/fr
Application filed by Eastern Michigan University filed Critical Eastern Michigan University
Priority to KR1019960705323A priority Critical patent/KR970702335A/ko
Priority to JP8522993A priority patent/JPH10501581A/ja
Priority to EP96905213A priority patent/EP0751978A1/fr
Priority to AU49029/96A priority patent/AU710344B2/en
Publication of WO1996023034A1 publication Critical patent/WO1996023034A1/fr
Priority to MXPA/A/1996/004247A priority patent/MXPA96004247A/xx

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    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers

Definitions

  • This invention is directed to polymeric vehicles and formulated coating compositions for coating binders which are high in solids and minimize the use of organic solvents to effect viscosities which permit the application of such polymeric vehicles or formulated coating compositions to a substrate as a protective paint by existing commercial application equipment. More particularly, this invention is directed to polymeric vehicles and formulated coating compositions which compositions include a nonmesogenic substantially linear oligoester diol, a hardener and crosslinker. These compositions are very high in solids and low in volatile organic compounds, and provide a coating binder with extremely good film properties.
  • One of the primary components in paint is the
  • film former that provides a film for the protective function for a substrate coated with the paint.
  • Film forming components of liquid paints include resins which have required organic solvents to provide the resins with suitable viscosities such that the paint can be applied by existing commercial application equipment.
  • Use of organic solvents raises at least two problems. In the past and potentially in the future, petrochemical shortages mitigate against the use of organic solvent in great volumes. Second, environmental concern mitigates against the use of organic solvents and requires such use be minimized. Environmental concern has become increasingly important. This concern not only extends to
  • VOCs U.S. Environmental Protection Agency
  • compositions and powdered coating compositions are liquid and are designed to minimize solvents.
  • Powdered coating compositions are solid powders and generally eliminate solvents. While each have advantages, each coating composition has disadvantages.
  • Coating compositions which include high solids polymeric vehicles based upon polyesters have become popular. In high solid polyesters as opposed to
  • polyester coating compositions are “conventional” polyester coating compositions.
  • high solids polyester coating compositions have enjoyed spectacular growth in manufacture and use. They still require organic solvents, however, and are a source of VOCs.
  • Powder coatings and UV-curable coatings are desirable ultrahigh or 100% solids coatings.
  • VOCs One way to reduce VOCs is to further reduce organic solvent content and increase the solids level of the coating composition to an ultra high solids level.
  • High viscosity is a major problem which needs to be solved in ultrahigh solids coatings. In high solids polyester coatings, the viscosity of
  • M n number average molecular weight of a polyester
  • M n number average molecular weight of a polyester
  • a dibasic acid to diol or polyol ratio of the order of 2:3 is typical.
  • loss of polyol during the production of the polyester can result in a significantly higher number average molecular weight than predicted from the starting ratio. It is
  • the low molecular weight fraction of resin in the polymeric vehicle may be volatile enough to evaporate when a thin film is baked. Such loss has to be counted as part of the VOC emissions.
  • the number of functional groups per molecule also affects the viscosity because of hydrogen bonding.
  • Host oligomers or polymers require high functionality to achieve a highly crosslinked film and reasonable Tgs to have adequate film properties for most applications.
  • the high functionality tends to increase the viscosity significantly.
  • An object of the invention is to provide a
  • the invention provides a liquid polymeric vehicle which may be a solution or a dispersion and which polymeric vehicle is effective for providing a high solids formulated coating composition.
  • the polymeric vehicle comprises a blend of at least one nonmesogenic substantially linear oligoester diol and at least one hardener which is a mesogenic polyol, phenolic ester alcohol (PHEA) or a crystalline polyol which blend is effective for reaction with a crosslinker which is reactive with the nonmesogenic oligoester and hardener.
  • PHEA phenolic ester alcohol
  • the viscosity of the polymeric vehicle which includes a blend of the oligoester, hardener and crosslinker will be in the range of from about 0.1 to about 20 Pa.s at from about 20oC to about 60oC at a shear rate of about 1000 sec. -1 in the absence of organic solvent.
  • the polymeric vehicle comprises from about 10 to about 50 weight percent hardener, based upon the combined weight of the hardener, oligoester and crosslinker, from about 15 to about 50 weight percent oligoester and from about 10 to about 40 weight percent crosslinker. If the hardener is a mesogenic polyol, the mesogenic polyol is present in an amount effective to provide the polymeric vehicle from about 5 to about 50 weight percent mesogenic groups, based upon the weight of the mesogenic polyol.
  • the oligoester diol and/or mixture of such diols has a number average molecular weight in the range of from about 275 to about 3000 and a polydispersity index of not more than about 2.6 and preferably not more than about 2.2.
  • the oligoester diol is liquid below about 50oC when in the environment of the hardener and crosslinker.
  • the oligoester is substantially linear which means it also may be linear.
  • hydroxyl groups or a hydroxyl group may be on R if R is within four carbon atoms of the terminal carbon of the main
  • the oligoester diol should not on average contain more than one branch (defined by R above) per molecule of diol residue in the main chain.
  • an oligoester made from a mixture of neopentyl glycol and completely linear diol must have at least 50 mole percent of the total diol residue of completely linear diol residue in the main chain of the
  • oligoester Further, not more than about 8% of the number of hydrogen atoms along the main longitudinal chain may be substituted with carbon atoms.
  • the branching by virtue of substitution such as R should not permit the branching index, as defined below, to be more than about 0.12. Generally R will be methyl.
  • the hardener is a mesogenic polyol which has two or more hydroxyl groups and which forms a dispersion or a solution with the oligoester when it is a part of the formulated coating composition.
  • q an integer from 1 to 3.
  • the hardener in the polymeric vehicle and the formulated coating composition is a crystalline polyol which has two or more hydroxyl groups, 5 to 200 carbon atoms, a number average molecular weight (M n ) in the range of from about 400 to 4000 and a polydispersity index of not more than about 2.6 and preferably not more than about 2.2.
  • the crystalline polyol is insoluble in the formulated coating composition at storage and at application, but is miscible in the polymeric vehicle at the intended baking temperature of the formulated coating composition which provides the coating binder.
  • the hardener may be a PHEA which is a phenolic ester alcohol which includes at least two ester linkages, at least one aliphatic hydroxyl group and at least one hydroxyl group extending from an aromatic ring of the molecule (a phenolic
  • the phenolic ester alcohol may be the reaction product of hydroxybenzoic acid, such as para hydroxybenzoic acid, and a monoglycidyl compound having a molecular weight in the range of from about 150 to 1000 such as the monoglycidyl compound with the formula
  • R represents a mixture of aliphatic groups.
  • R represents a mixture of aliphatic groups.
  • the three R groups in the glycidyl compound have a total of 8 carbon atoms and which the glycidyl compound is commercially available from Exxon Chemical Company under the trademark Glydexx ⁇ .
  • the PHEA has the structure
  • linear or substantially linear aliphatic oligoester diols have low viscosities relative to their molecular weight. It also has been found that these oligoester diols exhibit shear thinning at high shear rates. In crosslinked coatings, such diols
  • coatings that are too soft for most uses. It has been found, however, that the properties of these coatings may be enhanced to useful levels by blending a hardener that is a diol or polyol and which is crystalline, a PHEA and/or includes mesogenic groups, with the nonmesogenic oligoester diol and crosslinker. We have discovered that this blend may be made without increasing the viscosity of the blend so much that it can not be applied to a substrate.
  • the invention provides a method for controlling the viscosity of the polymeric vehicle at a specific shear rate by controlling the relative amounts of substantially linear nonmesogenic oligoester diol and hardener (mesogenic polyol, PHEA and/or crystalline polyol) such that when the nonmesogenic oligoester diol and hardener are combined with a cross- linker, the blend of the oligoester diol, hardener and crosslinker will be in relative amounts effective to provide a coating binder which will have a hardness of at least about B at a binder thickness of about one mil.
  • the polymeric vehicle of the invention will provide a coating binder with a hardness of at least about H.
  • the viscosity of the blend will be in the range of from about 0.1 to about 20 Pa.s at about 20 to about 60oC to provide a shear rate of at least about 1,000 and preferably in the range of about 1,000 to about 1 X 10 6 sec. -1 in the absence of organic solvent.
  • Polymer means a polymer which has linkages in the main chain of the polymer.
  • Oligomer means a compound that is a polymer, but has a number average weight not greater than about 10,000 with or without repeating monomeric units.
  • Non-oligomeric is a
  • Crosslinker means a di- or
  • polyfunctional substance containing functional groups that are capable of forming covalent bonds with hydroxyl groups that are present on the oligoenter diol and hardener which is the mesogenic polyol and/or crystalline polyol.
  • Amino resins, polyisocyanate and epoxy resins are members of this class; melamine resins are a
  • the crosslinking agent may be a blend, hence, there may be more than one substance which forms a blend of substances which forms covalent bonds with the hydroxyl groups of the oligoester and hardener.
  • Polymeric vehicle means polymeric and resinous components in the formulated coating, i.e., before film formation, including but not limited to the substantially linear oligoester diol, mesogenic polyol, crystalline polyol and crosslinker.
  • Coating binder means the polymeric part of the film of the coating after solvent has evaporated after baking and after
  • Formated coating composition means the polymeric vehicle and optional solvents, as well as pigments, catalysts and additives which may optionally be added to impart desirable application characteristics to the formulated coating and desirable properties such as opacity and color to the film.
  • high solids means at least or more than about 75 weight percent solids under ASTM test D-2369-92.
  • a "high solids formulated coating composition” or high solids polymeric vehicle means a nonaqueous composition containing at least or more than about 75 weight percent solids as per ASTM test D-2369-92.
  • the polymeric vehicle composition has a viscosity of not greater than about 0.3 Pa.s at a shear rate of about 25 sec. -1 at a temperature of about 30o C.
  • the formulated coating composition according to the invention will not have more than about 200 g/L VOCs under ASTM test D-3960-93.
  • Polydispersity index means the weight average molecular weight (M w ) divided by the number average molecular weight (M n ), PDI-M w /M n .
  • VOC volatile organic compounds.
  • Low VOC means less than about 200 grams VOCs per liter of
  • polymeric vehicle not including water.
  • the main longitudinal chain is terminated with a hydroxyl group, or alternatively, a hydroxyl group may be on R if R is within four carbon atoms of the terminal carbon atom of the main longitudinal chain. Most often R will be methyl.
  • the oligoester diol should not on average contain more than one branch (defined by R above) per molecule of diol residue in the main chain.
  • substantially linear oligoester diol may be completely linear and is made by polymerizing linear dicarboxylic acids such as HOOC(CH 2 ) n COOH with linear diols such as HO(CH 2 ) m OH.
  • the reaction mixture may contain, however, a proportion of "branched" comonomers, usually diols which bear branches (such as R set forth above) which are usually methyl. Not more than about 8 percent of the number of hydrogens along the main chain of the
  • oligoester can be substituted with carbon atoms.
  • the oligoester diol will have a branching index, as defined below, of not more than about 0.12.
  • the branching index is defined as ;
  • C s the average number of segments with single branches per molecule
  • C d the average number of segments with double branches per molecule
  • B l the average length, in carbon and oxygen atoms, of branches.
  • “Diol” is a compound or oligomer with two hydroxyl groups.
  • “Polyol” is a compound or oligomer with two or more hydroxyl groups.
  • polymer means a polymer with repeating monomeric units as described herein and includes oligomers as described herein.
  • solvent means an organic solvent
  • Organic solvent means a liquid which includes but is not limited to carbon and hydrogen which liquid has a boiling point in the range of from about 30oC to about 300oC at about one atmosphere pressure.
  • Volatile organic compounds are described by the U.S. Environmental Protection Agency at 40 C.F.R. 51.000 of the Federal Regulations of the United States of
  • chlorodifluoromethane CFC-22
  • trifluoromethane FC-23
  • 1,2-dichloro-1,1,2,2-tetrafluoroethane CFC-114
  • chloropentafluoroethane CFC-115; 1,1,1-trifluoro 2,2-dichloroethane (HCFC-123); 1,1,1,2-tetrafluoroethane (HF-134a); 1,1-dichloro 1-fluoroethane (HCFC-141b); 1-chloro 1,1-difluoroethane (HCFC-142b); 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124); pentafluoroethane (HFC-125); 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1-trifluoroethane (HFC-143a); 1,1-difluoroethane (HFC-152a); and perfluorocarbon compounds which fall into these classes:
  • “Film” is formed by application of the formulated coating composition to a base or substrate, evaporation of solvent, if present, and crosslinking.
  • Dispossion in respect to a polymeric vehicle, formulated coating composition, or components thereof means that the composition must include a liquid and particles which particles are detectable by dynamic light scattering.
  • Soluble means a liquid dissolved in a liquid or a solid dissolved in a liquid.
  • “Miscible” means a liquid which is dissolved or is soluble in a liquid.
  • Dissolved in respect to a polymeric vehicle, formulated coating composition or components thereof means that the material which is dissolved does not exist in a liquid in particulate form having at least about 5 weight percent particles having diameters greater than about 30nM which are as measured by dynamic light
  • Adduct of monoxirane means the product of an addition reaction between a monoxirane with another compound with a functional group reactive with the oxirane, such as a hydroxyl group.
  • Nonmesogenic refers to compounds, oligomers or polymers which do not have the formulas I, II and III defined above as mesogenic in an amount of more than above 5 weight percent based upon the weight of the compound.
  • the polymeric vehicle comprises a blend of a
  • nonmesogenic substantially linear oligoester diol and a hardener which is a mesogenic polyol, PHEA and/or a crystalline polyol which blend is effective for a
  • hardener and crosslinker will be in the range of from about 0.1 to about 20 Pa.s at from abut. 20oC to about
  • the polymeric vehicle provides a coating binder having a pencil hardness of at least about B when applied to a substrate at thickness of about 1 mil dry.
  • the polymeric vehicle provides a coating binder having a pencil
  • the polymeric vehicle comprises from about 10 to about 50 weight percent hardener, based upon the combined weight of the hardener, oligoester and crosslinker, from about 15 to about 50 weight percent oligoester diol and from about 10 to about 40 weight percent crosslinker. If the hardener is a mesogenic polyol, the mesogenic polyol is present in an amount effective to provide the hardener.
  • polymeric vehicle with from about 5 to about 50 weight percent mesogenic groups, based upon the weight of the mesogenic polyol. If the hardener is a blend of
  • mesogenic polyol and a crystalline polyol the ratio of mesogenic polyol and crystalline polyol and amount of the blend are in amounts effective for providing the
  • polymeric vehicle which provides a coating binder having a pencil hardness of at least about B when applied to a substrate at a thickness of about 1 mil dry.
  • the oligoester diol should not on average contain more than one branch (defined by R above) per molecule of diol residue in the main chain.
  • Not more than about 8 percent of the hydrogens along the main chain of the oligoester diol may be substituted with a carbon to provide the branching such as the methyl and ethyl branching.
  • the branching should be minimized to the lowest level that will prevent crystallization of the oligoester diol at temperatures above the intended application temperature of the polymeric vehicle and formulated coating composition. This temperature is usually from about 25oC to about 50oC and preferably above about 0oC.
  • the oligoester diol is liquid below about 50oC when in the environment of the hardener and crosslinker.
  • an oligoester in the polymeric vehicle is important because it has a low viscosity, as a part of the polymeric vehicle but has a sufficiently low
  • evaporation rate such that the oligoester has at least about 93 weight percent solids when tested by ASTM D-2369. This minimizes the VOC content of the oligoester where the VOCs result from the molecular weight fractions of the oligoester that evaporate upon baking.
  • the substantially linear oligoester diol may be made by esterifying linear dicarboxylic acids such as
  • DCC dicyclohexylcarbodiimide
  • transesterification reaction and a solution of p-toluenesulfonic acid in pyridine may be used as a
  • Diols which may be used to make the substantially linear oligoester diol include 1,3-propane diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, diethylene glycol, triethylene glycol and tetraethylene glycol.
  • Diacids which may be used to make the substantially linear oligoester diol include adipic acid, glutaric acid, azelaic acid, decanedioic acid, and dodecandioic acid. These monomers are completely linear and will provide completely linear oligoester diols. Completely linear oligoester diols do not have any branching at all. While the oligoester diols of this invention may be completely linear, they only have to be substantially linear and monomers with some branching may be mixed with the completely linear monomers.
  • Examples of monomers which may be mixed with the linear monomers to form substantially linear oligoester diols are 1,3-butanediol, 2-ethyl-1-6-hexanediol, 2,2, 4-trimethylpentanediol, neopentyl glycol, HOOCCH(CH 3 )CH 2 CH 2 COOK, and 2-ethyl-2-n-butyl-1,3-propanediol.
  • the substantially linear oligoester diols also may be made by the catalyzed transesterification reaction of the corresponding ester of the diacid with the diols as described above.
  • the corresponding esters of the diacids include dimethyl azeleate, dimethyl glutarate, dimethyl adipate, dimethyl decanedioate and dimethyl
  • substantially linear oligoester diol examples include a cotransesterified mixture of dimethyl azeleate with 1,4-butanediol and 1,6-hexanediol; a cotransesterified mixture of dimethyl azeleate and dimethyl adipate (1:1 molar ratio) and 1,4-butanediol which mixture provides a viscosity of 0.72 Pa.s at 3 rpm at 25oC; a cotransesterified mixture of dimethyl azeleate and diethyl dodecanedioate (1:1 molar ratio) with the diols 1,4-butanediol, diethylene glycol and 1,10-decanediol (2:1:1 molar ratio).
  • oligoesters which may be used in the invention have the general formulas:
  • the nonmesogenic linear oligoester diol in the polymeric vehicle has the general formula
  • a substantially linear oligoester diol which is useful in the invention has the general formula
  • the oligomer When is about 2, the oligomer has a branching index of about 0.097.
  • This monomer is an example of a
  • substantially linear monomer which has small branches which, while not intending to be bound by any theory, advantageously will suppress the melting point of the oligoester diol.
  • Oligoester diols may be made by the catalyzed transesterification reaction of mixed dimethyl esters of glutaric, adipic and azelaic acids with 1,4-butanediol or
  • 1,3-butanediol The use of mixed acids provides another procedure for suppressing the melting point of the oligoester diol.
  • oligoester diols were synthesized with mixed dimethyl esters and 1,4-butanediol, the viscosity of the liquid monomer ranges from about 0.245 to about 4.6 Pa.s at 25oC, when it has a number average molecular weight ranging from about 300 to about 1600.
  • the viscosity of this liquid monomer ranges from about 0.295 Pa.s to about 2.92 Pa.s at 25oC, when it has a number average molecular weight ranging from about 350 to about 930.
  • the amount of branching in the oligoester diol to effect a melting point reduction and crystallinity reduction as described above varies with the particular combination of "linear" monomers and the characteristics of the branched comonomer.
  • the mole ratio of the branched diol to linear diol should not need to exceed 1:1 for branched diols having a single methyl side chain, such as 1,2-propanediol, or 0.67:1 for branched diols having an ethyl side chain, such as a 1,2-butanediol or two methyl side chains, such as neopentyl glycol.
  • the mesogenic hardener forms a dispersion or a solution with the oligoester diol when it is a part of the formulated coating composition.
  • the number average molecular weight of the mesogenic polyol is in the range of from about 186 to about 4000 and has a polydispersity index of not more than about 2.6 and preferably not more than about 2.2.
  • the mesogenic polyol forms a solution in the
  • the molecular weight of the mesogenic polyol is in the range of from about 186 to about 1000 and has a polydispersity index of not more than about 2.6 and preferably not more than about 2.2.
  • the mesogenic polyol has mesogenic groups selected from the group consisting of general formulas I, II and III as set forth above.
  • the mesogenic polyol and the mesogenic polyol is in solution in the formulated coating composition, the mesogenic polyol in the formulated coating composition is present in an
  • mesogenic groups based upon the weight of the mesogenic polyol.
  • the ratio by weight percent of the mesogenic polyol to oligoester diol is in the range of from about 5/95 to about 50/50 and preferably from about 10/90 to about 30/70.
  • mesogenic polyol has the general formula
  • E is selected from the group consisting of
  • G is selected from the group consisting of -COO-,
  • F is selected from the group consisting of -O-, -COO- and -OOC-.
  • R is an aliphatic C 4 to C 30 group which has at least one hydroxyl group. Any hydroxyl group which is a part of R is not in an alpha position to F, or in other words is spaced from F by at least one carbon atom.
  • the mesogenic polyol has the general formula
  • E is selected from the group consisting of
  • R', G and F are as set forth above and R is the adduct of a monoxirane having not more than 25 carbon atoms.
  • a particularly useful monoxirane to terminate a mesogenic diol, including the diol having the general formula IV, has the general formula
  • R' ' represents a mixture of aliphatic groups the three R' ' groups in the oxirane having a total of 8 carbon atoms.
  • An adduct of the latter oxirane is particularly useful as R in the general formula R-F-E-F-R.
  • the latter oxirane is commercially available from the Exxon Chemical Company under the name of Glydexx N-10 ® . Hence, when E and F are such that their combination provides
  • Glydexx N-10 ® terminates each end of the E, F combination to provide the R of the general formula R-F-E-F-R for one mesogenic diol, a particularly preferred mesogenic oligomer having the following formula is provided.
  • the polymeric vehicle comprises a blend of the linear oligoester diol and the mesogenic polyol of the general formula R-F-E-F-R (IV) or monoxirane adduct terminated diols of formula R-F-E-F-R as set forth above.
  • the mesogenic diol or polyols as set forth in formula IV are made by reacting a mesogenic diol such as
  • Aliphatic terminated diols may be derived from epoxies such as Glydexx N-10 ® by reacting a diol with the epoxy to provide the mesogenic polyol as follows.
  • Mesogenic diols 1 and 2 above may also serve as useful hardeners.
  • the hardener is a crystalline polyol which may be an oligomer or may be nonoligomeric and which polyol which consists essentially of carbon, hydrogen, oxygen and nitrogen atoms, has two or more hydroxyl groups and has from 5 to about 200 carbon atoms. If it has nitrogen atoms, these atoms will be a part of an amide, urea or amidine group. If the crystalline polyol is an oligomer, it has a number average molecular weight in the range of from about 400 to about 4000 and a polydispersity index of not more than about 2.6 and preferably not more than about 2.2. If the crystalline polyol is not
  • the crystalline polyol has a molecular weight in the range from 120 to about 500.
  • Crystalline polyols of the invention are non-phenolic.
  • Non-phenolic means that, in the aspect of the invention where the crystalline polyol contains an aromatic ring such as a benzene ring, the crystalline polyol does not have hydroxyl groups attached directly to the benzene ring.
  • the crystalline polyol is dispersed in the
  • the crystalline polyol is a liquid and is miscible with the formulated coating composition at a temperature of at least about 80oC, and preferably in the range of from about 100oC to about 175oC.
  • the crystalline polyol displays one or more first order transitions at from about 80oC to about 175oC by DSC and displays crystallinity by WAXS. It is insoluble in the formulated coating composition at storage and at application, but is miscible in the polymeric vehicle at the intended baking temperature of the formulated coating composition which provides the coating binder.
  • the crystalline polyol has a melting point of from about 5oC to about 40oC lower than the intended baking temperature of the formulated coating composition or the curing temperature of the polymeric vehicle.
  • the latter baking temperature generally ranges from about 70 to about 175oC.
  • crystalline polyols examples include the following.
  • Useful hardeners having the latter general formula include
  • C(CH 2 OH) 4 and RC(CH 2 OH) 3 are crystalline polyols where R is methyl, ethyl, propyl and butyl.
  • the polydispersity index of the substantially linear oligoester may be obtained by synthesizing the oligomer through a direct esterification reaction, a transesterification reaction or by an esterification reaction using reactants such as
  • DCC dicyclohexylcarbodiimide
  • polydispersity index of 1.1 or even lower may be obtained.
  • the crosslinker may be solid, but generally is a liquid. In either circumstance, the crosslinker is miscible or soluble in a blend of oligoester diol and hardener without raising the viscosity of the blend of the oligoester diol/hardener/crosslinker or the
  • the crosslinker has a functionality which is reactive with active hydrogens such as the hydroxyl groups of the oligoester and hardener and should be effective to provide a coating binder with a hardness of at least about B and in an important aspect, at least about H at a binder thickness of about 1 mil.
  • the polymeric vehicle comprises at least about a
  • crosslinker which will react with the hydroxyls of the oligoester and hardener.
  • the crosslinker may be a polyisocyanate which generally are not blocked because blocking will raise the viscosity of the isocyanate such that it will not be functional or useful in the practice of the invention.
  • Amino resins (usually made from amidines, ureas or amides by reaction with formaldehyde and subsequently usually with an alcohol) also may be used as a crosslinker which will react with the hydroxyls of the linear oligoester and hardener which is a polyol.
  • crosslinker has an average functionality reactive with the hydroxyls of the oligoester and hardener of greater than about 2.4. When it is a liquid, the crosslinker generally has a viscosity of less than about 3.0 Pa.s at about 25oC, continues to be a liquid at about 10oC, and is miscible with the oligoester and hardener.
  • Suitable crosslinkers include, but are not limited to melamine formaldehyde types such as hexakis
  • HMMM (methoxymethyl) melamine resin
  • crosslinker may be solid under certain conditions as long as it is soluble in the oligoester diol/hardener blend and does not increase the viscosity of the oligoester diol/hardener/ crosslinker blend or
  • crosslinkers include a hexakis
  • HMMM (methoxymethyl) melamine
  • HMMM resin appears as a waxy solid with a melting point in the range of about 30oC and is sold by Cytec Chemical Company under the name Cyme l 300.
  • Cytec Chemical Company under the name Cyme l 300.
  • a similar melamine resin which sometimes appears to be a solid at about 25oC and which can be used in the invention is a highly monomeric, highly methylolated hexamethylolated melamine formaldehyde resin which is sold by Monsanto Chemical Company under the designation HM-2612.
  • a particularly useful crosslinker includes a blend of polyisocyanates based on hexamethylene
  • Particularly useful crosslinkers are blends of polyisocyanates and melamines.
  • a particularly useful blend comprises a blend of melamine and Luxate ® XHD 0700 in a ratio such as 2.0 parts melamine to 0.65 Luxate ® to 0.22 Luxate ® also is a particularly useful crosslinker.
  • K-FLEX UD320-100 is a 100% polyurethane-diol with hydroxyl equivalent weight 160, viscosity 7.0 Pa.s at 50oC. Its structure is thought to be
  • K-FLEX UD-320W has the same structure as K-FLEX UD320-100, is a polyurethanediol containing about 10% by weight of water with hydroxyl equivalent weight 178, viscosity 8.0 Pa.s at 25oC.
  • Hardeners such as diesters of neopentyl glycol (NPG) and parahydroxybenzoic acid (PHBA) which diesters are hereinafter referred to as AY-1, also are useful additional hardener for the coating composition, especially if small amounts of organic solvents are used in the formulated coating composition.
  • a particularly useful hardener which is a diester of NPG and PHBA has the structure
  • hardeners may not give desired film properties, the above-identified additional hardeners, are particularly useful with polymeric vehicles which include amino resins.
  • polymeric vehicles which include amino resins.
  • Each of the components of the polymeric vehicle are in amounts effective for providing it with the aforedescribed viscosity range and are effective for providing a coating binder with a pencil hardness of at least about B at a thickness of about 1 mil dry.
  • Isocyanates provide excellent film properties but may shorten the pot life of the polymeric vehicle or formulated coating composition.
  • the reaction between the oligoester, hardener and the crosslinker which provides the coating binder generally is a catalyzed reaction.
  • Typical catalysts for isocyanate crosslinking reactions include soluble tin catalysts such as dibutyl tin dilaurate and
  • Typical catalysts for the amino resin crosslinking reactions include para toluene sulfonic acid (p-TSA), dodecyl benzene sulfonic acid and dinonyl nathphalene disulfonic acid.
  • p-TSA para toluene sulfonic acid
  • the catalyst comprises from about 0.3 to about 1.5 weight percent of the blend of oligoester and crosslinker, based upon the weight of the oligoester, crosslinker and catalyst.
  • the oligoester also having a polydispersity index of not more than about 2.6 and preferably not more than 2.2 and preferably below about 1.8 and mixing the oligoester with the hardener and a crosslinker with the functionality and viscosity as aforesaid. Maintaining the substantial linearity of the oligoester,
  • the formulated coating compositions are made by mixing the polymeric vehicle with pigments, catalysts and additives such as defoamers, pigment dispersants, anticrating agents and rheology modifiers.
  • formulated coating compositions have a viscosity of not more than about 1.2 Pa.s at about 50oC at shear rates which may range from about 1 sec. -1 to about 100,000 sec. -1 depending upon the intended method of
  • the formulated coating composition may be applied to a substrate by spraying (which has very high shear rates), dipping (which has a low shear rate such as about 1 sec. -1 ), roll coating, brushing (which may have shear rates of from about 1000 to about 20,000 sec. -1 ) or using other known application equipment and thereafter thermosetting the coating composition by the application of heat in the temperature range of from about 20oC to about 300oC for about 0.5 to about 60 minutes.
  • Azelaic acid (95g, 2 mols), 1,4-butanediol (6U.23g, 3 mols) and para toluene sulfonic acid are charged into the flask, and xylene (2% of total wt.) is used for reflux.
  • xylene 2% of total wt.
  • the mixture is heated up to 160oC (below the boiling points of diols). The temperature is held at 160oC for five hours until 17 mL water is collected. Then the
  • the difference is the initial reaction temperature.
  • the initial temperature is held at the temperature below the boiling points of diols.
  • the melting point of azeleates is as follows.
  • the molecular weight distributions of azeleates were as follows.
  • azeleates containing a trifunctional polyol based on trimethylolpropane (TMP) triol (C1) are made via the following reaction:
  • Azelaic acid 50g, 1 mol
  • trimethylolpropane TMP 68.56g of 72.46g, 2mol
  • boric acid 0.4% of total wt.
  • p-TSA p-TSA
  • Azeleates containing a trifunctional polyol based on TMP triol and 1,4- butanediol (C2) are made via the following reaction:
  • reaction follows the same procedure that C1 used. Diol, azelaic acid, 90% of TMP, and boric acid or p-TSA were charged into the flask at the initial stage. After six hours, the rest of the 10% TMP is added into the flask. A transparent liquid is
  • Linear oligoester diols (4 diol-azeleate and 7 diol-adipate) and azeleate containing a trifunctional polyol (C 2 ) described in Example II are used as
  • Hexa(methyoxymethyl) melamine resin (Resimene 747), a fully methylolated, monomeric melamine resin in which hexakis (methoxymethyl) melamine is a
  • melamine resin (Resimene 755), a methylolated and butylolated melamine resin in which hexakis
  • K188 which are proprietary diols were obtained from King Industries, Norwalk, Connecticut.
  • K-Flex 188 has the structure
  • K-Flex 128 also is a polyester made from a
  • the catalyst p-TSA, is first dissolved into small amount (about 0.5 ml) of acetone, and then is added into a well-mixed coating mixture. After the catalyst is added, the formulations are well stirred again.
  • each untreated steel Q-panel is cleaned with acetone or xylene three times.
  • Coatings are prepared by drawing down on untreated steel Q-panels with a #30 wire-wrapped, draw-down bar. Coatings applied are preheated in the temperature range from 40oC to 60oC, meanwhile, steel panels and draw-down bar also are preheated to about 40oC or 50oC.
  • Viscosities are measured on a Brookfield LVDVII+ viscometer equipped with thermal cello. Samples measured included polyol, crosslinker and catalyst.
  • 4-Diol azeleate (4DA) (M n - 695) (30 g) is placed in a 100-mL beaker and heated to 150oC on a hotplate.
  • THECA (6 g) is placed in another 100-mL beaker and heated at 150oC in an oven until it melts, then it is poured into hot liquid 4DA under fast magnetic stirring. The mixture is cooled down to room
  • Resimene 755 or 797 were added at a ratio of 65/35 (4DA/melamine). The mixture was then stirred for 40 hours. Resimene 797 is methylolated melamine
  • formaldehyde resin having as its principal reactive group -N- (CH 2 OCH 3 ) 2 . It contains 20 weight % of a polyol additive. It totals 92% solids-weight.
  • DNNDSA is a liquid and is easy to mix into the resin.
  • the properties are listed in Table 17. It was found that the use of DNNDSA improved glass and leveling and that, when formulated with Resimene 797, the coating film had the best improvement in film properties, the hardness was 2H-3H and adhesion was 3B on untreated panels.
  • DA 4-Diol azeleate
  • 6GT 6-glycol-terephthalate, 3 g is placed in an aluminum dish and heated at 130oC in an oven until it melts, then it is poured into liquid 4DA. The mixture is cooled down to room temperature under magnetic stirring. Melamine resins 755 or 797 are added at ratio of 65/35 (4DA/melamine;. The mixture is then stirred for 2 hours.
  • the D-sorbitol was not dispersed and together with water formed a fluffy suspension in the solution.
  • oligoester diols were as follows. Dimethyl azelate was obtained from Aldrich and redistilled, the distilled diester was composed of dimethyl esters of heptanedioic (1.8%), octanedioic (4.1%), azelaic (83.6%),
  • decanedioic (3.5%) and undecanedioic (7.1%) acids as determined by GC/MS.
  • Dimethyl glutarate and dimethyl adipate were obtained from Du Pont, as ''DBE-5" and "DBE-3", respectively, they are reported to be mixtures of the dimethyl esters of succinic (SA), glutaric (GA), and adipic (AA) acids in the following proportions:
  • DBE-3 SA, ⁇ 1%; GA, 5-15 %; AA, 85-95%;
  • DBE-5 dimethyl glutarate >98.5%.
  • DBE-3 and DBE-5 are liquids at 25oC. and solids at 0oC. 1,4-butanediol (99%) and zinc acetate dihydrate (98%) were obtained from Aldrich Chemical Co.
  • dimethyl azelate 108 g., 0.5 mol
  • DBE-3 87 g., 0.5 mol
  • DBE-5 80 g., 0.5 mol
  • 1,4-butanediol 270 g., 3.0 mol
  • zinc acetate dihydrate 1.09 g., 0.2% of total reactant weight.
  • the stirred mixture was heated by an electrothermal heating mantle with a controller from 150oC. to 170oC. for 3 hours, and then heated to 200oC, and maintained for 1 hour.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un véhicule polymère efficace dans la production d'une composition pour revêtement à haute teneur en matières solides. Ledit véhicule est constitué d'un mélange d'au moins un diol oligoester non mésogénique sensiblement linéaire et d'au moins un durcisseur qui est un polyol, un alcool-ester phénolique ou un polyol crystallin de type mésogénique. Le mélange en question est efficace lorsqu'il est mis en réaction avec un agent de réticulation réactif à l'oligoester et au durcisseur non mésogénique.
PCT/US1996/000982 1994-01-25 1996-01-24 Vehicule polymere pour revetements a haute teneur en matieres solides WO1996023034A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR1019960705323A KR970702335A (ko) 1994-01-25 1996-01-24 고 고체 코팅을 위한 중합체성 담체(polymeric vehicle for high solids coatings)
JP8522993A JPH10501581A (ja) 1995-01-24 1996-01-24 高固形分被覆物用ポリマービヒクル
EP96905213A EP0751978A1 (fr) 1995-01-24 1996-01-24 Vehicule polymere pour revetements a haute teneur en matieres solides
AU49029/96A AU710344B2 (en) 1995-01-24 1996-01-24 Polymeric vehicle for high solids coatings
MXPA/A/1996/004247A MXPA96004247A (en) 1995-01-24 1996-09-23 Polymeric vehicle for coatings with high content of soli

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
USPCT/US95/01058 1995-01-24
PCT/US1995/001058 WO1995020004A1 (fr) 1994-01-25 1995-01-24 Vehicule polymere pour revetements a haute teneur en solides
US08/477,091 1995-06-07
US08/477,091 US5641854A (en) 1994-01-25 1995-06-07 Polymeric vehicle for high solids coatings

Publications (1)

Publication Number Publication Date
WO1996023034A1 true WO1996023034A1 (fr) 1996-08-01

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PCT/US1996/000982 WO1996023034A1 (fr) 1994-01-25 1996-01-24 Vehicule polymere pour revetements a haute teneur en matieres solides

Country Status (5)

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EP (1) EP0751978A1 (fr)
JP (1) JPH10501581A (fr)
AU (1) AU710344B2 (fr)
CA (1) CA2185456A1 (fr)
WO (1) WO1996023034A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5910563A (en) * 1994-01-25 1999-06-08 Exxon Chemical Patents, Inc. Water thinned polymeric vehicle for coating compositions with low amounts of volatile organic compounds
US5955550A (en) * 1994-01-25 1999-09-21 Exxon Chemical Patents, Inc. Polymeric vehicle for providing solventless coating compositions
US5969085A (en) * 1994-01-25 1999-10-19 Exxon Chemical Patents, Inc. Polymeric vehicle for high solids coatings
US5976706A (en) * 1995-10-10 1999-11-02 Exxon Chemical Patents Inc. Low viscosity, high solids polyesterdiols and compositions containing same
US6087464A (en) * 1995-04-19 2000-07-11 Exxon Chemical Patents, Inc. Polymeric vehicles which include a polyol, a phenolic ester alcohol and isocyanate compound
US6103826A (en) * 1995-04-19 2000-08-15 Eastern Michigan University Clearcoat compositions containing phenolic ester compounds
US6541594B2 (en) 2000-12-19 2003-04-01 Basf Corporation Coating compositions containing crosslinkable monomeric difunctional compounds having at least thirty carbon atoms
US6740706B2 (en) 2001-12-07 2004-05-25 Basf Corporation Method for obtaining coating compositions having reduced VOC
US6812316B2 (en) 2000-12-19 2004-11-02 Basf Corporation Powder coating compositions and powder slurry coating compositions containing monomeric difunctional compounds
US7163984B2 (en) 2000-12-19 2007-01-16 Basf Corporation Waterborne coating compositions containing monomeric difunctional compounds
US7205029B2 (en) 2000-12-19 2007-04-17 Basf Corporation Method of providing cured coating films free of popping defects
US7321013B2 (en) 2000-12-19 2008-01-22 Basf Corporation Method for obtaining coating compositions having reduced VOC
US7368501B2 (en) 2000-12-19 2008-05-06 Basf Corporation Method for improving environmental durability of materials
US7696285B2 (en) 2000-12-19 2010-04-13 Basf Coatings Ag Carbamate functional reactive polymer composition
US20120199198A1 (en) * 2009-10-26 2012-08-09 Hebrink Timothy J Structured film and articles made therefrom

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994851A (en) * 1972-10-26 1976-11-30 Ppg Industries, Inc. High solids polyester coating composition
FR2335573A1 (fr) * 1975-12-15 1977-07-15 Akzo Nv Composition de revetement pigmentee a haute teneur en corps solides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10501582A (ja) * 1995-01-24 1998-02-10 イースターン ミシガン ユニヴァーシティー 無溶剤被覆組成物を得るのに有効なポリマービヒクル

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994851A (en) * 1972-10-26 1976-11-30 Ppg Industries, Inc. High solids polyester coating composition
FR2335573A1 (fr) * 1975-12-15 1977-07-15 Akzo Nv Composition de revetement pigmentee a haute teneur en corps solides

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5910563A (en) * 1994-01-25 1999-06-08 Exxon Chemical Patents, Inc. Water thinned polymeric vehicle for coating compositions with low amounts of volatile organic compounds
US5955550A (en) * 1994-01-25 1999-09-21 Exxon Chemical Patents, Inc. Polymeric vehicle for providing solventless coating compositions
US5969085A (en) * 1994-01-25 1999-10-19 Exxon Chemical Patents, Inc. Polymeric vehicle for high solids coatings
US6087464A (en) * 1995-04-19 2000-07-11 Exxon Chemical Patents, Inc. Polymeric vehicles which include a polyol, a phenolic ester alcohol and isocyanate compound
US6103826A (en) * 1995-04-19 2000-08-15 Eastern Michigan University Clearcoat compositions containing phenolic ester compounds
US5976706A (en) * 1995-10-10 1999-11-02 Exxon Chemical Patents Inc. Low viscosity, high solids polyesterdiols and compositions containing same
US6812316B2 (en) 2000-12-19 2004-11-02 Basf Corporation Powder coating compositions and powder slurry coating compositions containing monomeric difunctional compounds
US6541594B2 (en) 2000-12-19 2003-04-01 Basf Corporation Coating compositions containing crosslinkable monomeric difunctional compounds having at least thirty carbon atoms
US6962730B2 (en) 2000-12-19 2005-11-08 Basf Corporation Coating composition containing crosslinkable monomeric difunctional compounds having at least thirty carbon atoms
US7163984B2 (en) 2000-12-19 2007-01-16 Basf Corporation Waterborne coating compositions containing monomeric difunctional compounds
US7205029B2 (en) 2000-12-19 2007-04-17 Basf Corporation Method of providing cured coating films free of popping defects
US7321013B2 (en) 2000-12-19 2008-01-22 Basf Corporation Method for obtaining coating compositions having reduced VOC
US7368501B2 (en) 2000-12-19 2008-05-06 Basf Corporation Method for improving environmental durability of materials
US7691951B2 (en) 2000-12-19 2010-04-06 Basf Corporation Method for obtaining coating compositions having reduced VOC
US7696285B2 (en) 2000-12-19 2010-04-13 Basf Coatings Ag Carbamate functional reactive polymer composition
US6740706B2 (en) 2001-12-07 2004-05-25 Basf Corporation Method for obtaining coating compositions having reduced VOC
US20120199198A1 (en) * 2009-10-26 2012-08-09 Hebrink Timothy J Structured film and articles made therefrom

Also Published As

Publication number Publication date
JPH10501581A (ja) 1998-02-10
CA2185456A1 (fr) 1996-08-01
EP0751978A1 (fr) 1997-01-08
AU4902996A (en) 1996-08-14
AU710344B2 (en) 1999-09-16

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