WO1998018856A1 - Compositions de reticulation liquides contenant des melanges de resines aminoplastes/et de carbamates de 1,3,5-triazine - Google Patents

Compositions de reticulation liquides contenant des melanges de resines aminoplastes/et de carbamates de 1,3,5-triazine Download PDF

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Publication number
WO1998018856A1
WO1998018856A1 PCT/US1997/016121 US9716121W WO9818856A1 WO 1998018856 A1 WO1998018856 A1 WO 1998018856A1 US 9716121 W US9716121 W US 9716121W WO 9818856 A1 WO9818856 A1 WO 9818856A1
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Prior art keywords
crosslinker
resin
triazine
compositions
crosslinker composition
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PCT/US1997/016121
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English (en)
Inventor
Sidney Binder
Kuang-Jong Wu
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Cytec Technology Corp.
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Application filed by Cytec Technology Corp. filed Critical Cytec Technology Corp.
Priority to EP97942434A priority Critical patent/EP0935635A1/fr
Priority to AU44133/97A priority patent/AU4413397A/en
Priority to BR9712600-4A priority patent/BR9712600A/pt
Priority to CA002270384A priority patent/CA2270384A1/fr
Priority to JP52045798A priority patent/JP2001506675A/ja
Publication of WO1998018856A1 publication Critical patent/WO1998018856A1/fr
Priority to NO992089A priority patent/NO992089L/no

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/508—Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
    • C08G59/5086—Triazines; Melamines; Guanamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds

Definitions

  • This invention relates generally to crosslinker compositions containing substantially homogeneous mixtures of 1 ,3,5-triazine carbamates and aminoplast resins and methods of preparation thereof.
  • the invention also relates to a process for preparing curable coating compositions derived from the inventive crosslinker compositions as well as a method of coating substrates.
  • amino-1 ,3,5-triazines are described in the literature as having uses in a wide variety of fields. Certain of these derivatives, such as aminoplast resins including alkoxymethyl derivatives of melamine and guanamines, are useful as crosslinkers or reactive modifiers in curable compositions which contain resins having active hydrogen groups.
  • alkoxymethylated melamines and guanamines provide excellent results in a number of aspects, they also have the disadvantage of releasing formaldehyde as a volatile by-product under curing conditions.
  • Crosslinking agents which minimize the release of formaldehyde but which also retain the advantageous performance characteristics of alkoxymethylated melamines and guanamines would be particularly advantageous and are highly desired.
  • organic solvent-based coatings prepared from organometallic, base or acid catalyzed systems using 1 ,3,5-triazine carbamate crosslinkers. Also disclosed therein is the use of the 1 ,3,5-triazine carbamates as co-crosslinkers in combination with conventional aminoplast resin crosslinkers to improve the acid etch resistance and lower formaldehyde emission of traditional organic solvent-based aminoplast resin crosslinked systems.
  • Solvent-based coating compositions are typically prepared by mixing a substantially homogeneous solution of the crosslinking agent in an appropriate organic solvent with the remaining ingredients.
  • the present invention meets the aforementioned industry need by providing a crosslinker composition comprising a liquid, substantially homogenous mixture of: ( ⁇ ) a 1 ,3,5-tr ⁇ az ⁇ ne carbamate,
  • the crosslinker composition having a solids content of at least about 65 wt% based on the total weight of the crosslinker composition, the combination of (i) and (n) comprising at least 50 wt% based on the total weight of the crosslinker composition, and the weight ratio of ( ⁇ ):(i ⁇ ) being in the range of from 1 :99 to 99:1.
  • inventive crosslinker compositions may also contain other optional ingredients, for example, cure catalysts, light stabilizing additives, antioxidants, anitfoaming agents and other additives and adjuvants normal to the particular chosen end use of the crosslinker composition, to the extent that the crosslinker composition remains within the above parameters.
  • cure catalysts for example, cure catalysts, light stabilizing additives, antioxidants, anitfoaming agents and other additives and adjuvants normal to the particular chosen end use of the crosslinker composition, to the extent that the crosslinker composition remains within the above parameters.
  • the present invention also includes a process for preparing a substantially homogeneous liquid crosslinker composition
  • a process for preparing a substantially homogeneous liquid crosslinker composition comprising the step of admixing a 1 ,3,5- tnazine carbamate, an aminoplast resin and, optionally, an organic solvent at a temperature and for a length of time sufficient to produce said substantially homogeneous liquid crosslinker composition having a solids content of at least about 65 wt% based on the total weight of the crosslinker composition, the combination of (i) and (n) comprising at least 50 wt% based on the total weight of the crosslinker composition, and the weight ratio of (i):( ⁇ ) being in the range of from 1 :99 to 99:1.
  • liquid curable composition comprising a substantially homogenous mixture of (I) a resin component comprising a poly(act ⁇ ve hydrogen and/or epoxy) compound; and (II) the substantially homogeneous liquid crosslinker composition described above.
  • curable compositions in accordance with the present invention may be utilized in a wide variety of fields as described in the a number of the previously incorporated references.
  • a particularly preferred end use is as a one- or two-component sprayable coating for elevated temperature cure applications such as, for example, automotive original equipment manufacture (OEM) pigmented basecoats and clearcoats.
  • OEM automotive original equipment manufacture
  • the crosslinker compositions of the present invention are substantially homogeneous liquid compositions comprising a 1 ,3,5-triazine carbamate, an aminoplast resin and, optionally, an organic solvent.
  • the crosslinker compositions in accordance with the present invention can be prepared using any combination and/or any ratio of the above ingredients provided that such combination produces a substantially homogeneous liquid composition meeting the parameters described above.
  • the term "liquid" as used in the context of the present invention defines mixtures which are pourable at ambient temperature.
  • Such mixtures possess a viscosity of less than about 32,000 centipoise (cps) at 25°C, and more preferably a viscosity of less than 16,000 centipoise (cps) at 25°C, as measured by a Brookfield Viscometer in accordance with ASTM D2196.
  • the crosslinker compositions of the present invention are high solids compositions, containing a total solids of at least about 65 wt%, more preferably at least about 70 wt%, and especially at least about 75 wt%, based on the total weight of the crosslinker composition, as measured by ASTM D4713 (method B).
  • the inventive crosslinker compositions are substantially organic solvent free (at least 95 wt%, and preferably essentially 100 wt%, solids content), the aminoplast resin is a liquid aminoplast resin, and the weight ratio of 1 ,3,5-triazine carbamate to aminoplast resin is from about 1 :99 to about 80:20, more preferably from about 1 :99 to about 50:50, and especially from about 5:95 to about 25:75.
  • the inventive crosslinker compositions comprise an organic solvent in an amount up to about 35 wt% (and more preferably from about 10 to about 30 wt%), and from about 50 to about 90 wt% (and more preferably from about 65 to about 90 wt%) of the combination of the 1 ,3,5-triazine carbamate and the aminoplast resin, with the weight ratio of 1 ,3,5-triazine carbamate to aminoplast resin being from about 20:80 to about 99:1 , and more preferably from about 25:75 to about 90:10.
  • the 1 ,3,5-triazine carbamates suitable for use in the present invention are materials known from previously incorporated US4939213, US5084541 , US5288865, US5556971 , US5565243, US5574103, EP-A-0624577, EP-A-0649842, WO96/04258, W096/11915, W096/15185 and WO97/08235.
  • Preferred for use in the present invention are those 1 ,3,5- triazine carbamates of the following general formula, as well as oligomers thereof:
  • R is selected from the group consisting of -NHCOOR 3 , hydrogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amido, sulfonamido, amino, hydrocarbylamino, dihydrocarbylamino and hydrocarbyleneamino (cyclic amino); and each R ⁇ R 2 and R 3 is independently selected from a hydrocarbyl group.
  • hydrocarbyl in the context of the present invention, and in the above formula, broadly refers to a group which contains at least carbon and hydrogen atoms and includes, for example aliphatics, cycloaliphatics, aromatics and mixed character groups.
  • Hydrocarbyl includes such groups as, for example, alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl and cycloalkenyl, preferably having up to 20 carbon atoms. As exemplified below, these groups may also have a substituent group such as, for example, a hydroxyl, amino, halogen, cyano, sulfoxide, sulfone, carbonyl, ester and/or amide. As also exemplified below, these groups may contain a heteroatom in the chain, such as an oxygen, sulfur or nitrogen.
  • R is selected from -NHCOOR 3 ; hydrogen; a hydrocarbyl having from 1 to 20 carbon atoms; a hydrocarbyloxy having from 1 to 20 carbon atoms (such as methoxy and phenoxy); a hydrocarbylthio group having 1 to 20 carbon atoms (such as methylthio and phenylthio); an amido group having from 1 to 20 carbon atoms (such as acetamido); a sulfonamido group having from 1 to 20 carbon atoms (such as benzene sulfonamido); an amino group; a hydrocarbylamino group having from 1 to 20 carbon atoms (such as methylamino, butylamino, methylolamino, methoxymethylamino and butoxymethylamino); a dihydrocarbylamino group wherein each hydrocarbyl group has 1 to 20 carbon atoms (such as dimethyiamino, dibuty
  • Preferred hydrocarbyls are alkyls having from 1 to 20 carbon atoms (e.g., methyl and butyl), aryls having from 6 to 20 carbon atoms (e.g., phenyl), cycloalkyls having from 4 to 20 carbon atoms (e.g., cyclohexyl), alkenyls having from 2 to 20 carbon atoms (e.g., vinyl) and aralkyls having from 7 to 20 carbon atoms (e.g., benzyl).
  • R is selected from -NHCOOR 3 , hydrogen, an alkyl of 1 to 20 carbon atoms, a cycloalkyl of 5 to 20 carbon atoms, an alkenyl of 3 to 20 carbon atoms, an aryl of 6 to 20 carbon atoms, an aralkyl of 7 to 20 carbon atoms and an amino group.
  • R is -NHCOOR 3 .
  • R 1 , R 2 and R 3 may be mentioned, for example, hydrocarbyl groups having from 1 to 20 carbon atoms such as alkyl (e.g., methyl and butyl), aryl (e.g., phenyl), cycloalkyl (e.g., cyclohexyl), alkenyl (e.g., vinyl), aralkyl (e.g., methyl phenyls), alkaryl (e.g., phenylmethyl), hydroxyalkyl (e.g., methylol), hydroxyaryl (e.g., hydroxyphenyl), alkoxyalkyl (e.g., methoxymethyl and butoxymethyl), aryloxyalkyl (e.g., phenoxymethyl), hydroxyalkoxyalkyl (e.g., hydroxypropoxymethyl) and hydroxyaryioxyalkyl (e.g., hydroxyphenoxymethyl).
  • alkyl e.g., methyl and
  • R ⁇ R 2 and R 3 are alkyls having 1 to 8 carbon atoms, alkenyls having 2 to 8 carbon atoms, cyclic alkyls and alkenyls having from 4 to 12 carbon atoms, alkoxyalkyls having from 2 to 16 carbon atoms, aryls having from 6 to 18 carbon atoms, aralkyls having from 7 to 20 carbon atoms and alkaryls having 7 to 20 carbon atoms.
  • Especially preferred 1 ,3,5-triazine carbamate crosslinkers for use in this invention are those of the above formula wherein R is -NHCOOR 3 , and wherein R ⁇ R 2 and R 3 are independently an alkyl having 1 to 8 carbon atoms, and particularly methyl and/or butyl, which includes which includes tris-(butoxycarbonylamino)-1,3,5-triazine, tris-(methoxycarbonylamino)-1 ,3,5-triazine and tris-(methoxybutoxycarbonylamino)-1 ,3,5- triazine.
  • a 1 ,3,5-triazine carbamate crosslinkers having a methyl to butyl molar ratio in the range of from about 0.50 to about 1.5 (as determined by Nuclear Magnetic Resonance (NMR) spectroscopy), and particularly those having methyl to butyl ratios in the range of from about 0.65 to about 1.2.
  • aminoplast resins may be mentioned the partially or substantially fully methylolated, partially or substantially fully etherified aminoplast resins based on melamine, guanamines, glycolurils and urea.
  • aminoplast resins are well-known to those of ordinary skill in the art (see, for example, previously incorporated US5565243,
  • melamines include, most commonly, melamines, guanamines such as benzo-, aceto-, and cyclohexylcarbo-guanamines, glycolurils and ureas, as well as the at least partially
  • aminoplast resin also includes oligomers thereof.
  • melamine-based aminoplast resins may be mentioned those having the following general formula:
  • each R 4 is independently selected from H, an alkylol group and an alkoxyalkyl group.
  • Preferred melamines are those wherein each R 4 is independently selected from H, a methylol group and an alkoxymethyl group having from 1 to 8 carbon atoms in the alkoxy group.
  • guanamine-based aminoplast resins may be mentioned those of the following general formula:
  • Z is selected from H, an alkyl group of from 1 to 20 carbon atoms, an aryl group of from 6 to 20 carbon atoms, and an aralkyl group of from 7 to 20 carbon atoms, and wherein each R 5 is independently selected from H, an alkylol group and an alkoxyalkyl group.
  • Preferred guanamines are those wherein each R 5 is independently selected from H, a methylol group and an alkoxymethyl group having from 1 to 8 carbon atoms in the alkoxy group, and particularly wherein Z is selected from a phenyl group (benzoguanamines), a methyl group (acetoguanamines) and a cyclohexyl group (cyclohexylcarboguanamines).
  • Suitable glycoluril-based aminoplast resins include those having the general formula:
  • Y is selected from H, an alkyl group of from 1 to 20 carbon atoms, an aryl group of from 6 to 20 carbon atoms, and an aralkyl group of from 7 to 20 carbon atoms
  • each R 6 is independently selected from H, an alkylol group and an alkoxyalkyl group.
  • Preferred glycolurils are those wherein each R 6 is independently selected from H, a methylol group and an alkoxymethyl group having from 1 to 8 carbon atoms in the alkoxy group.
  • urea-based aminoplast resins may be mentioned those of the following general formula:
  • each R 7 is independently selected from H, an alkylol group and an alkoxyalkyl group.
  • Preferred ureas are those wherein each R 7 is independently selected from H, a methylol group and an alkoxymethyl group having from 1 to 8 carbon atoms in the alkoxy group.
  • commercially available aminoplast resins of the type described above may be mentioned those sold under the trademarks CYMEL ® and BEETLE ® of Cytec Industries, Inc. (West Paterson, New Jersey).
  • Organic solvents suitable for use in the crosslinker compositions of the present invention include common organic solvents including those described in the various incorporated references. Preferred are those solvents of the type typically found in coatings applications including, for example, alcohols, ketones, esters, ethers, amides, sulfones, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and the like, such as disclosed in previously incorporated US4939213, US5084541 ,
  • Particularly preferred organic solvents include ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether; amides such as N,N-dimethyl acetamide; N-methyl pyrrolidone; N,N-dimethyl formamide; hexamethyl phosphoramide; hydrocarbons such as toluene and xylene; sulfones such as dimethyl sulfone; sulfolane; esters such as methyl acetate, ethyl acetate and ethyl formate; and lower alcohols.
  • ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether
  • amides such as N,N-dimethyl acetamide; N-methyl pyrrolidone; N,N-dimethyl formamide; hexamethyl phosphoramide
  • hydrocarbons such as toluene and xy
  • Alcohols of 1 to 8 carbon atoms are preferred, and include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isomers thereof and mixtures thereof.
  • the most preferred alcohol is n-butanol.
  • Solvents having a plurality of functionalities such as ethylene glycol monomethyl ether, methoxypropyl acetate, hydroxypropyl acetate and the like, and mixed solvents, are also usable.
  • inventive crosslinker compositions may also contain a variety of other optional ingredients, for example, cure catalysts, light stabilizing additives, antioxidants, anitfoaming agents and other additives and adjuvants normal to the particular chosen end use of the crosslinker composition.
  • cure catalysts for 1 ,3,5-triazine carbamate crosslinked systems include acidic and organometallic catalysts of the type well-known to those skilled in the relevant coatings art.
  • acidic catalysts may be mentioned sulfonic acids (such as p-toluene sulfonic acid or dodecyl benzene sulfonic acid), aryl and alkyl acid-phosphates and pyrophosphates, carboxylic acids, sulfonimides and mineral acids.
  • sulfonic acids such as p-toluene sulfonic acid or dodecyl benzene sulfonic acid
  • aryl and alkyl acid-phosphates and pyrophosphates such as carboxylic acids, sulfonimides and mineral acids.
  • Latent acidic catalysts such as amine-blocked p-toluene sulfonic acid, amine-blocked dodecyl benzene sulfonic acid, methyl p-toluenesulfonate, benzoin p-toluesulfonate and the like are particularly useful as acid catalysts for producing compositions which are stable at room temperature and have a very long shelf life.
  • organometallic catalysts may be mentioned organotin compounds such as dibutyltin di-2-ethylhexoate, dibutyltin diisooctyl maleate, dibenzyltin di-2- ethylhexoate, dibutyltin dilaurate, dimethyltin dilaurate, tetrabutyl diacetoxy distannoxane, tetramethyl diacetoxy distannoxane, tetrapropyl diacetoxy distannoxane, dibutyltin dichloride, and the like. Combinations of the above mentioned catalysts are also suitable in the compositions of the present invention.
  • the cure catalyst when used, should be present in the crosslinker compositions in an amount so as to result in a final formulated curable system containing from about 0.001 wt% to about 6 wt%, and preferably up to about 3 wt%, of the catalyst. Typically, this will result in the crosslinker composition comprising the cure catalyst in an amount up to about
  • auxiliaries and additives typically utilized in the coatings industry include foam inhibitors, levelling aids, pigments, dispersants such as pigment dispersing aids, dyes, UV absorbers (including hydroxy aryl triazine types (such as CYAGARD® UV 1164 of Cytec Industries Inc.), benzotriazole types and benzophenone types), heat stabilizers, other stabilizing additives such as antioxidants, hindered amine light stabilizers (such as Sanduvor® 3055 and 3058 of Clariant) and the like.
  • foam inhibitors levelling aids
  • pigments such as pigment dispersing aids, dyes
  • UV absorbers including hydroxy aryl triazine types (such as CYAGARD® UV 1164 of Cytec Industries Inc.), benzotriazole types and benzophenone types), heat stabilizers, other stabilizing additives such as antioxidants, hindered amine light stabilizers (such as Sanduvor® 3055 and 3058 of Clariant) and the like.
  • antioxidants such as
  • crosslinker compositions of the present invention are prepared by admixing a
  • a solution of the 1 ,3,5-triazine carbamate in an organic solvent and an aminoplast resin and other optional ingredients are admixed.
  • neat 1 ,3,5-triazine carbamate and neat aminoplast resin are admixed directly, without solvent, and thereafter an organic solvent and/or other components are optionally admixed.
  • solid 1 ,3,5-triazine carbamate, an aminoplast resin and other optional ingredients (besides a solvent) are admixed, and thereafter an organic solvent is optionally admixed.
  • a solution of aminoplast resin in an organic solvent, the 1 ,3,5-triazine carbamate and other optional ingredients are all admixed.
  • the crosslinker compositions can also be prepared by further modifying a composition by increasing or decreasing the concentration of one or more components, for example, by admixing an additional amount of organic solvent or 1 ,3,5-triazine carbamate or by removing a portion of the solvent from any of the above crosslinker compositions or by sequentially carrying out both the admixing and the removing steps to produce a higher or lower solids crosslinker composition.
  • the substantially homogeneous crosslinker compositions of the invention can be combined with a reactive resin component to form curable compositions suitable for numerous uses including, for example, as coatings and adhesives, in decorative laminated boards, and in the formation of crosslinked molded articles such as engineering composites.
  • curable compositions can readily be prepared via methods and in relative amounts which are recognizable by those of ordinary skill in the art in the relevant field depending upon the particular end use chosen.
  • the reactive resin component and the crosslinker component should preferably be admixed in the curable compositions in an equivalents ratio (equivalents of reactive functionality) of from about 0.5:1 to about 2:1 , and more preferably from about 0.8:1 to about 1.2:1.
  • reactive resins for use in the coating compositions are compounds containing a plurality of active hydrogen and/or epoxy functionalities ("polyfunctional (active hydrogen and/or epoxy) resins").
  • Active hydrogen functionality refers to groups which contain active hydrogens capable of reacting with, for example, the carbamate groups of the 1 ,3,5-triazine carbamates (or functionality which may be generated by the carbamate groups under cure conditions, such as isocyanate functionality), and/or with the imino, alkylol and/or alkoxymethyl groups of the aminoplast resins, under the cure conditions of the coatings.
  • active hydrogen functionalities are generally well known to those skilled in the coatings art and includes groups such as hydroxyl, carboxyl, mercapto, amino, amido and carbamato groups. Preferred are hydroxyl, carboxyl and amino, and particularly hydroxyl.
  • backbone resins are generally well known to those skilled in the art and are described in the previously incorporated US4939213, US5084541 , US5565243, US5574103, W096/15185 and WO97/08235.
  • the preferred active hydrogen-containing resins are hydroxy group containing materials containing on average at least two, and preferably more than two, hydroxy groups per molecule.
  • the preferred polyfunctional hydroxy group containing materials are acrylic or polyester backbone resins.
  • Illustrative examples include acrylic resins which may be obtained by the copolymerization of acrylic or methacrylic esters with hydroxyfunctional acrylic or methacrylic esters such as hydroxyethyl acrylate or methacrylate, optionally with simultaneous use of additional vinyl compounds such as, for example, styrene.
  • Illustrative examples of the polyfunctional hydroxy group containing materials also include polyester resins which may be obtained, for example, by the reaction of polycarboxylic acids with excess quantities of polyhydric alcohols.
  • suitable polyfunctional hydroxy group containing resins also include polyurethane prepolymers, alkyds, as well as hydroxy group containing epoxy prepolymers such as those resulting from the reaction of a polyfunctional epoxy group containing compound with an amine or with a polyfunctional carboxylic acid derivative.
  • the hydroxyl functionalities of such resins are pendently or terminally attached, imparting the resins preferably the following characteristics: weight average molecular weights (Mw) of from about 750 to about 7000, and more preferably from about 2000 to about 5000; and hydroxyl numbers of from about 20 to about 300 mg KOH/g resin and more preferably from about 60 to about 200 mg KOH/g resin.
  • active hydrogen containing resins include DORESCO ® TA 39-21 acrylic resin (Dock Resins, Linden, N.J.), JONCRYL ® 500 acrylic resin (S.C. Johnson & Sons, Racine, Wl), ACRYLOID ® AT-400 acrylic resin (Rohm & Haas, Philadelphia, PA), CYPLEX ® 1531 polyester resin (Cytec Industries, West Paterson, NJ), CARGILL 3000 and 5776 polyester resins (Cargill, Minneapolis, MN), TONE ® polyester resin (Union Carbide, Danbury, CT), K-FLEX ® XM-2302 and XM-2306 resins (King Industries, Norwalk, CT), CHEMPOL ® 11-1369 resin (Cook Composites and Polymers (Port
  • SCX-800-B hydroxyfunctional solid acrylic resins (S.C. Johnson & Sons, Racine, Wl), ALFTALAT ® AN 745 hydroxyfunctional polyester resin, a product of Hoechst Corporation and the like.
  • the polyfunctional epoxy compounds usable as the resin component in the curable compositions of the present invention contain, on average, at least two and preferably more than two epoxy functionalities per molecule, and includes polyfunctional epoxy group containing materials which are monomeric, oligomeric, polymeric or a mixture thereof.
  • Such polyfunctional epoxy compounds are in general well-known to those of ordinary skill in the art, as exemplified by US2872427, US3730930, US3752870, US3781380, US3787521 , US4011381 , US4346144, US4607069, US4650718, US4681811 , US4703101 ,
  • difunctional epoxy resins including glycidyl ethers of dihydric phenols like the bisphenol-A/epichlorohydrin reaction products such as diglycidyl bisphenol-A; vinyl cyclohexene diepoxides such as 4-vinyl-1-cyclohexene diepoxide; 1 ,2,5,6-diepoxycyclooctane; 1 ,2,7,8-diepoxyoctane; dicyclopentadiene diepoxide; 1 ,4- divinyl benzene diepoxide; cyclohexene-4-methyl cyclohexene-4-carboxylate diepoxide; glycidylated diol type polyfunctional epoxy group containing materials such as hexane diol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether,
  • Suitable monomeric polyfunctional epoxy compounds include trifunctional epoxy resins (trisepoxides) such as tri-(4-glycidyl oxyphenyl)methane and triglycidyl isocyanurate; and higher polyfunctional epoxides such as glycidylated pentaerythritol and sorbitol.
  • trifunctional epoxy resins such as tri-(4-glycidyl oxyphenyl)methane and triglycidyl isocyanurate
  • higher polyfunctional epoxides such as glycidylated pentaerythritol and sorbitol.
  • epoxy resins sold under the trade designation Epon ® of Shell Chemical Company (Houston, TX) such as Epon ® 828 resin having an equivalent weight in the range of 185 to 192.
  • Epon ® 828 resin having an equivalent weight in the range of 185 to 192.
  • the oligomeric polyfunctional epoxy group containing materials include oligomeric forms of the monomeric materials, oligomers of diepoxides such as low molecular weight bis-phenol-A oligomers, prepolymers thereof, reaction products of amines with diepoxides, and the like.
  • the polymeric polyfunctional epoxy group containing materials include, for example, polymers of epoxy group containing unsaturated monomers and copolymers thereof with unsaturated comonomers which do not contain epoxy groups.
  • the epoxy group containing unsaturated monomers may be mentioned glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether.
  • the unsaturated comonomers which do not contain epoxy groups may be mentioned the alkyl esters of acrylic and methacrylic acid containing from 1 to 20 carbon atoms in the alkyl group, such as methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and ethylhexyl methacrylate; vinyl aromatic compounds such as styrene, methyl styrene and vinyl toluene; vinyl and vinylidene halides such as vinyl and vinylidene chlorides, vinyl esters such as vinyl acetate; allyl alcohol; and hydroxyalkyl acrylates and methacrylates containing from 1 to 20 carbon atoms in the hydroxyalkyl group, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate
  • copolymerization reaction may be carried out by known methods such as that described in various of the aforementioned incorporated reference as well as in US3787521 , US4181642, EP-A-0480120 and EP-A-0256369, which are also incorporated by reference herein as if fully set forth.
  • glycidyl methacrylate copolymer type polyfunctional epoxy group containing materials include Synthacryl ® VCS 1436 resin a product of Hoechst-Celanese Corporation, Charlotte, NC; Estron ® GMA-252 resin (Mw: 8300; EW: 250; Tg: 36), a product of Estron Chemicals, Calvert City, KY; Almatex ® PD 6100 (Mw: 12500; EW: 1030; Tg: 63), Almatex ® PD 6300 , Almatex ® PD 71 10, Almatex ® PD 7210, Almatex ® PD 7310, Almatex ® PD 7610 (Mw: 7000; EW: 510; Tg: 45) and Almatex ® PD 1700 resins, products of Mitsui Toatsu Company, Inc. of Japan, and available from Anderson Development Company, Adrian, Ml; and Blemmer ® CP-15 (Mw: 12300; EW:
  • the polyfunctional materials may additionally have thereon aqueous dispersion promoting groups such as carboxylic or sulfonic functionalities and higher molecular weights are generally usable, such as disclosed in previously incorporated W096/15185 and WO97/08235, as well as GB1530022, EP-A-0568134, EP- A-0663413, US5075370 and US5342878, all of which are further incorporated by reference herein as if fully set forth.
  • a liquid resin component is generally preferred, however, solid materials may also be used, particularly in cases when the solids are soluble in the particular formulation used.
  • the coating compositions prepared by the process of the present invention may optionally comprise a variety of additional ingredients.
  • they may comprise other well known auxiliaries and additives typically utilized in the coatings industry including, for example, foam inhibitors, levelling aids, pigments, pigment dispersing aids, dyes, UV absorbers and other stabilizing additives, and the like. These other additives are discussed in general above, are well known to those skilled in the relevant art and need not be discussed further.
  • the coatings of the present invention may be prepared by adding into a commonly used organic coatings solvent the components of the coating composition and the optional ingredients, if present, in any convenient order.
  • any conventional type of coating may be prepared by any conventional method of coating using the coating compositions described herein, including solvent based liquid coatings, waterborne coatings, high temperature coil coatings, and the like.
  • the present coating compositions may contain a solvent of the type typically found in coatings applications including alcohols, ketones, esters, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and the like.
  • the coating compositions are formulated to produce a solids content level suitable for convenient application with minimal material loss, preferably at a solids content level in the range of from about 20 weight percent to about 85 weight percent, and more preferably at a solids content level in the range of from about 45 weight percent to about 65 weight percent, depending on the method of application chosen.
  • the preferred method of application is by spraying, and one skilled in the art can, with the aid of the present description, formulate the coating compositions so as to be spray applicable.
  • the crosslinker composition and the active hydrogen containing material can be employed in varying amounts, when these components comprise the primary film- forming components of a subsequently formed coating, it is preferred that they be present in the coating compositions in amounts such that the molar ratio of the reactive functionality of the crosslinker component to the reactive functionality of the resin component is in the range of from about 0.5:1 to about 2:1 , and especially in the range of from about 0.8:1 to about 1.2:1.
  • the overall reactive functionality ratio be within the above indicated ranges.
  • coating compositions containing a liquid medium such as a solvent and a substrate are contacted. Contacting may be carried out by dipping, spraying, padding, brushing, flowcoating, electrocoating or electrostatic spraying. After contacting, the solvent is allowed to partially evaporate to produce a uniform coating on the substrate. Thereafter, the compositions may be cured by further application of heat at a temperature and length of time sufficient to produce substantially fully cured coatings.
  • cure temperatures are in the range of from about 25°C to about 450°C. In liquid coatings applications, the cure temperature is typically in the range of from about 80°C to about 160°C. In coil coatings applications, the cure temperature is typically in the range of from about 250°C to about 450°C.
  • Cure time preferably is in the in the range of from about 1 second to about 30 minutes but may vary depending on the temperature chosen for cure.
  • a fully cured coil coating may be obtained by either curing at 260°C for 1 minute or by curing at 417°C for 20 seconds.
  • Typical cure times for liquid coatings are in the in the range of from about 5 minutes to about 30 minutes.
  • Waterborne coatings can be prepared in a manner similar to that described in the previously incorporated W096/15185 and WO97/08235, using the high solids, homogeneous crosslinker compositions of the present invention as the crosslinker component.
  • the reactive resins suitable for use in waterborne coatings applications include those which possess sufficient anionic hydrophilizing functionality to render the curable coating composition water dispersible.
  • the preferred hydrophilizing groups for most applications are those which generate anions upon neutralization and, particularly, the carboxyl and sulfonic groups. Especially preferred are carboxyl groups.
  • the anion generating groups present on the resin must at least in part be neutralized.
  • Suitable neutralizing agents for accomplishing this include, for example, organic and inorganic bases such as sodium and potassium hydroxide, sodium and potassium carbonate, and amines such as ammonia, primary, secondary and tertiary amines. Tertiary amines are preferred.
  • waterborne coating compositions can be obtained by adding an aqueous dispersion-promoting material to the curable compositions of the present invention.
  • aqueous dispersion-promoting materials can be readily identified by those skilled in the art.
  • Preferred are an organic compound with such an alkyl chain or aromatic group substituted with the hydrophilic group. This includes, for example, long- chain aliphatic alcohols (e.g., ethylhexanol, octanol, dodecanol, and the like), benzyl alcohol and other aromatic alcohols, ester-alcohols (e.g., hydroxyalkyl esters of alkanoic acids), and the like.
  • long chain alkyl alcohols having at least 8 carbon atoms such as ethylhexanol
  • hydroxyalkyl esters of alkanoic acids containing a total of at least 8 carbon atoms such as a C 8 -hydroxyalkyl esters of methyipropionic acid commercially available from Eastman Chemical Company under the trade designation Texanol ® .
  • the present invention further includes a method of coating substrates.
  • the coating method comprises applying onto a substrate the coating compositions described above, and thereafter curing the so applied coating compositions to produce cured coatings and coated articles.
  • any conventional coating method may be employed to prepare coatings, including methods such as roller-coating, dipping, and spraying.
  • the especially preferred systems in accordance with the present invention are formulated for spray application.
  • the coating compositions of the present invention may be utilized in a wide variety of fields.
  • a particularly preferred end use is as a one- or two-component coatings for elevated temperature cure applications such as, for example, automotive OEM clearcoats or pigmented basecoats.
  • Other potential applications include, for example, coatings for wire, appliances, furniture, pipes, machinery and the like.
  • Suitable substrates include glass, temperature resistant plastics, and metals such as steel and aluminum.
  • the methyl and butyl carbamate contents (%) of the 1 ,3,5-triazine carbamate were calculated from HPLC/MS analysis as follows.
  • HPLC High pressure liquid chromatographic analysis
  • MS Mass spectroscopic analysis identified the various components, and hence, the number of methyl and/or butyl groups in each tris- or bis- derivative.
  • Part A The solution of Part A was diluted to 50 wt% in n-butanol, and 2150 g was placed in a round bottom flask attached to a rotary evaporator. Volatiles were removed under reduced pressure at 60-70°C until about an 80 wt% solids residue was obtained (approximately 900 ml distillate was collected).
  • the clear liquid was transferred to a mixing tank containing deaerated melamine powder (260 lbs) to form a uniform slurry and then the slurry was returned to the 1000 gallon reactor and heated at about 90°C for one hour.
  • the reaction mixture was then cooled to 28°C, the pH adjusted to 5, and allowed to phase separate.
  • the organic layer was filtered through a 0.5 micron filter to remove insolubles and washed with water (2 x 250 gallons). Sufficient volatiles were then removed to produce the following product: Solids (Pan Solids Method, weight %) 50.6
  • Homogeneous liquid crosslinker compositions were prepared by combining a 50 wt% solution of the solid 1 ,3,5-triazine carbamate (from Example 1 , Part B) in n-butanol, a commercially available aminoplast resin crosslinker and an additional amount of solid 1 ,3,5-triazine carbamate (from Example 1 , Part B) in the amounts shown in TABLE I.
  • the appearance, viscosity and the final composition of the crosslinker compositions prepared in accordance with the present invention are also shown in TABLE I.
  • CYMEL ® 303 Resin is a product of Cytec Industries, West Paterson, N.J.
  • CYMEL ® 1135 Resin is a product of Cytec Industries, West Paterson, N.J.
  • Formula F contains a 50 wt % solution of the solid 1 ,3,5-triazine carbamate in n- butanol (from Example 1 , Part B) as the sole crosslinker, and formulation G contains Crosslinker Composition A of EXAMPLE 2 in accordance with the present invention.
  • FORMULATION F G contains Crosslinker Composition A of EXAMPLE 2 in accordance with the present invention.
  • DORESCO ® TA 39-21 acrylic resin is a product of Dock Resins, Linden, N.J.
  • CYCAT ® 600 Cure Catalyst is a product of Cytec Industries, West Paterson, N.J.
  • Arcosolv ® PM Acetate is a product of Arco Chemical Company.
  • the coating formulations were coated by wire cater applicator onto two Bondrite ® 1000 treated cold rolled steel panels (Advanced Coating Technologies, Inc., Hillsdale, Ml), and cured for 30 minutes at 140°C. The resulting cured films were tested for performance. Solvent resistance was measured by methyl ethyl ketone (MEK) double rubs "to mar” and "to remove” the coating. Highly crosslinked coatings require 200+ (i.e., more than 200) MEK rubs to mar. When two solvent resistance values are shown, the first is the number of rubs to mar the coating, and the second is the number of rubs to remove the coating. When only one value is shown, the coating did not mar and the number shown is the number of rubs to remove it. The results are shown in the TABLE 2.
  • MEK methyl ethyl ketone
  • Homogeneous liquid crosslinker compositions H, I, J and K were prepared by combining solid 1 ,3,5-triazine carbamate (Example 1 , Part B) and CYMEL ® 301 aminoplast resin (100 % solids) or CYMEL ® 303 aminoplast resin (100 % solids) or CYMEL ® 1131 aminoplast resin (100 % solids) without solvent, in the amounts shown in TABLE 3, along with the appearance and the wt% of the 1 ,3,5-triazine carbamate in the final composition.
  • CYMEL ® 303 Resin 0 9.0 0 0
  • CYMEL ® 1131 Resin is a product of Cytec Industries, West Paterson, N.J.
  • Homogeneous liquid crosslinker compositions L, M and N were prepared by combining a 50.6 weight % solution of a 1 ,3,5-triazine carbamate in n-butanol (from Example 1 , Part C), CYMEL ® 303 aminoplast resin (100 % solids) or CYMEL ® 1131 aminoplast resin (100 % solids), and an organic solvent.
  • the amounts used, the wt % of 1 ,3,5-triazine carbamate in the final composition, and the appearance of the final crosslinker composition are shown in TABLE 4.
  • the initially prepared clear solutions remained clear for at least a month. TABLE 4
  • a high solids, pourable, homogeneous liquid crosslinker composition O was prepared by combining a 50 wt % solution of a 1 ,3,5-triazine carbamate (prepared from the solid 1 ,3,5-triazine carbamate of Example 1 , Part B and n-butanol), CYMEL ® 303 aminoplast resin (100 % solids) and an additional amount of the solid 1 ,3,5-triazine carbamate (from Example 1 , Part B) in the amounts shown in TABLE 5. The appearance, viscosity and the final composition of the high solids homogeneous liquid crosslinker composition is also shown in TABLE 5.

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Abstract

Cette invention se rapporte à des compositions de réticulation liquides à haute teneur en solides, contenant des mélanges de résines aminoplastes/et de carbamates de 1,3,5-triazine, ainsi qu'à des procédés de préparation de telles compositions. Lesdites compositions de réticulation liquides conviennent particulièrement à la préparation de compositions polymérisables telles que des compositions de revêtement à haute teneur en solides qui doivent être appliquées par pulvérisation dans la fabrication de matériel automobile (OEM) et dans d'autres applications associées.
PCT/US1997/016121 1996-10-30 1997-09-18 Compositions de reticulation liquides contenant des melanges de resines aminoplastes/et de carbamates de 1,3,5-triazine WO1998018856A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP97942434A EP0935635A1 (fr) 1996-10-30 1997-09-18 Compositions de reticulation liquides contenant des melanges de resines aminoplastes/et de carbamates de 1,3,5-triazine
AU44133/97A AU4413397A (en) 1996-10-30 1997-09-18 Liquid cross-linker compositions containing 1,3,5-triazine carbamate/aminoplas t resin mixtures
BR9712600-4A BR9712600A (pt) 1996-10-30 1997-09-18 Composições reticuladora, lìquida curável, e, de revestimento lìquida pulverizável
CA002270384A CA2270384A1 (fr) 1996-10-30 1997-09-18 Compositions de reticulation liquides contenant des melanges de resines aminoplastes/et de carbamates de 1,3,5-triazine
JP52045798A JP2001506675A (ja) 1996-10-30 1997-09-18 １，３，５―トリアジンカーバメート／アミノプラスト樹脂混合物を含有する液状架橋剤組成物
NO992089A NO992089L (no) 1996-10-30 1999-04-29 Vµskeholdige tverrbindingsblandinger inneholdende blandinger av 1,3,5-triazinkarbamat og aminoplastharpiks

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US5965670A (en) * 1997-12-24 1999-10-12 Ppg Industries Ohio, Inc. Curable-film forming compositions having improved mar and acid etch resistance
EP0990685A1 (fr) * 1998-10-01 2000-04-05 Basf Corporation Compositions sous forme de pâtes à base de résine à fonction carbamate solide particulaire dispersée dans une résine aminoplaste liquide
WO2001040368A1 (fr) * 1999-12-03 2001-06-07 Cytec Technology Corp. Agents reticulants, depourvus de formaldehyde, a base de 1,3,5-triazine carbamates, et compositions durcissantes les contenant
US8471007B2 (en) * 2004-04-14 2013-06-25 Basf Se Method for producing 1,3,5-triazine carbamates and ureas
EP2774987A1 (fr) * 2006-08-17 2014-09-10 Affymetrix, Inc. Quantification des acides nucléiques à partir des échantillons des tissus

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DE102004018546A1 (de) * 2004-04-14 2005-11-03 Basf Ag Strahlungshärtbare 1,3,5-Triazincarbamate und -harnstoffe
DE102008061139A1 (de) * 2008-12-09 2010-06-10 Borealis Agrolinz Melamine Gmbh Verfahren zur Herstellung von Triazincarbamaten unter Verwendung von Chlorformiaten
WO2011014011A2 (fr) * 2009-07-28 2011-02-03 주식회사 동진쎄미켐 Composition de photorésine comprenant une substance du durcissement réticulable
US11692105B2 (en) * 2017-10-09 2023-07-04 Basf Coatings Gmbh Electrocoats containing at least one triazine compound
CN115109454A (zh) * 2022-06-23 2022-09-27 长春人造树脂厂股份有限公司 三(烷氧基羰基氨基)三嗪组合物、包含其的涂料组合物及其制备方法

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Publication number Priority date Publication date Assignee Title
US5965670A (en) * 1997-12-24 1999-10-12 Ppg Industries Ohio, Inc. Curable-film forming compositions having improved mar and acid etch resistance
EP0990685A1 (fr) * 1998-10-01 2000-04-05 Basf Corporation Compositions sous forme de pâtes à base de résine à fonction carbamate solide particulaire dispersée dans une résine aminoplaste liquide
WO2001040368A1 (fr) * 1999-12-03 2001-06-07 Cytec Technology Corp. Agents reticulants, depourvus de formaldehyde, a base de 1,3,5-triazine carbamates, et compositions durcissantes les contenant
US8471007B2 (en) * 2004-04-14 2013-06-25 Basf Se Method for producing 1,3,5-triazine carbamates and ureas
EP2774987A1 (fr) * 2006-08-17 2014-09-10 Affymetrix, Inc. Quantification des acides nucléiques à partir des échantillons des tissus

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AU4413397A (en) 1998-05-22
CA2270384A1 (fr) 1998-05-07
NO992089D0 (no) 1999-04-29
BR9712600A (pt) 1999-10-26
MX9903123A (en) 1999-10-01
EP0935635A1 (fr) 1999-08-18

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