WO1996033229A1 - Compositions contenant des polyols, des esters phenoliques et des isocyanates - Google Patents

Compositions contenant des polyols, des esters phenoliques et des isocyanates Download PDF

Info

Publication number
WO1996033229A1
WO1996033229A1 PCT/US1996/005178 US9605178W WO9633229A1 WO 1996033229 A1 WO1996033229 A1 WO 1996033229A1 US 9605178 W US9605178 W US 9605178W WO 9633229 A1 WO9633229 A1 WO 9633229A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
polymeric vehicle
recited
aliphatic
ester
Prior art date
Application number
PCT/US1996/005178
Other languages
English (en)
Inventor
Vijay Swarup
Frank N. Jones
Albert I. Yezrielev
Ramachandran P. Subrayan
Original Assignee
Exxon Chemical Company
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 US08/621,171 external-priority patent/US6087464A/en
Application filed by Exxon Chemical Company filed Critical Exxon Chemical Company
Priority to JP53182896A priority Critical patent/JP2001527586A/ja
Priority to EP96913793A priority patent/EP0769030A4/fr
Priority to AU56640/96A priority patent/AU5664096A/en
Publication of WO1996033229A1 publication Critical patent/WO1996033229A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3221—Polyhydroxy compounds hydroxylated esters of carboxylic acids other than higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/728—Polymerisation products of compounds having carbon-to-carbon unsaturated bonds and having isocyanate or isothiocyanate groups or groups forming isocyanate or isothiocyanate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • C08G18/8067—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds phenolic compounds
    • 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
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms

Definitions

  • the present invention relates to polymeric vehicles for coating films or binders where the polymeric
  • thermosetting vehicles include at least one phenolic ester alcohol, at least one polyol and at least one isocyanate compound with multi-isocyanate
  • the invention is directed to polymeric vehicles which include at least one phenolic ester alcohol, at least one isocyanate compound with multi-isocyanate functionality, at least one polyol and at least one amino resin.
  • film former that provides a film for the protective function of a substrate coated with paint.
  • 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 solvents raises at least two problems. First, 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.
  • Thermosetting coating compositions particularly coating compositions which include polyester, alkyd, acrylic and epoxy polymers are often materials of choice for making film formers for various substrates to which the coating composition is applied.
  • compositions provide a protective function for the substrate.
  • coating compositions are generally formulated to provide a balance of properties which will maximize hardness, flexibility, hydrolytic stability, solvent resistance, corrosion resistance,
  • thermosetting provide films with desired film properties such as hardness, flexibility, solvent resistance, acid resistance, corrosion resistance, hydrolytic stability,
  • compositions which are solventless or which are thinned by organic solvents and/or water.
  • the present invention is directed to a polymeric vehicle, a formulated coating composition and a coating binder made from the polymeric vehicle and a method for making the polymeric vehicle
  • the polymeric vehicle includes at least one phenolic ester alcohol having at least one phenolic hydroxyl group and at least one aliphatic hydroxyl group; at least one polyol having a polydispersity index (PDI) of greater than one; and at least one isocyanate compound having an average of more than one reactive isocyanate per molecule.
  • PDI polydispersity index
  • the latter combination enhances film properties such as hardness, hydrolytic stability, corrosion resistance and
  • the polyol has an average hydroxyl functionality of from about 2 to about 100 hydroxyls per molecule, a PDI of greater than 1 and a molecular weight of at least 200.
  • polyol is a polyester, alkyd or acrylic polymer.
  • the isocyanate compound has an
  • isocyanate functionality of from about 1.9 to about 20 isocyanate groups per molecule.
  • the isocyanate serves to crosslink and interconnect the polyol and the
  • phenolic ester alcohol as follows: PHEA-isocyanate- polyol.
  • the isocyanate functionality is reactive with the hydroxyls of the phenolic ester alcohol and polyols.
  • the phenolic ester alcohol, polyol and isocyanate compound may be blended in amounts effective for the blend providing a polymeric vehicle and/or formulated coating composition having less than about 3.5 pounds per gallons of composition.
  • the polymeric vehicle includes an amino resin having a crosslinking
  • the isocyanate compound has an average isocyanate functionality of about 2 or 3.
  • the isocyanate group generally reacts with the aliphatic hydroxyl group of the PHEA and polyol and the phenolic hydroxyl group reacts with the amino resin to provide a crosslinked structure with the following components which are connected to provide predominantly the
  • the phenolic ester alcohol has the general formula which includes at least two ester linkages and at least one aliphatic hydroxyl group which is a secondary or primary hydroxyl group and which is described in the following general formula
  • R 4 is selected from the group consisting of hydrogen, halogen, hydroxyl, C 1 to C 8 alkyl and C 1 to C 8 alkoxy
  • R 5 is a direct bond or a C 1 to C 20 organic radical which may incorporate another phenol, aliphatic
  • R 6 is hydrogen or a C 1 to C 20 organic radical which may include an ester group, or a direct bond which may form with R 7 part of a 5 or 6 carbon atom cyclic ring structure
  • R 7 is CH 2 R 8 wherein R 8 is selected from the group consisting of hydroxy, OR 9 , OOCR 10 and R 11 wherein R 9 is a primary or secondary aliphatic group containing 3 to 20 carbon atoms which may include one or more ester linkages or an aromatic group containing 6 to 20 carbon atoms
  • R 10 is a primary, secondary or tertiary aliphatic group containing 4 to 20 carbon atoms which may include one or more ester linkages or an aromatic group
  • R n is a C 2 to C 20 organic radical which may include one or more ester linkages and where the organic radical may form with R 6 part of a 5 or 6 carbon atom cyclic ring structure.
  • R 5 or R 8 has the ester groups.
  • the phenolic ester alcohol is the reaction product of
  • hydroxybenzoic acid such as para hydroxybenzoic acid
  • a monoglycidyl compound having a molecular weight in the range of from about 110 to 1000 such as the
  • R represents a mixture of aliphatic groups, most preferably the three R groups in the glycidyl compound having a total of 8 carbon atoms.
  • a glycidyl compound is commercially available from Exxon Chemical Company under the trademark Glydexx ® .
  • An important phenolic ester alcohol for use in the invention has the general formula "C" .
  • each component is in relative amounts effective for providing an acceptable coating binder which generally will have a pencil hardness of at least about HB and preferably F, an impact resistance of at least about 20-inch pounds direct, preferably 30, and at least about 20-inch pounds reverse, preferably 30, at a film thickness of about 0.5 mil dry.
  • the crosslinker may be a solid, but generally is a liquid.
  • the viscosity of the blend which forms the polymeric vehicle, such as the phenolic ester alcohol, isocyanate and polyol, is in the range of from about 0.1 to about 20 Pa.s at about 20 to about 60oC at a shear rate of at least 1000 sec. -1 without organic solvent and/or water.
  • the polymeric vehicle may have from about 5 to about 70 weight percent, based upon the weight of the polymeric vehicle, phenolic ester alcohol, from about 5 to about 40 weight percent, based upon the weight of the polymeric vehicle, isocyanate compound and at least about 15 weight percent and preferably from about 15 to about 75 weight percent, based upon the weight of the polymeric vehicle, polyol.
  • the polymeric vehicle includes from about 5 to about 55 weight percent of an amino resin.
  • the polymeric vehicle will generally comprise from about 3 to about 45 weight percent amino resin.
  • Polymers means a polymer which has
  • Acrylic polymer means a homo or copolymer of hydroxy substituted acrylic acid or acrylate, and/or hydroxy and alkyl substituted acrylic acid or acrylate as further described below.
  • the isocyanate compound has an average isocyanate functionality of from about 1.9 to about 20 isocyanate groups per molecule which isocyanate functionality is reactive with the hydroxyls of the phenolic ester alcohol.
  • the isocyanate compound may be a biuret, an isocyanurate and/or a blocked or unblocked isocyanate.
  • Bouret means an isocyanate reacted with water in a ratio of three equivalents of isocyanate to one
  • An “isocyanurate” is a six-membered ring having nitrogens at the 1, 3 and 5 positions and keto groups at the 2, 4 and 6 positions, the nitrogens being
  • Amino resin means amino resins usually made from amidines, ureas or amides by reaction with formaldehyde and subsequently usually with an alcohol. Melamine resins are a subclass of amino resins and may also be referred to as “melamine-formaldehyde resin” or “alcoholated melamine-formaldehyde resin.” Amino resin amounts may be adjusted in amounts effective to obtain the properties desired and to control the viscosity of the polymeric vehicle which viscosity will also be a function of the molecular weights of the phenolic ester alcohol, isocyanate and polyol in the blend which form the polymeric vehicle.
  • Crosslinking agent means a compound having di- or polyfunctional isocyanate groups or a polyfunctional amino resin.
  • the isocyanate compound or amino resin contains isocyanate or crosslinking functional groups that are capable of forming covalent bonds with hydroxyl groups that are present on the phenolic ester alcohol and/or polyol in the polymeric vehicle.
  • crosslinking agent may be a blend; hence, there may be more than one substance which forms a blend of
  • Amino reins and polyisocyanates are such crosslinking agents.
  • Polymeric vehicle means polymeric and resinous components in the formulated coating, i.e., before film formation, including but not limited to the phenolic ester alcohol, the polyol and additional hardeners which may be added.
  • Coating binder means the polymeric part of the film of the coating after solvent has evaporated and after crosslinking.
  • 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.
  • Residue means that portion of a molecule that is left after a reaction which in general eliminates some atoms from the reactant or moves the atom to different positions among the reactants.
  • a urethane linkage forms by way of reaction of an alcohol and isocyanate. The residue of the alcohol and isocyanate forming the urethane linkage.
  • An amine may react with an alcohol with the loss of water. The new molecule is a residue of the alcohol and amine.
  • VOC volatile organic compounds
  • Dial is a compound, oligomer or polymer with two hydroxyl groups.
  • Polyol is a compound, oligomer or polymer with two or more hydroxyl groups.
  • solvent means an organic solvent
  • Organic solvent means a liquid which includes but is not limited to carbon and hydrogen and has a boiling point in the range of from about 30oC to about 300oC at about one atmosphere pressure.
  • Volatile organic compounds are defined by the U.S. Environmental Protection Agency at 40 C.F.R. 51.000 of the Federal Regulations of the United States of America as any compound of carbon, excluding carbon monoxide, carbon dioxide, carbonic acid, metallic carbides or carbonates, and ammonium carbonate, which participates in atmospheric photochemical reactions.
  • 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
  • a "film” is formed by application of the formulated coating composition to a base or substrate, evaporation of solvent, if present, and crosslinking.
  • the invention includes a polymeric vehicle
  • isocyanate functionality of from about 1.9 to about 20 isocyanate groups per molecule which isocyanate
  • the phenolic ester alcohol has about one
  • each of these components in the polymeric vehicle are present in an amount effective to provide a coating binder with a hardness of at least about HB at a thickness of about 0.5 mil dry.
  • the viscosity of the blend which constitutes the polymeric vehicle which includes the phenolic ester alcohol, polyol and
  • isocyanate compound will be in the range of from about 0.1 to about 20 Pa.s at about 20 to about 60oC at 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 and/or water.
  • the blend of the phenolic ester alcohol, polyol and isocyanate compound provides the polymeric vehicle with improved coating properties such as hardness,
  • the polymeric vehicle and formulated coating compositions which include the polymeric vehicle of the invention may include organic solvents, water, or may not require water or organic solvents to provide a formulated coating composition with a viscosity such that the formulated coating composition may be applied by existing application equipment.
  • the phenolic ester alcohol, polyol and isocyanate compound are at low molecular weights, such as when the phenolic ester alcohol has a number average molecular weight in the range of from about 110 to about 1,000, the blend of the phenolic ester alcohol and isocyanate not only improves film properties, it does so while maintaining or
  • the need is reduced for organic solvents and/or water to lower the viscosity of the polymeric vehicle or formulated coating composition to permit the application of the formulated coating composition to a substrate.
  • the phenolic ester alcohol and isocyanate compound may be used as a reactive diluent in
  • the phenolic ester alcohol and isocyanate compound may be used as a blend which is a reactive diluent in the polymeric vehicle which includes the polyol. Moreover, by controlling the molecular weights of the phenolic ester alcohol,
  • the blend may be used as a reactive diluent which controls VOC and may be added to a polymeric vehicle to lower VOCs to levels of at least about 5 weight percent.
  • phenolic ester alcohol, isocyanate compound, amino resin, if any, and polyol being in amounts effective for maintaining VOCs in the formulated coating composition (which includes the polymeric vehicle) to less than about 3.5 pounds of VOC per gallon of formulated coating composition while at least
  • resistance of the coating binder to at least about 20- inch pounds direct and at least about 20-inch pounds indirect at a film thickness of about 0.5 mil dry.
  • the invention is effective for providing formulated coating compositions having less than 2.5 pounds of VOC per gallon of formulated coating composition and in some cases less than 2.0 pounds of VOC per gallon of
  • the invention is effective for providing solventless liquid formulated coating compositions (not more than about 3 weight percent organic solvent) where the polymeric vehicle in the formulated coating composition comprises the
  • phenolic ester alcohol and isocyanate compound each at low molecular weight, a polyol having a molecular weight of at least 200, an average hydroxyl functionality of from about 2 to about 100 hydroxyls per molecule and an amino resin.
  • the blend of the phenolic ester alcohol, polyol and isocyanate compound is compatible with and permits the use of other diphenolic hardeners to improve coating properties, but yet also permits the use of the additional hardeners in a formulated coating composition which may include solvents.
  • a diphenolic polyol ester reaction product of hydroquinone and parahydroxy benzoic acid known as SK101
  • SK101 has low solvent dispersibility or solubility, requires high-cure temperatures and often makes coatings intractable.
  • the use of the blend of the invention permits the use of other diphenolic hardeners such as SK101 which has the structure to improve hardness yet reduces the other problems attendant with the use of such hardeners.
  • the phenolic ester alcohol has at least one phenolic hydroxyl group, and at least one aliphatic hydroxyl group. In an important aspect, it has two ester groups and about one aliphatic hydroxyl group.
  • the phenolic ester alcohol is represented by the general formula "A"
  • R 4 is selected from the group consisting of hydrogen, halogen, hydroxyl, C 1 to C 8 alkyl and C 1 to C 8 alkoxy
  • R 5 is a direct bond or a C 1 to C 20 organic radical which may incorporate another phenol, aliphatic
  • R 6 is hydrogen or a C 1 to C 20 organic radical which may include an ester group, or a direct bond which may form with R 7 part of a 5 or 6 carbon atom cyclic ring structure
  • R 7 is CH 2 R 8 wherein R 8 is selected from the group consisting of hydroxy, OR 9 , OOCR 10 and R 11 wherein R 9 is a primary or secondary aliphatic group containing 3 to 20 carbon atoms which may include one or more ester linkages or an aromatic group containing 6 to 20 carbon atoms
  • R 10 is a primary, secondary or tertiary aliphatic group containing 4 to 20 carbon atoms which may include one or more ester linkages or an aromatic group
  • R 11 is a C 2 to C 20 organic radical which may include one or more ester linkages and where the organic radical may form with R 6 part of a 5 or 6 carbon atom cyclic ring structure.
  • R 5 or R 8 has the ester groups.
  • a phenolic ester alcohol which is particularly important to the invention is represented by general formula C above.
  • an ester group means
  • a phenol carboxylic acid reactant which may be reacted with the epoxy compound has the general formula:
  • R 4 and R 5 are as described above.
  • suitable phenol carboxylic acids include hydroxybenzoic acids, acids where R 5 is alkylene such as phenyl acetic acid, hydroxy phenyl propionic acid, hydroxyphenyl stearic acid, and acids where in R 5 encompasses
  • R 4 in formula A is hydrogen, R 5 is a direct bond.
  • R 6 is hydrogen and R 7 is CH 2 OH, a hydrocarbon moiety or an organic moiety
  • the phenolic ester alcohol is the ester reaction product of a hydroxybenzoic acid and an epoxy compound.
  • Suitable hydroxybenzoic acids include ortho-hydroxybenzoic acid (salicylic acid), meta-hydroxybenzoic acid and para- hydroxybenzoic acid (PHBA), with para-hydroxybenzoic acid being most preferred.
  • the epoxy compound may be selected from the group consisting of glycidyl esters, glycidyl alcohols, glycidyl ethers, linear epoxies and aromatic epoxies. These include glycidol, glycidyl ethers of the
  • glycidyl or oxirane compounds having the structure: ,
  • R 12 is an organic radical having 1-12 carbon atoms which can include ether, ester, hydroxyl or epoxy groups.
  • epoxy materials include epoxidized alpha- olefins and bis aromatic epoxies such as the reaction product of bisphenol A or F with epichlorohydrin.
  • Suitable epoxy compounds particularly include monoepoxides containing a terminal glycidyl group or polyepoxides containing internal oxirane or glycidyl groups or terminal glycidyl groups.
  • Suitable epoxy compounds include glycidyl acrylate or methacrylate monomers, alkyl glycidyl ether monomers, and low
  • molecular weight copolymers of one or more of these monomers with one or more ethylenically unsaturated monomers such as acrylates, methacrylates, vinyl
  • Suitable epoxy compounds include the ester reaction products of epichlorohydrin with mono- or dibasic aliphatic or aromatic carboxylic acids or anhydrides containing from about 1 to 20 carbon atoms.
  • Inclusive of such acids are aliphatic acids such as acetic, butyric, isobutyric, lauric, stearic, maleic and myristic acids and aromatic acids such as benzoic, phthalic, isophthalic and terephthalic acids as well as the corresponding anhydrides of such acids.
  • Preferred such acids are primary, secondary or tertiary aliphatic carboxylic acids containing from 5 to 13 carbon atoms.
  • the epoxy compound is the glycidyl ester of a mixed aliphatic, mostly tertiary, mono carboxylic acid with an average of 9 to 11 carbon atoms such glycidyl ester being available from Exxon Chemical Co., under the trade name GLYDEXX ® or from Shell
  • Still other epoxy compounds include glycidyl ether reaction products of epichlorohydrin with aliphatic or aromatic alcohols or polyols containing from about 1 to 20 carbon atoms.
  • Suitable alcohols include aromatic alcohols such as bisphenol, bisphenol A, bisphenol F, phenolphthalein and novolac resins; aliphatic alcohols such as ethanol, isopropanol, isobutyl alcohol, hexanol, stearyl alcohol and the like; and aliphatic polyols such as ethylene glycol, propylene glycol and butylene glycol.
  • epoxy compounds which may be used include the mono-epoxides of C 8 to C 20 alpha mono-olefins.
  • the epoxy compound may also comprise epoxidized fatty compounds.
  • epoxidized fatty compounds include epoxidized fatty oils, epoxidized fatty acid esters of monohydric alcohols, epoxidized fatty acid esters of polyhydric alcohols, epoxidized fatty
  • alicyclic epoxide and polyepoxide materials include dicyclopentadiene diepoxide, limonene diepoxide, and the like. Additional useful epoxides include for example, vinyl cyclohexane dioxide, bis (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane carboxylate and 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4- epoxy) cyclohexane-metadioxane.
  • the hydroxybenzoic acid/epoxy reaction product may be formed by reacting the hydroxybenzoic acid and the epoxy compound to provide a phenolic ester alcohol with one aliphatic hydroxyl group, optionally in a solvent therefor, at a temperature ranging from about 90' to about 120oC to initiate such reaction.
  • a temperature ranging from about 90' to about 120oC to initiate such reaction.
  • the reaction temperature can rise to a temperature of about 150* to 175oC usually without application of external heat.
  • the reaction temperature then is maintained at about 150oC to 170oC (and preferably less than about 200oC) until the reaction has been determined to be substantially complete.
  • Reaction products of reduced discoloration can be produced by control of the maximum temperature of the exothermic reaction. This can be achieved by a staged and/or incremental addition of one of the reactants, e.g. the epoxy reactant, so that the reaction
  • reaction temperature is maintained at a temperature of about 150oC or below.
  • the remainder of that reactant may then be added in stages or continuously while maintaining the reaction temperature below about 150oC. This process modification gives rise to reaction products having lower Color Index values.
  • Diisocyanates which may be used as isocyanate compounds in the invention additional to HDI include isophorone diisocyanate (IPDI), tetramethylxylene diisocyanate (TMXDI), and other aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate; cycloalkylene diisocyanates such as 1,3- cyclopentane-diisocyanate, 1,4-cyclohexane-diisocyanate and 1,3-cyclohexane-diisocyanate; and aromatic
  • diisocyanates such as m-phenylene diisocyanate, p- phenylene diisocyanate, 4,4'-diphenyldiisocyanate, 1,5- naphthalene diisocyanate, 4,4'-diphenylmethane
  • the isocyanate compound may have blocked isocyanate groups.
  • Agents which block the isocyanate groups and "deblock" at elevated temperature are known and are used in the invention. These include oxines, lactams, imines, carbamates such as acetone oxime, methyl ethyl ketoxime, and ⁇ -caprolactam.
  • the polyisocyanates may be dimerized or trimerized diisocyanates such as trimerized HDI or IPDI and
  • triisocyanates such as triphenylmethane-4,4',4"- triisocyanate, 1,3,5-triisocyanatobenzene, 1,3,5- triisocyanatocyclohexane, 2,4,6-triisocyanatotoluene and ⁇ -isocyanatoethyl-2,6-diisocyanatocaproate; and
  • tetraisocyanates such as 4,4'-diphenyldimethylmethane- 2,2',5,5'-tetraisocyanate.
  • They also may be polymers or copolymers with vinyl monomers of isocyanate functional monomers such as O and
  • unblocked or blocked biurets such as the biuret of hexamethylene diisocyanate (HDI) which biuret has the structure
  • diisocyanate and water may be used as polyisocyanates.
  • the polyols which are used in the invention are selected from the group consisting of polyesters, alkyd polymers, acrylic polymers and epoxy polymers.
  • the polyols have a PDI of greater than one and an number average molecular weight (M n ) of at least about 200, and may generally range from about 200 up to about 30,000, more preferably from about 280 up to about 15,000, and most preferably from about 300 up to about 3,000 to 6,000.
  • Glass transition temperatures (Tg) of these materials may generally range from as low as -90oC up to +100oC or higher.
  • the diester and polyester polyols may be prepared by well known condensation processes using a molar excess of diol. Preferably the molar ratio of diol to
  • dicarboxylic acid is p + 1:p wherein p represents the number of moles of dicarboxylic acid.
  • the reaction may be conducted in the absence of or presence of a suitable polycondensation catalyst as is known in the art.
  • Polyesters also can be made from carboxylic acids and oxiranes, such as n
  • R H, alkyl, aryl
  • diols used to make the polyester polyols are one or more of the following: neopentyl glycol; ethylene glycol; hexamethylenediol; 1,2-cyclohexanedimethanol; 1,3-cyclohexanedimethanol; 1,4-cyclohexanedimethanol;
  • diethylene glycol triethylene glycol; tetraethylene glycol; dipropylene glycol; polypropylene glycol;
  • polyols examples include triols such as glycerine, timethylol ethane, trimethylol propane, pentaerythritol and the like.
  • the diols are reacted with carboxyl groups to make the polyesters.
  • the carboxyl groups may be present in the form of anhydride groups, lactone groups, or equivalent ester forming derivatives such as the acid halide or methyl ester.
  • the dicarboxylic acids or derivatives are preferably one or more of the following: phthalic anhydride, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, adipic acid, succinic acid, glutaric acid, fumaric acid, maleic acid,
  • cyclohexane dicarboxylic acid azelaic acid, sebasic acid, dimer acid, caprolactone, propiolactone
  • pyromellitic dianhydride substituted maleic and fumaric acids such as citraconic, chloromaleic, mesaconic, and substituted succinic acids such as aconitic and
  • polyesters are produced using a combination of aromatic and aliphatic dicarboxylic acids or a
  • the most preferred acids used for the purposes of this invention are linear saturated or unsaturated aliphatic dicarboxylic acids having from 2 to 10 carbon atoms such as succinic, glutaric, adipic, and similar materials.
  • the acrylic polymers which may be used as the polyol component in the present invention are acrylic copolymer resins.
  • the acrylic copolymer resin is prepared from at least one hydroxy-substituted alkyl (meth) acrylate and at least one non-hydroxy-substituted alkyl (meth) acrylate.
  • the hydroxy-substituted alkyl (meth) acrylates which can be employed as monomers comprise members selected from the group consisting of the following esters of acrylic or methacrylic acid and aliphatic glycols: 2-hydroxyethyl acrylate, 3-chloro-2- hydroxypropyl acrylate; 1-hydroxy-2-acryloxy propane; 2- hydroxypropyl acrylate; 3-hydroxy- propylacrylate; 2,3- dihydroxypropylacrylate; 3-hydroxybutyl acrylate; 2- hydroxybutyl acrylate; 4-hydroxybutyl acrylate;
  • diethyleneglycol acrylate diethyleneglycol acrylate; 5-hydroxypentyl acrylate; 6- hydroxyhexyl acrylate; triethyleneglycol acrylate; 7- hydroxyheptyl acrylate; 1-hydroxy-2-methacryloxy
  • acrylic resins are hydroxy-substituted alkyl (meth) acrylates having a total of 5 to 7 carbon atoms, i.e., esters of C 2 to C 3 dihydric alcohols and acrylic or methacrylic acids.
  • esters of C 2 to C 3 dihydric alcohols i.e., esters of C 2 to C 3 dihydric alcohols and acrylic or methacrylic acids.
  • hydroxy-substituted alkyl (meth) acrylate monomers are 2-hydroxyethyl methacrylate, 2- hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 2- hydroxypropyl methacrylate, and 2-hydroxypropyl
  • non-hydroxy-substituted alkyl (meth) acrylate monomers which may be employed are alkyl (meth) acrylates.
  • Preferred nonhydroxy unsaturated monomers are esters of C 1 to C 12 monohydric alcohols and acrylic or methacrylic acids, e.g., methyl methacrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, glycidyl methacrylate, etc.
  • particularly suitable monomers are butyl acrylate, butyl methacrylate and methyl methacrylate.
  • the acrylic copolymer polyol resins used in the present invention may include in their composition other monomers such as acrylic acid and methacrylic acid, monovinyl aromatic hydrocarbons containing from 8 to 12 carbon atoms (including styrene, alpha-methyl styrene, vinyl toluene, t-butyl styrene, chlorostyrene and the like), vinyl chloride, vinylidene chloride, acrylonitrile, epoxy-modified acrylics and methacrylonitrile.
  • monomers such as acrylic acid and methacrylic acid, monovinyl aromatic hydrocarbons containing from 8 to 12 carbon atoms (including styrene, alpha-methyl styrene, vinyl toluene, t-butyl styrene, chlorostyrene and the like), vinyl chloride, vinylidene chloride, acrylonitrile, epoxy-modified acrylics and methacrylonitrile.
  • the acrylic copolymer polyol preferably has a number average molecular weight not greater than 30,000, more preferably between about 280 and 15,000, and most preferably between about 300 and 5000.
  • Alkyd polymers may be used as the polyol component of this invention. These alkyd resins usually have a number average molecular weight in the range of from about 500 to about 20,000, are oil
  • modified polyester resins are broadly the product of the reaction of a dihydric alcohol and a dicarboxylic acid or acid derivative and an oil, fat or carboxylic acid derived from such oil or fat which acts as a modifier.
  • Such modifiers are drying oils, semi-drying oils or non-drying oils.
  • the dicarboxylic acid, or corresponding anhydrides may be selected from a variety of aliphatic carboxylic acids or mixtures of aliphatic and aromatic dicarboxylic acids. Suitable acids and acid anhydrides include, by way of example, succinic acid, adipic acid, phthalic anhydride,
  • isophthalic acid trimellitic acid (anhydride) and bis 3,3', 4,4'-benzophenone tetracarboxylic anhydride.
  • drying oil or fatty acid there is suitably employed a saturated or unsaturated fatty acid of 12 to 22 carbon atoms or a corresponding triglyceride, that is, a corresponding fat or oil, such as those contained in animal or vegetable fats or oils.
  • Suitable fats and oils include tall oil, castor oil, coconut oil, lard, linseed oil, palm oil, peanut oil, rapeseed oil, soybean oil and beef tallow.
  • Such fats and oils comprise mixed triglycerides of such fatty acids as caprylic, capric, lauric, myristic, palmitic, and stearic and such unsaturated fatty acids as oleic, eracic, ricinoleic, linoleic and linolenic.
  • these fats and oils are usually mixtures of two or more members of the class.
  • Alkyd resins made with saturated monocarboxylic acids and fats are especially preferred.
  • Epoxy polymers having a number average molecular weight in the range of from about 500 to about 6,000 may be used as the polyol component of this invention.
  • a well-known epoxy resin which may be used in the invention is made by condensing epichlorohydrin with bisphenol A, diphenylol propane. An excess of
  • epichlorohydrin is used, to leave epoxy groups on each end of the low-molecular weight polymer:
  • the viscosity of the polymer is a function of molecular weight, the higher the molecular weight the more viscous the polymer.
  • hydroxyl-containing compounds including resorcinol, hydroquinone, glycols, and glycerol may be used in lieu of bisphenol A.
  • Methylol (alkoxymethyl) amino crosslinking agents are suitable for use in the present invention and are well known commercial products, and are generally made by the reaction of di (poly) amide (amine) compounds with formaldehyde and, optionally, a lower alcohol.
  • the amino resins have from about 3 to about 30 crosslinking groups per molecule.
  • Suitable amino-crosslinking resins include one or a mixture of the following materials.
  • R CH 3 (Cymel) ® 300, 301, 303);
  • R CH 3 , H (Cymel ® 370, 373, 380, 385).
  • the preferred melamine is hexamethoxymethyl melamine.
  • R CH 3 , H (BeetleTM 60, BeetleTM 65); or
  • R C 4 H 9 (BeetleTM 80).
  • the amino resin may be a liquid or solid.
  • the amino resin if the amino resin is a solid, that solid is soluble in such blend of the polymeric vehicle and the viscosity of the formulated coating composition and polymeric vehicle should not exceed the ranges described herein.
  • the amino resin when it is a liquid, it preferably has a viscosity of less than about 3.0 Pa.s at about 25oC.
  • HMMM highly alkylated hexamethoxy-methylmelamine
  • HMMM resin appears to be a waxy solid under most conditions with a melting point in the range of about 30oC and is sold by Cytec Chemical Company under the name Cymel 300.
  • a similar crosslinker which is a melamine resin which can be used in the invention is a highly monomeric, highly methylolated hexamethylolated melamine formaldehyde resin which appears to be a solid under most conditions at 25oC and is sold by Monsanto Chemical Company under the designation HM-2612. Solvents And Optional Ingredients In the Polymeric
  • Suitable optional solvents which may be included in the curable compositions of the invention comprise toluene, xylene, ethylbenzene, tetralin, naphthalene, and solvents which are narrow cut aromatic solvents comprising C 8 to C 13 aromatics such as those marketed by Exxon Chemical
  • Aromatic 100 Aromatic 100
  • Aromatic 150 Aromatic 200
  • Suitable solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, methyl heptyl ketone, isophorone, isopropanol, n-butanol, sec. -butanol, isobutanol, amyl alcohol, isoamyl alcohol, hexanols, and heptanols.
  • Additional suitable oxygenated solvents include propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, ethyl ethoxypropionate, dipropylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and like materials.
  • Other such solvents include alkyl esters such as ethyl acetate, n- propyl acetate, butyl acetate, amyl acetate, mixtures of hexyl acetates such as sold by Exxon Chemical Company under the name EXXATE ® 600 and mixtures of heptyl acetates sold under the name EXXATE ® 700.
  • the list should not be considered as limiting, but rather as examples of solvents which are useful in the present invention.
  • the type and concentration of solvents are generally selected to obtain formulation viscosities and evaporation rates suitable for the application and baking of the coatings.
  • Suitable pigments which may be included in the compositions of this invention are those opacifying pigments normally used in paint and coating formulations and include titanium dioxide, zirconium oxide, zircon, zinc oxide, iron oxides, antimony oxide, carbon black, as well as chrome yellows, greens, oranges, mixed metal oxides, ceramic pigments and the like.
  • Preferred pigments include rutile TiO 2 and particularly weather- resistant coated types of TiO 2 .
  • the pigments may also be blended with a suitable extender material which does not contribute significantly to hiding power.
  • Suitable extenders include silica, barytes, calcium sulfate, magnesium silicate (talc), aluminum oxide, aluminum hydroxide, aluminum silicate, calcium silicate, calcium carbonate (mica), potassium aluminum silicate and other clays or clay-like materials.
  • Satisfactory baking schedules such as 38oC to 150oC for formulations of the present invention vary widely including, but not limited to, low temperature bakes of about 20 to 30 minutes at temperatures between 90oC and 105oC for large equipment applications and high
  • the polymeric vehicles may be cured at about 25oC when the crosslinker is an isocyanate and the melamine is not relied upon to crosslink.
  • the substrate and coating should be baked at a
  • the desired degree of completion also varies widely and depends on the particular combination of cured film properties required for a given
  • catalyzed crosslinking also may be effected at ambient temperatures using many
  • Acid catalysts may be used to cure systems
  • hexamethoxymethyl melamine and other amino crosslinking agents and a variety of suitable acid catalysts are known to one skilled in the art for this purpose. These include, for example, p-toluene sulfonic acid, methane sulfonic acid, nonylbenzene sulfonic acid, dinonylnapthalene disulfonic acid, dodecylbenzene sulfonic acid, phosphoric acid, phosphorous acid, phenyl acid phosphate, butyl phosphate, butyl maleate, and the like or a compatible mixture of them. These acid catalysts may be used in their neat, unblocked form or combined with suitable blocking agents such as amines. Typical examples of unblocked catalysts are the King Industries, Inc., products with the tradename K-CURE ® . Examples of blocked catalysts are the King Industries, Inc., products with the tradename NACURE ® .
  • Catalysts for isocyanates include soluble tin salts such as dibutyltin dilaurate and dibutyltin diacetate, divalent zinc salts such as zinc diacetate, and tertiary bases including tertiary amines, such as
  • the amount of catalyst employed typically varies inversely with the severity of the baking schedule. In particular, smaller concentrations of catalysts are usually required for higher baking temperatures or longer baking times. Typical catalyst concentrations for moderate baking conditions (15 to 30 minutes at 150oC) would be about 0.01 to 0.2 wt% catalyst solids per polymer plus crosslinking agent solids. Higher concentrations of catalyst up to about 5 wt% may be employed for cures at lower temperature or shorter times. Formulations containing sufficient residual esterification catalyst, such as phosphorous acid, may not require the inclusion of any additional crosslinking catalyst to effect a proper cure at lower curing
  • Desmodur N3300 - From Miles Corporation is a
  • disulfonic acid in isobutanol is obtained from King Industries ("Nacure-155").
  • Cymel 300 An HMMM resin sold by Cytec
  • HMMM resin appears to be a waxy solid under most conditions with a melting point in the range of about 30oC.
  • An oligoester diol was made from 1,4-butanediol and a 50/50 (mol/mol) mixture of dimethyl glutarate and dimethyl adipate.
  • the following foraulations using the latter oligoesterdiol (Mn 329) , hardener, a phenolic ester alcohol as described in Example I (PHEA), the isocyanate Desmodur N3300 and melamine-formaldehyde resin, Cymel 300 were prepared in order to prepare formulations that have little or no sagging.
  • the aliphatic-OH groups of the PHEA appear to react with the isocyanate groups at ambient or mildly elevated
  • the PHEA was dissolved in the oligoesterdiol followed by Cymel 300 at room temperature.
  • DNNDSA, melamine catalyst, and BYK-302 were added and the formulation was uniformly mixed.
  • Desmodur N3300 was added and mixed the formulation uniformly.
  • a solution of dibutyltin dilaurate (DBTDL) in oligoesterdiol (9.07 wt. %) was added. Low amounts of DBTDL catalyst was added to allow the
  • the acid catalyst DNNDSA allows the phenol to condense with the melamine resin.
  • Desmodur N3300 was used to completely react with the aliphatic -OH groups of the diol and also that of PHEA.
  • the amount of Cymel 300 used is 2X the phenol -OH equivalent.
  • PHEA was dissolved in the oligoesterdiol followed by Cymel 300 at room temperature.
  • DNNDSA, BYK-302 and acetone were added and the formulation was uniformly mixed.
  • Desmodur N3300 was added and mixed the formulation uniformly.
  • a solution of dibutyltin dilaurate (DBTDL) in oligoesterdiol RS93 (9.07 wt. %) was added.
  • DBTDL dibutyltin dilaurate
  • oligoesterdiol RS93 9.07 wt. % was added.
  • the acid catalyst DNNDSA allows the phenol to condense with the melamine resin.
  • Desmodur N3300 was taken to completely react with the aliphatic -OH groups of the diol and also that of PHEA.
  • the amount of Cymel 300 taken is 2X the phenol -OH equivalent.
  • the NVW was calculated without considering the acetone content. Some acetone might have already evaporated during the formulation thereby causing higher NVW values.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un véhicule polymère, une formulation de composition de revêtement et un liant de revêtement faits dudit véhicule polymère, ainsi qu'un procédé permettant de produire ledit véhicule, lequel comprend un polyol, un composé isocyanate et un alcool d'ester phénolique possédant au moins un groupe hydroxyle aliphatique et au moins un groupe hydroxyle phénolique.
PCT/US1996/005178 1995-04-19 1996-04-16 Compositions contenant des polyols, des esters phenoliques et des isocyanates WO1996033229A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP53182896A JP2001527586A (ja) 1995-04-19 1996-04-16 ポリオール、フェノールエステルアルコール及びイソシアネート化合物を含むポリマービヒクル
EP96913793A EP0769030A4 (fr) 1995-04-19 1996-04-16 Compositions contenant des polyols, des esters phenoliques et des isocyanates
AU56640/96A AU5664096A (en) 1995-04-19 1996-04-16 Compositions containing polyols, phenolic esters and isocyanates

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US42520595A 1995-04-19 1995-04-19
US08/425,205 1995-04-19
US08/621,171 1996-03-21
US08/621,171 US6087464A (en) 1995-04-19 1996-03-21 Polymeric vehicles which include a polyol, a phenolic ester alcohol and isocyanate compound

Publications (1)

Publication Number Publication Date
WO1996033229A1 true WO1996033229A1 (fr) 1996-10-24

Family

ID=27026607

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/005178 WO1996033229A1 (fr) 1995-04-19 1996-04-16 Compositions contenant des polyols, des esters phenoliques et des isocyanates

Country Status (5)

Country Link
EP (1) EP0769030A4 (fr)
JP (1) JP2001527586A (fr)
AU (1) AU5664096A (fr)
CA (1) CA2190634A1 (fr)
WO (1) WO1996033229A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0784607A1 (fr) * 1995-08-09 1997-07-23 Exxon Chemical Patents Inc. Vehicules polymeres renfermant un diluant reactif d'urethane phenolique
WO1997034863A1 (fr) * 1996-03-21 1997-09-25 Exxon Chemical Patents Inc. Vecteur polymere en milieu aqueux pour compositions de revetement contenant un sel amine ou ammonium d'un alcool d'ester phenolique
US5976706A (en) * 1995-10-10 1999-11-02 Exxon Chemical Patents Inc. Low viscosity, high solids polyesterdiols and compositions containing same
US8163850B2 (en) 2009-02-06 2012-04-24 Eastman Chemical Company Thermosetting polyester coating compositions containing tetramethyl cyclobutanediol
US8168721B2 (en) 2009-02-06 2012-05-01 Eastman Chemical Company Coating compositions containing tetramethyl cyclobutanediol
US8324316B2 (en) 2009-02-06 2012-12-04 Eastman Chemical Company Unsaturated polyester resin compositions containing 2,2,2,4-tetramethyl-1,3-cyclobutanediol and articles made therefrom
US9029461B2 (en) 2009-02-06 2015-05-12 Eastman Chemical Company Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol
US9029460B2 (en) 2009-02-06 2015-05-12 Stacey James Marsh Coating compositions containing acrylic and aliphatic polyester blends
US9487619B2 (en) 2014-10-27 2016-11-08 Eastman Chemical Company Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol
US9598602B2 (en) 2014-11-13 2017-03-21 Eastman Chemical Company Thermosetting compositions based on phenolic resins and curable poleyester resins made with diketene or beta-ketoacetate containing compounds
US9650539B2 (en) 2014-10-27 2017-05-16 Eastman Chemical Company Thermosetting compositions based on unsaturated polyesters and phenolic resins
US9988553B2 (en) 2016-02-22 2018-06-05 Eastman Chemical Company Thermosetting coating compositions
US10011737B2 (en) 2016-03-23 2018-07-03 Eastman Chemical Company Curable polyester polyols and their use in thermosetting soft feel coating formulations
US10526444B2 (en) 2015-09-25 2020-01-07 Eastman Chemical Company Polymers containing cyclobutanediol and 2,2-bis(hydroxymethyl)alkylcarboxylic acid
US10676565B2 (en) 2015-05-19 2020-06-09 Eastman Chemical Company Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5398754B2 (ja) * 2011-02-04 2014-01-29 太陽ホールディングス株式会社 ウレタン樹脂、それを含有する熱硬化性樹脂組成物及びその硬化物

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3836491A (en) * 1971-01-26 1974-09-17 Ashland Oil Inc Novel compositions comprising polyisocyanates and hydroxybenzoic acid capped polymers curable with tertiary amines and process of curing same
US4331782A (en) * 1981-03-05 1982-05-25 Ashland Oil, Inc. Hydroxybenzoic acid-epoxy adduct capping agents for polyester resins
US4877838A (en) * 1988-01-25 1989-10-31 The Glidden Company High solids coatings with reactive epoxy ester diluent
US5235006A (en) * 1987-03-27 1993-08-10 North Dakota State University Mesogens and polymers with mesogens
US5239018A (en) * 1989-09-06 1993-08-24 Exxon Chemical Patents Inc. Liquid polymer and polyol compositions, and process for preparing phenol-functional polymer

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3789044A (en) * 1971-01-26 1974-01-29 Ashland Oil Inc Novel cured compositions prepared from the reaction of a polyisocyanate and a hydroxybenzoic acid capped epoxide-containing material
US5610263A (en) * 1994-01-25 1997-03-11 Eastern Michigan University Water thinned polymeric vehicle for coating compositions with low amounts of volatile oragnic compounds
AU6768896A (en) * 1995-08-09 1997-03-05 Exxon Chemical Patents Inc. Polymeric vehicles which include a phenolic urethane reactive diluent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3836491A (en) * 1971-01-26 1974-09-17 Ashland Oil Inc Novel compositions comprising polyisocyanates and hydroxybenzoic acid capped polymers curable with tertiary amines and process of curing same
US4331782A (en) * 1981-03-05 1982-05-25 Ashland Oil, Inc. Hydroxybenzoic acid-epoxy adduct capping agents for polyester resins
US5235006A (en) * 1987-03-27 1993-08-10 North Dakota State University Mesogens and polymers with mesogens
US4877838A (en) * 1988-01-25 1989-10-31 The Glidden Company High solids coatings with reactive epoxy ester diluent
US5239018A (en) * 1989-09-06 1993-08-24 Exxon Chemical Patents Inc. Liquid polymer and polyol compositions, and process for preparing phenol-functional polymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0769030A4 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0784607A1 (fr) * 1995-08-09 1997-07-23 Exxon Chemical Patents Inc. Vehicules polymeres renfermant un diluant reactif d'urethane phenolique
EP0784607A4 (fr) * 1995-08-09 2000-03-15 Exxon Chemical Patents Inc Vehicules polymeres renfermant un diluant reactif d'urethane phenolique
US5976706A (en) * 1995-10-10 1999-11-02 Exxon Chemical Patents Inc. Low viscosity, high solids polyesterdiols and compositions containing same
WO1997034863A1 (fr) * 1996-03-21 1997-09-25 Exxon Chemical Patents Inc. Vecteur polymere en milieu aqueux pour compositions de revetement contenant un sel amine ou ammonium d'un alcool d'ester phenolique
US8524834B2 (en) 2009-02-06 2013-09-03 Eastman Chemical Company Coating compositions containing tetramethyl cyclobutanediol
US8168721B2 (en) 2009-02-06 2012-05-01 Eastman Chemical Company Coating compositions containing tetramethyl cyclobutanediol
US8324316B2 (en) 2009-02-06 2012-12-04 Eastman Chemical Company Unsaturated polyester resin compositions containing 2,2,2,4-tetramethyl-1,3-cyclobutanediol and articles made therefrom
US8519055B2 (en) 2009-02-06 2013-08-27 Eastman Chemical Company Thermosetting polyester coating compositions containing tetramethyl cyclobutanediol
US8163850B2 (en) 2009-02-06 2012-04-24 Eastman Chemical Company Thermosetting polyester coating compositions containing tetramethyl cyclobutanediol
US9029461B2 (en) 2009-02-06 2015-05-12 Eastman Chemical Company Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol
US9029460B2 (en) 2009-02-06 2015-05-12 Stacey James Marsh Coating compositions containing acrylic and aliphatic polyester blends
US9487619B2 (en) 2014-10-27 2016-11-08 Eastman Chemical Company Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol
US9650539B2 (en) 2014-10-27 2017-05-16 Eastman Chemical Company Thermosetting compositions based on unsaturated polyesters and phenolic resins
US9598602B2 (en) 2014-11-13 2017-03-21 Eastman Chemical Company Thermosetting compositions based on phenolic resins and curable poleyester resins made with diketene or beta-ketoacetate containing compounds
US10676565B2 (en) 2015-05-19 2020-06-09 Eastman Chemical Company Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol
US10526444B2 (en) 2015-09-25 2020-01-07 Eastman Chemical Company Polymers containing cyclobutanediol and 2,2-bis(hydroxymethyl)alkylcarboxylic acid
US9988553B2 (en) 2016-02-22 2018-06-05 Eastman Chemical Company Thermosetting coating compositions
US10011737B2 (en) 2016-03-23 2018-07-03 Eastman Chemical Company Curable polyester polyols and their use in thermosetting soft feel coating formulations

Also Published As

Publication number Publication date
EP0769030A1 (fr) 1997-04-23
AU5664096A (en) 1996-11-07
JP2001527586A (ja) 2001-12-25
EP0769030A4 (fr) 1997-10-22
CA2190634A1 (fr) 1996-10-24

Similar Documents

Publication Publication Date Title
US6087464A (en) Polymeric vehicles which include a polyol, a phenolic ester alcohol and isocyanate compound
CA2023289C (fr) Composes de polymeres et de polyols liquides, procede de preparation et polymere a fonction phenol
US6646049B2 (en) High-solids thermoset binders formed using hyperbranched polyols as reactive intermediates, coating compositions formed therewith, and methods of making and using same
US5587428A (en) Polymeric vehicle effective for providing solventless coating compositions
WO1996033229A1 (fr) Compositions contenant des polyols, des esters phenoliques et des isocyanates
US5610263A (en) Water thinned polymeric vehicle for coating compositions with low amounts of volatile oragnic compounds
US6051674A (en) Polymeric vehicles which include a phenol blocked isocyanate having aliphatic hydroxyl fucntionality
US5910563A (en) Water thinned polymeric vehicle for coating compositions with low amounts of volatile organic compounds
US5780556A (en) Thermoset coating compositions having improved hardness and curing properties
US5973072A (en) Polymeric vehicles which include a phenolic urethane reactive diluent
US6103826A (en) Clearcoat compositions containing phenolic ester compounds
CA1245670A (fr) Enduit a base de polyester a forte teneur de solides
US5955550A (en) Polymeric vehicle for providing solventless coating compositions
JP2003525966A (ja) ハイソリッドエポキシ、メラミンおよびイソシアネート組成物
AU749637B2 (en) Compositions containing polyols, phenolic esters and isocyanates
EP0784607A1 (fr) Vehicules polymeres renfermant un diluant reactif d'urethane phenolique
MXPA97002516A (en) Permanent memory
US6005135A (en) Water-borne polymeric vehicle for coating compositions containing an amine or ammonium salt of phenolic ester alcohols
MXPA97002546A (en) Polymeric vehicles that include a reagent diluent of uretano fenol
ESTER Jones et al.
AU718252C (en) Water thinned polymeric vehicle for coating compositions with low amounts of volatile organic compounds
MXPA97007985A (en) Coating compositions thermofraguadasteniendo better hardness

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML

WWE Wipo information: entry into national phase

Ref document number: 2190634

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 1996913793

Country of ref document: EP

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWP Wipo information: published in national office

Ref document number: 1996913793

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWW Wipo information: withdrawn in national office

Ref document number: 1996913793

Country of ref document: EP