WO1997015615A1 - Esters d'epoxyresine durcissable a autodispersion - Google Patents

Esters d'epoxyresine durcissable a autodispersion Download PDF

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Publication number
WO1997015615A1
WO1997015615A1 PCT/US1996/016818 US9616818W WO9715615A1 WO 1997015615 A1 WO1997015615 A1 WO 1997015615A1 US 9616818 W US9616818 W US 9616818W WO 9715615 A1 WO9715615 A1 WO 9715615A1
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WO
WIPO (PCT)
Prior art keywords
oil
epoxy resin
epoxy
equivalents
self
Prior art date
Application number
PCT/US1996/016818
Other languages
English (en)
Inventor
Kartar S. Arora
Grannis S. Johnson
James Aloye
Original Assignee
Henkel Corporation
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 US08/735,298 external-priority patent/US5760108A/en
Application filed by Henkel Corporation filed Critical Henkel Corporation
Priority to AU74605/96A priority Critical patent/AU7460596A/en
Priority to EP96936764A priority patent/EP0857188A4/fr
Publication of WO1997015615A1 publication Critical patent/WO1997015615A1/fr

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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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a method of making aqueous epoxy resin ester dispersions.
  • the dispersions are useful in preparing coating compositions comprising the same.
  • Epoxy resins have come into widespread use as components in coating
  • Coatings which comprise cured epoxy resins are valued for their durability, chemical resistance, and excellent adhesion to a broad range of substrates
  • Particularly desirable from an environmental point of view are epoxy resins which may be applied to a substrate with either minimal or no release of volatile organic components Toward this end, there has been much research
  • One class of aqueous epoxy dispersions empioys one or more additives
  • dispersants or emuisifiers or surfactants which are necessary to stabilize the epoxy resin in the dispersion or emulsion form
  • Representative examples include an aqueous epoxy dispersion as described in U S Patent No 3,301 ,804 (employing the reaction product of a DO ⁇ C acid ester derived from
  • a cationic emulsifying agent selected from the group consisting of imidazolines and amides and a non-ionic emulsifying agent
  • PROX-E-141 can act as a dispersant for epoxy resin in water, but then will react along with the epoxy resin when exposed to an amine functional curing agent
  • self-emulsifying epoxy resin which is the addition product of reactants comprising (a) 40-90 parts by weight of diglycidyl ether of dihydric phenol, (b) 5-35 parts by weight of dihydric phenol, and (c) 2-15 parts
  • dispersion can also contain 1-25 weight percent based on resin solids of a water-immiscible C 8 -C 20 aliphatic monoepoxide reactive diluent.
  • U.S. Patent No. 4,608,406 describes stable aqueous epoxy resin dispersions comprised of (1 ) an aqueous medium; and (2) between about 50 to about 70 weight percent of self-emulsifying epoxy resin which is the addition
  • reaction product of (a) 40-90 parts by weight of a diglycidyl ether of a dihydric phenol; (b) 5-35 parts of a dihydric phenol; (c) 2-15 parts by weight of a diglycidyl ether of a polyoxyalkylene glycol; and (d) 2 to 15 parts by weight of an alkyl phenol-formaldehyde novolac resin wherein the molecular weight of the
  • the stable dispersions can be modified by the addition of about 1 to about 25 weight percent of an aliphatic monoepoxide reactive diluent In an attempt to improve freeze-thaw stability, the stable aqueous epoxy resm dispersions can be modified by the addition of about 5-20 weight percent, based on resin solids weight, of a water-miscible solvent which, preferably, is a 2 to 8 carbon glycol or glycol ether.
  • U.S. Patent No. 4,107,112 discloses a binder composition for binding soil particles, the composition comprising an epoxy resin
  • ester which is the reaction product of a bisphenol A-glycidyl ether type epoxy resin with linseed fatty acids in which the molar ratio of fatty acid to bisphenol A units is between about 0.5 to 1.0, together with free linseed fatty acids, a solvent, preferably a volatile solvent, an emulsifying agent, and water, the water
  • compositions in its concentrated form prior to subsequent mixing with additional water prior to, or during, mixture with soil. It is stated that it is preferred that the composition
  • reaction product of (A) from about 50% to about 65% by weight based upon the total weight of (A) and (B) of an epoxy resin ester of a partially conjugated
  • unsaturated fatty acid and (B) from about 50% to about 35% by weight based upon the total weight of (A) and (B) of a blend of reactive monomer possessing reactive double bonds, at least one of which must be a ⁇ unsaturated mono-basic
  • the monomer (B) portion consists of a mixture of 20-28% of unsaturated monobasic acids having a polymerizable double bond and 80% to 72% reactive monomers having a polymerizable double bond and serves to make tne resin water dilutable.
  • the latex is the predominant film-forming ingredient in the composition and is combined with
  • film-forming ingredients including a water-soluble epoxy ester, preferably derived from bisphenol A, diglycidyl ether, drying oil fatty acids and a polycarboxylic acid or anhydride, e.g. maleic anhydride, and water-soluble
  • aminoplast resins preferably methoxylated melamine formaldehyde resin and butoxylated urea formaldehyde resin.
  • the epoxy ester preferably methoxylated melamine formaldehyde resin and butoxylated urea formaldehyde resin.
  • trimellitic acid or anhydride or, most preferably, maleic anhydride, to introduce free carboxyl groups which, of course, form water-soluble salts in alkaline medium
  • dispersion can be prepared from the product of reacting a self-dispersing curable epoxy resin based on a polyoxyalkyleneamine with a fatty acid selected from the group consisting of drying oil and semi- ⁇ rymg oil fatty acids
  • the self-dispersing curable epoxy resin is based on a polyoxyalkyleneamine
  • a polyoxyalkyleneamine was present as a
  • the self-dispersing curable epoxy resm ester of the invention is used as a coating composition in the form of an aqueous dispersion When cured, films of the self-dispersing curable epoxy resm ester dispersion form a protective coating.
  • Drying and semidrying oil fatty acids are natural or synthetic fatty acids
  • Natural drying and semidrying oil fatty acids having two or more double bonds separated by single methylene groups or two or more conjugated double bonds.
  • each ester molecule typically yields a mixture of different fatty acids, a portion of which may be fatty acids of the non- drying type, i.e. having no double bonds separated by single methylene groups nor two or more conjugated double bonds.
  • Dehydrated castor oil is an example of a synthetic drying oil derived by the dehydration of ricinoleic acid.
  • Drying oils are generally considered to be those which dry to a solid film upon exposure to air.
  • Semidrying oils are those which dry to a tacky film and
  • the oil is a drying oil.
  • Typical drying or semidrying oil fatty acids used in this invention are used in this invention.
  • fish oils is that the oil is a drying oil if the average number of methylene groups between two double bonds or pairs of conjugated double bonds per t ⁇ ester
  • glycerol molecule is greater than 2.2 (thus, there would be an average of 0.73
  • Typical drying or semidrying oil fatty acids used in this invention will have an average number of methylene groups between two double bonds or pairs of conjugated double bonds pertriester glycerol molecule from about 1.5 to about 6 (i.e. from
  • drying oil fatty acids are linoleic and linolenic acids which are available from vegetable sources such as linseed oil. Eicosenoic and docosenoic acids having from four to six double bonds separated by single
  • methylene groups are available from marine oils and alpha-eleostea ⁇ c acid with three conjugated double bonds is available from tung oil Examples of sources
  • drying oil or semi-drying oil fatty acids are vegetable sources, e.g. safflower oil, sunflower oil. sesame oil, poppy seed oil, grape-seed oil. corn oil. cotton
  • linoleic acid greater than 50 wt.% of linoleic acid.
  • a preferred fatty acid is EMERSOL ®
  • 315 linoleic acid available from Henkel Corporation, Cincinnati, Ohio, and having 60 wt.% linoleic acid, 9 wt.% linolenic acid, 25 wt. % oleic acid, 4
  • the self-dispersing curable epoxy resin are based upon a polyoxyalkyleneamine.
  • the self-dispersing curable epoxy resin based upon a polyoxyalkyleneamine.
  • the epoxy resin is prepared by reacting an
  • the epoxy resin composition is prepared
  • the polyoxyalkyleneamine reactant comprises one or more amino-
  • reactant is soluble or at least partially soluble in water.
  • reactants employed in the invention are the Jeffamine (Reg. TM) brand of
  • Polyoxyalkyleneamines of this invention have the structural formula
  • R 2 represents a polyoxyalkylene chain having the structural formula:
  • R 4 is a monovalent organic radical selected from the group consisting of
  • 'a' designates a number of ethoxy groups (CH 2 -CH 2 -O)
  • 'b' designates a number of monosubstituted ethoxy groups (CH 2 -CH(R 4 )-O)
  • polyoxyalkylene chain the sum of 'a' and 'b' is equal to or greater than 10
  • R 3 designates H or a monovalent organic radical selected from the
  • the polyoxyalkyleneamine is adducted with
  • the preferred polyoxyalkyleneamines have R 1 r R 3 and
  • R 4 each equal to methyl, and either (i) a ratio of 'a' and "b" of about 4: 1 ,
  • the molecular weight of the polyoxyalkyleneamine is less than about
  • polyoxyalkyleneamine is less than about 4,000, or (iii) a ratio of 'a' and 'b'
  • polyoxyalkyleneamine is less than about 6,000, or (iv) a ratio of 'a' and 'b' of about 7:3, wherein the ethoxy and iso-propoxy groups are present in
  • molecular weight of the polyoxyalkyleneamine is less than about 4,000.
  • the most preferred polyoxyalkyleneamine is Jeffamine (Reg. TM) M-
  • this polyoxyalkyleneamine is prepared by reacting methanol with
  • polyoxyalkyleneamine has an approximate molecular weight of 2,000 and
  • the polyoxyalkyleneamine is directly reacted
  • the polyoxyalkyleneamine will react with an epoxy resin.
  • the polyoxyalkyleneamine will react with an epoxy resin.
  • Preferred polyoxyalkyleneamines have R R 3
  • polyoxyalkyleneamine is from about 3,000 to about 4,000, or (ii) a random sequence of ethoxy and iso-propoxy groups wherein the ratio of 'a' and 'b'
  • weight of the polyoxyalkyleneamine is from about 3,000 to about 4,000
  • molecular weight of the polyoxyalkyleneamine is from about 5,000 to about
  • molecular weight of the polyoxyalkyleneamine is from about 5,000 to about
  • ethoxy and iso-propoxy groups are arranged substantially in two blocks and
  • the molecular weight of the polyoxyalkyleneamine is from about 9,000 to
  • a ratio of 'a' to 'b' of about 7:3 e.g. a weight ratio of
  • the molecular weight of the polyoxyalkyleneamine is from about 9,000
  • the most preferred polyoxyalkyleneamines are the Jeffamine (Reg.
  • TM polyoxyalkyleneamines from Texaco Chemical Company, Bellaire Texas. According to Texaco, these polyoxyalkyleneamines are prepared by reacting
  • polyoxyalkyleneamine has an approximate molecular weight of 3,000 and
  • a weight ratio of ethylene oxide to propylene oxide of about 1 9: 1 .
  • Another type of polyoxyalkyleneamine suitable for this invention has
  • R designates a monovalent organic radical selected from the group
  • R 2 represents a polyoxyalkylene chain having the structural formula:
  • R 5 is a monovalent organic radical selected from the group
  • 'a' designates a number of ethoxy groups (CH 2 -CH 2 -O),
  • polyoxyalkylene chain the sum of 'a' and 'b' is equal to or greater than 10 but less than or equal to 200, and where the sequence of ethoxy and
  • R 3 designates H or a monovalent organic radical selected from the
  • R 4 is an aliphatic, cycloaliphatic or aromatic group containing 6 to 1 8
  • n 1 or 2.
  • polyoxyalkyleneamines can be obtained from monoethers of
  • polyoxyalkylene diols or polyoxyalkylene diols and diisocyanates are Suitable
  • R designates a monovalent organic radical selected from the group
  • R 2 represents a polyoxyalkylene chain having the structural formula:
  • R 5 is a monovalent organic radical selected from the group
  • 'a' designates a number of ethoxy groups (CH 2 -CH 2 -O)
  • 'b' designates a number of monosubstituted ethoxy groups (CH 2 -CH(R 5 )-O)
  • R 3 designates H or a monovalent organic radical selected from the
  • n 1 or 2.
  • polyoxyalkylene diol is reacted with a diisocyanate to form an isocyanate-
  • polyoxyalkyleneamines are those derived from reactions of diisocyanates with homopolymers of ethylene oxide or copolymers of ethylene oxide and propylene oxide
  • Preferred copolymers of ethylene oxide and propylene oxide are those available as PluronicTM and PluronicTM R surfactants
  • PluronicTM surfactants are block copolymers of ethylene oxide and propylene oxide with different molecular weight and amount of ethylene oxide and
  • suitable polyoxyalkyleneamines are PluronicTM F88 F98 and F108
  • diisocyanate are reacted in the presence of catalysts such as organotin compounds and tertiary amines.
  • catalysts such as organotin compounds and tertiary amines.
  • This reaction can be performed with or without organic solvents.
  • Suitable organic solvents are those containing no reactive
  • ketones are ketones, esters, aromatic hydrocarbons, ethers, etc
  • Preferred solvents are
  • reaction products for monoethers of polyoxyalkylene diol also contain the bis-adduct of monoether of polyoxyalkylene diol as well as reactants namely monoether of polyoxylkylenediol and diisocyanate However the reaction
  • hydrolysis of isocyanate group containing mono-adduct is performed with water in the presence of a mineral acid such as hydrochloric acid
  • a mineral acid such as hydrochloric acid
  • Suitable diisocyanates for the preparation of adducts include aliphatic, cycloaliphatic, or aromatic diisocyanates such as 1 ,6-hexamethylene
  • the polyepoxide reactant comprises one or more compounds each
  • the polyepoxide reactant has at least 2 epoxide groups present in the molecule, and may have as many as 6 epoxide groups present in the molecule
  • Techniques to prepare suitable polyepoxide compounds are known in the art, and include reacting compounds
  • Suitable aliphatic polyepoxide compounds are commercially available from Henkel Co ⁇ oration, Ambler, Pennsylvania, under the trademarks
  • R 6 designates a linear, branched or cyclic aliphatic or alicyclic organic
  • 'd' is equal to or greater than 2 but no more than or equal to 6 and where 'd' is
  • R ⁇ designates a linear, branched or cyclic aliphatic or alicyclic
  • R ⁇ designates a linear, branched or cyclic aliphatic or alicyclic trivalent organic radical having from 3 to 14 carbon atoms, and specifically includes the hydrocarbon portions of the t ⁇ hyd ⁇ c alcohols glycerol, 1 ,1 ,1- tris(hydroxymethyl)ethane, and 2-ethyl-2-(hydroxymethyl)-1 ,3-propanediol which
  • R 6 designates a linear branched or cyclic aliphatic or
  • R 6 designates a linear, branched or cyclic aliphatic or alicyclic pentavalent organic radical having from 6 to 30
  • R 6 designates a linear, branched or cyclic aliphatic or alicyclic hexavalent organic radical having from 8 to 30 carbon atoms, and specifically includes the hydrocarbon portion of the hexahydric alcohol dipentaerythritoi which remains after the hydroxyl groups
  • R 7 represents a divalent polyoxyalkylene chain having the structural formula: -O-(CH 2 -CH 2 -O).-(CH 2 -CH(R 8 )-O),
  • R 8 is a monovalent organic radical selected from the group
  • 'e' designates a number of ethoxy groups (CH 2 -CH 2 -O), f designates a number of monosubstituted ethoxy groups (CH 2 -CH(R 8 )-
  • the most preferred aliphatic polyepoxide compound is the reaction product of pentaerythritol, propylene oxide and epichlorohydrin, having an
  • epoxide equivalent weight (EEW) of about 230
  • Suitable aromatic polyepoxides include those disclosed in co-pending application U.S. Serial No. 08/366,343, filed 29 December 1994, entitled "Aqueous Self-Dispersible Epoxy Resin Based on Epoxy-Amine Adducts Containing Aromatic Polyepoxide" which is incorporated herein by reference.
  • epoxy novolac resins such as Araldite EPN 1138 and 1139
  • epoxy cresol novolac resins such as Araldite ECN 1235, 1273, 1280 and 1299
  • epoxy phenol novolac resins such as Araldite PV 720, epoxy resin 0510, Araldite MY 720 and 721 , and Araldite PT 810 all of which are available from Ciba-Geigy. Tetrad C and Tetrad X resins available from Mitsubishi Gas
  • the epoxy resin used in the practice of this invention comprises one or more epoxy resins having two (2) or more epoxide groups and one (1 ) or more six-carbon aromatized rings present in the molecule, as represented by the structural formula
  • R 9 represents a 'g' valent C 6 -C 50 organic radical comprising at least one six-carbon aromatized ring (e g when g is 2 R 9 can be -CH 2 - O - ⁇ -C(CH 3 ) 2 - ⁇ -O- CH 2 - or R 9 can be -CH 2 - O - ⁇ -CH 2 - ⁇ -O-CH 2 - wherein ⁇ represents a phenyl
  • Suitable epoxy resms are commercially available from a variety of sources and include EPON (Reg TM) epoxy resins from Shell Chemical Company, Houston Texas, and DER (Reg TM) or DEN (Reg TM) epoxy resins from Dow Chemical Company, Midland, Michigan
  • polycarboxylic acids which may be used include, for example, phthalic acid, isophthalic acid or terephthalic acid II) Polygly ⁇ dyl or poly(beta-methylglyc ⁇ dyl) ethers obtainable by reacting a compound having at least two free phenolic hydroxy groups with
  • epichlorohydrin or beta-methyl-epichlorohyd ⁇ n respectively, under alkaline conditions, or in the presence of an acid catalyst and with subsequent alkali treatment
  • the epoxy compounds of this type may be derived from mononuclear phenols, such as, for example, resorcinol or hydroquinone, or they are based on polynuclear phenols, such as, for example, b ⁇ s(4-hydroxyphenyl)methane, 4,4'- dihydroxybiphenyl, b ⁇ s(4-hydroxyphe ⁇ yl)sulfone 1 , 1 ,2,2-tetrak ⁇ s(4-
  • hydroxyphenyl propane and from novolacs obtainable by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfuraldehyde, with
  • phenols such as phenol, or with phenols that are substituted in the nucleus by halide atoms or 0,-0, 8 (preferably C,- C 9 ) alkyl groups, such as, for example, 4-chiorophenol, 2-methylphenol or 4-tert-butylphenol or by condensation with
  • epoxy resms that have an epoxy content of from 2 to 10 equivalents/mole and that are glycidyl ethers or glycidyl esters of aromatic or alkylaromatic compounds.
  • epoxy resins are preferably used.
  • polyglycidyl ethers of bisphenols such as, for example, of 2,2-bis(4- hydroxyphenyl)propane (bisphenol A) or b ⁇ s(4-hydroxyphenyl)methane
  • Preferred epoxy resins have an epoxide equivalent weight of less than
  • the polyhydric phenol reactant comprises one or more compounds each
  • the polyhydric pnenol reactant may contain substituents such as alkyl, aryl, sulfido, sulfonyl. halo, and the like.
  • polyhydric phenol is represented by the structural formula:
  • R 10 represents an 'h' valent Ce-Cso organic radical comprising at least one six-carbon aromatized ring, and 'h' represents a number of phenolic hydroxyl
  • Suitable polyhydric phenol compounds are commercially available from Dow Chemical Company, Midland Michigan, and Shell Chemical Company, Houston, Texas.
  • phenol-formaldehyde novolac resins and the like
  • dihydric phenols are 2,2-b ⁇ s(4-hydroxyphenyl)propane (bisphenol A) and b ⁇ s(4- hydroxyphenyl )methane (bisphenol F) for reasons of cost and availability
  • the structure of the amine-epoxy adduct is a complex mixture dependent on the structures of the polyoxyalkyleneamine and the polyepoxide
  • the structure and composition of the self-dispersing curable epoxy resin will depend on the identity of the amine-epoxy adduct, the identity of the
  • the epoxy resin is reacted with drying oil or semidrying oil fatty acids to esterify at least a portion of the epoxy groups of the epoxy resin.
  • the amount of fatty acids will be essentially equal on a stoichiometric basis to the epoxy equivalents of the epoxy resin, e.g. a ratio of from about 0.9:1 to about 1.1 :1 , typically from about 0.95:1 to about 1.05: 1. and more typically from about 0.98:1 to about 1.02:1 , fatty acid equivalents per epoxy equivalents.
  • the reaction may typically be accomplished by first adding an organic cosolvent to the crude epoxy resin reaction mixture and then adding the fatty acids to the resulting mixture, but the use of the organic cosolvent is optional.
  • the reaction is typically accomplished at elevated temperature, e.g. 120°C to
  • the course of the reaction can be followed by measuring the acid number of the product and terminating the reaction when a sufficiently low acid number is attained, e.g. an acid number of less than about 5, more typically less than about 2.
  • the self-dispersing curable epoxy resin of the present invention may be combined with a non-reactive, organic cosolvent
  • the cosolvent serves to reduce the viscosity of the self-dispersible curable epoxy resin before its
  • organic cosolvent may perform is the prevention of agglomeration of dispersed resin particles which stabilizes the dispersion of the resin.
  • Suitable cosolvents consist of non- solvents as well as solvents for the self-dispersible epoxy resins.
  • the cosolvent may be miscible, partly miscible or immiscible with water. Mixtures of two or more organic cosolvents can also be employed in this invention.
  • organic cosolvents include the lower fatty acid esters or alkyl ethers of monohydric and dihydric alcohols (or polyethers thereof), wherein the alkyl group comprises C r C 8 linear or branched aliphatic or alicyclic chains and lower alkyl ketones, e.g. ketones having a total of from 3 to 6 carbon atoms, preferably methyl lower-alkyl ketones, wherein said lower alkyl group has from 1 to 3 carbon atoms.
  • the choice of cosolvent can affect the pot-life of the self-
  • dispersing curable epoxy resin For example, for a given resin it may be possible to increase the pot-life by substituting for a cosolvent such as Ektasolve EP (Eastman Chemicals) with one of the following cosolvents (the greater
  • an amine-epoxy adduct is first prepared by combining the
  • respective self-dispersing epoxy resin is prepared by combining the amine- epoxy adduct, the polyhydric phenol and the epoxy resin, and heating the mixture in the presence of a catalyst, e g potassium hydroxide, triphenyl phosphine, benzyl dimethylamine and the like, to a temperature of about 150°C with stirring An exothermic reaction will then occur and cooling is applied to maintain the reaction temperature at about 150-160°C
  • a catalyst e g potassium hydroxide, triphenyl phosphine, benzyl dimethylamine and the like
  • the mixture is then heated to 190°C The mixture is then maintained at 190°C for
  • reaction temperature of about 150°C is maintained until the acid number of the reaction
  • the polyoxyalkyleneamine is reacted directly with the epoxy resin to prepare a self-dispersing curable epoxy resin which is then esterified
  • the conditions employed for such reactions may be similar to the
  • the aqueous epoxy resm ester dispersion of the invention can be prepared by charging the self-dispersing curable epoxy resin ester, as a mixture with an organic cosolvent, to a reaction vessel, then heating the resin to about 50-100°C with stirring. Water is then mixed with the mixture of organic cosolvent and self-dispersing curable epoxy resin ester to form an aqueous pre-
  • emulsion which will typically be a disperse oil phase having a larger particle size.
  • the relative amounts of the resin ester water and organic cosolvent can be any suitable resin ester water and organic cosolvent.
  • each of resin ester, water and organic cosolvent will range between about 20% to about 50% each, more typically from about 35% to about 45% resm ester, and about 25% to about 35% each of water and organic cosolvent
  • the particle size of the oil phase in the aqueous dispersion can be any particle size.
  • the particle size reduction is preferably accomplished by subjecting the aqueous dispersion to high shear, e.g. in a homogenizer such as that disclosed in U.S. Patent No.
  • the reduction of particle size should be effective to reduce the mean (weight average) particle size of the oil phase in the aqueous dispersion to less than about 5 microns, preferably less than about 3 microns and typically less than 1 micron, e.g. typically from about 0.1 to about 3 microns.
  • One or more reactive diluents can be mixed into the pre-emulsion prior to reduction of particle size or they can be added to the aqueous dispersion after the reduction of the particle size.
  • organic cosolvent chosen, but temperatures that will cause degradation or
  • the aqueous dispersion of self-dispersing resm ester will typically exhibit excellent chemical and physical stability over an extended shelf-life, e.g. of from five to six months.
  • the resin ester should not display layer formation for a period of at least one month from the preparation of the aqueous dispersion, i.e there should be no formation of a macro-
  • the coating composition of the invention is prepared by diluting the
  • the coating composition also preferably contains a drier reactive with the drying oil fatty acid portion of the ester
  • driers are salts of metals such as cobalt, lead, manganese, cerium, copper, chromium, iron, tin, vanadium and zirconium
  • metals such as cobalt, lead, manganese, cerium, copper, chromium, iron, tin, vanadium and zirconium
  • metal salts of complex fatty acids present singly or as mixtures.
  • useful driers are the octoates, resinates, naphthenates,
  • neodecanoates tallates and iinoleates and mixtures thereof of metals such as cobalt, manganese, cerium, zirconium and mixtures thereof.
  • the coatings of the present invention will typically contain one or more said driers, present in a total
  • a small amount, e.g. 0.1-1.0 wt. %, of a drier activator may be included in order
  • An aqueous epoxy resin ester paint composition of the present invention may further contain additives conventionally employed in coating technology, such as organic pigments, inorganic pigments, surfactants, thickeners, and the like.
  • resms can be mixed with the coating composition
  • examples of such other resins are the aminoplast and phenolplast resins Suitable
  • aminoplast resins are the reaction products of ureas and melamines with aldehydes further ethe ⁇ fied in some cases with a ⁇ alcohol
  • Examples of aminoplast resin components are urea, ethylene urea thiourea, melamine benzoguanamine and acetoguanamine Aldehydes include formaldehyde acetaldehyde and propionaldehyde
  • the aminoplast resins can be used in the
  • alkylol form but, preferably, are utilized in the ether form wherein the etherifying agent is a monohydric alcohol containing from 1 to 8 carbon atoms
  • suitable aminoplast resins are methylol urea dimethoxymethylol urea, butylated polymeric urea-formaldehyde resms, hexamethoxymethyl melamine, methylated polymeric melamine-formaldehyde resms and butylated polymeric
  • Phenolplast resins are the reaction products of phenols and aldehydes which contain reactive methylol groups These compositions can be monomeric
  • phenol phenol
  • phenol phenol
  • aldehydes are formaldehyde, acetaldehyde and propionaldehyde.
  • Particularly useful phenolplast resins are polymethylol phenols wherein the phenolic group is etherified with an alkyl, e g , methyl or ethyl, group.
  • reaction mixture is heated slowly to 125°-130°C with stirring and held at this temperature for about 2 5 hours.
  • the product amine polyepoxide adduct has 04 meq /gm of total amine and 0.33
  • thermocouple equipped with overhead stirrer, thermocouple, heating mantle, means to
  • control temperature such as Jack-o-maticTM, condenser, nitrogen atmosphere and addition flasks.
  • the resin kettle was charged with a liquid epoxy resin (DER 331, Dow Chemical Co., Midland, Michigan, a liquid diglycidyl ether of bisphenol A having an epoxy equivalent weight of about 190 grams/eq.), bis-phenol A, the
  • Component Composition parts by weight
  • a pigmented coating was formulated from the epoxy ester of Example 4 above according to the following formula.
  • anticorrosive pigment Halox Pigments, Inc.
  • anticorrosive pigment Nyco Minerals, Inc.
  • control temperature such as Jack-o-maticTM condenser nitrogen atmosphere and addition flasks.
  • the resin kettle was charged with 250 parts by weight of a
  • liquid epoxy resin (DER 331 , Dow Chemical Co , Midland, Michigan, a liquid diglycidyl ether of bisphenol A having an epoxy equivalent weight of about 190 grams/eq.), 123.4 parts by weight of bis-phenol A 43 8 parts by weight of the amine-epoxide adduct used in Examples 1 -3 and 0 4 parts by weight of catalyst (triphenyl phosphine or ethyl triphenylphosphonium iodide) The mixture was
  • the epoxy equivalent weight is found to be 1700 gram/eq.
  • the mixture was cooled to 150°C and 98 parts by weight of 2-propoxyethanol was added and stirred until

Abstract

L'invention concerne un type d'ester à époxyrésine durcissable autodispersante, dont le procédé de fabrication consiste à faire réagir une époxyrésine durcissable autodispersante à base de polyoxyalcèneamine avec un acide gras choisi dans le groupe des acides gras du type des huiles siccatives ou semi-siccatives. Etant donnée que l'époxyrésine durcissable autodispersante renferme un constituant de polyoxyalcèneamine, cet élément a pu jouer le rôle de précurseur chimique de l'époxyrésine ou de produits de départ pour cette résine. L'ester d'époxyrésine durcissable autodispersante se présente sous la forme d'une dispersion aqueuse susceptible d'être utilisée comme composition de revêtement donnant une fine pellicule après séchage.
PCT/US1996/016818 1995-10-27 1996-10-25 Esters d'epoxyresine durcissable a autodispersion WO1997015615A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU74605/96A AU7460596A (en) 1995-10-27 1996-10-25 Self-dispersing curable epoxy resin esters
EP96936764A EP0857188A4 (fr) 1995-10-27 1996-10-25 Esters d'epoxyresine durcissable a autodispersion

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US802595P 1995-10-27 1995-10-27
US60/008,025 1995-10-27
US08/735,298 US5760108A (en) 1996-10-22 1996-10-22 Self-dispersing curable epoxy resin esters, dispersions thereof and coating compositions made therefrom
US08/735,298 1996-10-22

Publications (1)

Publication Number Publication Date
WO1997015615A1 true WO1997015615A1 (fr) 1997-05-01

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PCT/US1996/016818 WO1997015615A1 (fr) 1995-10-27 1996-10-25 Esters d'epoxyresine durcissable a autodispersion

Country Status (3)

Country Link
EP (1) EP0857188A4 (fr)
AU (1) AU7460596A (fr)
WO (1) WO1997015615A1 (fr)

Cited By (3)

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Publication number Priority date Publication date Assignee Title
FR2878251A1 (fr) * 2004-11-22 2006-05-26 Cognis Deutschland Gmbh Compositions durcissables par irradiation et leur utilisation
WO2015058669A1 (fr) * 2013-10-21 2015-04-30 北京金汇利应用化工制品有限公司 Procédé de préparation de résine aqueuse ester d'époxy et son utilisation
CN114870413A (zh) * 2022-04-14 2022-08-09 杭州特种纸业有限公司 一种钢纸用氯化锌溶液循环利用方法

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US4154709A (en) * 1978-03-06 1979-05-15 Hitachi Chemical Company, Ltd. Water-dispersible epoxy modified alkyd resins
US5565505A (en) * 1993-06-30 1996-10-15 Henkel Corporation Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom

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US4358551A (en) * 1981-07-17 1982-11-09 Celanese Corporation Aqueous air-drying cationic epoxy ester coating compositions
AU1403595A (en) * 1993-12-27 1995-07-17 Henkel Corporation Self-dispersing curable epoxy resins and coatings
US5604269A (en) * 1993-12-27 1997-02-18 Henkel Corporation Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom
US5565506A (en) * 1994-03-01 1996-10-15 Henkel Corporation Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom

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Publication number Priority date Publication date Assignee Title
US4154709A (en) * 1978-03-06 1979-05-15 Hitachi Chemical Company, Ltd. Water-dispersible epoxy modified alkyd resins
US5565505A (en) * 1993-06-30 1996-10-15 Henkel Corporation Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom

Non-Patent Citations (1)

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Title
See also references of EP0857188A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2878251A1 (fr) * 2004-11-22 2006-05-26 Cognis Deutschland Gmbh Compositions durcissables par irradiation et leur utilisation
WO2006056331A1 (fr) * 2004-11-22 2006-06-01 Cognis Ip Management Gmbh Compositions durcissables par rayonnement
US8524808B2 (en) 2004-11-22 2013-09-03 Igm Group B.V. Radiation curable compositions
WO2015058669A1 (fr) * 2013-10-21 2015-04-30 北京金汇利应用化工制品有限公司 Procédé de préparation de résine aqueuse ester d'époxy et son utilisation
CN114870413A (zh) * 2022-04-14 2022-08-09 杭州特种纸业有限公司 一种钢纸用氯化锌溶液循环利用方法

Also Published As

Publication number Publication date
EP0857188A4 (fr) 1999-02-03
EP0857188A1 (fr) 1998-08-12
AU7460596A (en) 1997-05-15

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