CA2166414A1 - Self-dispersing curable epoxy resins and coatings - Google Patents
Self-dispersing curable epoxy resins and coatingsInfo
- Publication number
- CA2166414A1 CA2166414A1 CA002166414A CA2166414A CA2166414A1 CA 2166414 A1 CA2166414 A1 CA 2166414A1 CA 002166414 A CA002166414 A CA 002166414A CA 2166414 A CA2166414 A CA 2166414A CA 2166414 A1 CA2166414 A1 CA 2166414A1
- Authority
- CA
- Canada
- Prior art keywords
- amine
- epoxy
- self
- epoxy resin
- reactive equivalents
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
-
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
Abstract
A self-dispersing curable epoxy composition is prepared upon contacting (a) 1.0 reactive equivalents of an epoxy resin, (b) from about 0.01 to 1.0 reactive equivalents of a polyhydric phenol, and (c) between 0.005 and 0.025 reactive equivalents of an amine-epoxy adduct, wherein the amine-epoxy adduct is formed upon contacting 1.0 equivalent of an aliphatic polyepoxide and between 0.3 and 0.9 reactive equivalents of a polyoxyalkyleneamine. The self-dispersing curable epoxy resin forms an aqueous dispersion upon mixing with water. When cured, the dispersion is useful as a coating composition.
Description
~WO95/01387 , ~ h~ 2 1 664 1 4 PCT/US94/06770 "SELF-DISPERSING CURABLE EPOXY RESINS AND COATINGS"
Cross-Rerere"ce to Related APPlications This application is a continuation-in-part of U.S. Serial No. 08/086,288, filed June 30, 1993, the ~lisclosllre of which is incorporated by reference herein.
Field Of The Invention The present invention relates to coating compositions made from aqueous epoxy dispersions. More specifically, this invention relates to self-dispersing curable epoxy resins, and to aqueo! ~s dispersions and coating 5 compositions comprising the same.
WO 95/01387 ~ 2 1 6 6 ~ 1 4 PCT/US94/06770 ~
Back~round of the Invention Epoxy resins have come into widespread use as components in coating compositions. Coatings which comprise cured epoxy resins are valued for their durability, chemical resislance, and excellent adhesion to a 5 broad range of substrates. Particularly desitable 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 directed to the development of aq~ ~eo~ ~s dispersions and emulsions of epoxy resins.
One class of ~l leo! ls epoxy dispersions employs one or more additives, also known as dispersanls or emulsifiers or su, rac~anls, which are necess~y to stabilize the epoxy resin in the dispersion or emulsion form.
Represenlalive examples include an a~ueo~ ~s epoxy dispersion as described in U.S. Patent No. 3,301,804 (employing the reaction product of a boric acid 15 ester derived from boric acid with both an alkylene glycol and a beta-dialkyl-substituted aminoalkanol as an emulsifier), U.S. Patent No. 3,634,348 (employing a phosphate ester as an emulsifying agent), U.S. Patent No.
3,249,412 (employing in combination a cationic emulsifying agent selected from the group consisling of imidazolines and amides and a non-ionic 20 emulsifying agent), and Specialty Chemicals Bulletin SC-021 titled "Water-Reducible Coatings via Epoxy Resin Modification with Jeffamine (Reg. TM) ED-2001 and Jeffamine (Reg. TM) M-1000" available from Texaco Chemical Company, Bellaire, Texas. Another example comes from the technical literature of Synthron Inc., Morgantown, North Carolina, which discloses the ~WO 95/01387 ~ '~ 2 1 6 6 4 1 4 PCT/US94/06770 use ol' PROX-E-141, a diglycidyl ether of Pluronic (Reg. TM) F88 diol (an ethylene oxide - propylene oxide - ethylene oxide block copolymer available from E3ASF Pe, ror",a,lce Chemicals, Par~i,upany, New Jersey) as a reactive dispersant for epoxy resins. PROX-E-141 can act as a dispersant for epoxy 5 resin Dn water, but then will react along with the epoxy resin when exrosed to an amine functional curing agent.
The use of an additive to provide stability to an aqueous epoxy dispersion is preferably avoided as such additives add additional cost, formulation complexity, and may potentially interfere with the performance of 10 a coating derived from the ~queous epoxy dispersion.
It is known to prepare aqueous epoxy dispersions from self-emulsifying epoxy resins. For example, U.S. Patent No. 4,315,044 describes a stable epoxy dispersion co",posilion comprising (1) an ~ eo~s medium; and (2) between about 50-70 weight peroenl of self-emulsifying epoxy resin which is 15 the addition product of r~acta, ll~ coi "~., ising (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 by weight of diglycidyl ether of polyoxyalkylene glycol, where~in the molecular weight of the epoxy resin is in the range between about 500-20,000. The dispersion can also contain 1-25 weight percent 20 based on resin solids of a water-immiscible C8-C20 aliphatic monoepoxide reactive diluent.
U.S. Patent No. 4,608,406 describes stable aqueous epoxy resin dispel~ions comprised of (1) an aqueous medium; and (2) between about 50 to about 70 weight percent of self-emulsifying epoxy resin which is the WO 95/01387 ~ t ~ 2 1 6 6 4 1 4 PCT/US94/06770 ~
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 epoxy resin is in the range of about 1000 to about 20 000. The stable dispersions can be modified by the addition of about 1 to about 25 weight per~nt of an aliphatic ",o"oepoxide reactive diluent.
In an allelllpt to improve freeze-thaw stability, the stable aqueous ~epoxy resin dispersions can be modified by the addition of about 5-20 weight percent based on resin solids weight, of a water-miscible solvent which, prererably, is a 2 to 8 carbon glycol or glycol ether.
There remains a need for further improvements in terms of the freeze-thaw r~sisLa"ce of aqueous epoxy resin dispersions and in terms of the cor, osio"
~sislance and ~;I ,er"ical resislance of coalings derived from aqueous epoxy resin dispersions which are adapted for application as industrial maintenance coating systems.
Accordingly, it is a primary object of this invention to provide a self-dispersing curable epoxy resin which may be dispersed in water without the necessity for an additive to stabilize the epoxy dispersion.
Another object of this invention is to provide ~ eous dispersions of self-dispersing curable epoxy resins which exhibit long term stability under ambient storage conditions.
~O 95/01387 .~ . a t~ ~ 2 1 6 6 4 1 4 PCT/US94/06770 Yet another object of this invention is to provide coating compositions incorporating a self-disper~ing curabie epoxy resin, where the coating composition exhibits excellent properties when cured.
Other objects and advanlages of the present invention shall become 5 apparent from the accor"~,anying des~ri~tion and examples.
SummarY of the Invention It has been found that a self-dispersing curable epoxy composition can be prepared upon conlacting (a) 1.0 reactive equivalents of an epoxy resin, (b) from about 0.01 to 1.0 reactive equivalents of a polyhydric phenol, and (c) from about 0.005 to 0.5 reactive equivalents of an amine-epoxy ~dd~ ~ct, wherein the amine-epoxy ~dd~ ~ct is formed upon conlacling 1.0 equivalents of an aliphatic polyepoxide and from about 0.3 and 0.9 reactive equivalents of a polyoxyalkyleneamine.
The self-disper-~;ing curable epoxy resin of the invention forms an ~queQu-s disper~ion upon mixing with water. When cured, films of the self-dispersing curable epoxy resin are useful as a coating composition.
Detailed Desc, i~lion of the Invention The self-dispersing curable epoxy resin formulation of the invention is prepared upon co"lacling (a) 1.0 reactive equivalents of an epoxy resin, (b) from about 0.01 to 1.0 reactive equivalents, preferably from about 0.4 to 0.6 reactive equivalents of a polyhydric phenol, and (c) from about 0.005 to 0.5 reactive equivalents (typically from about 0.005 to 0.05 reactive equivalents, WO 95/01387 i m ~ 2 1 6 6 4 1 4 PCT/US94/06770 ~
more typically from about 0.005 to 0.025 reactive equivalents, and preferably from about 0.005 to 0.015 reactive equivalents) of an amine-epoxy adduct, wherein the amine-epoxy adduct is formed upon conlcicti,-9 1.0 equivalents of an aliphatic polyepoxide and from about 0.3 to 0.9 reactive equivalents, 5 preferaL,ly from about 0.6 and 0.8 reactive equivalents of a poîyoxyalkyle"ean ,ine.
The PolYoxYalkvleneamine The polyoxyalkyleneamine reactant com,c rises one or more amino-compounds where the amino-compound comprises both an amine group and 10 a s~ Ihst~ntially water-soluble polyether chain. The polyoxyalkyleneamine reactanl is soluble or at least partialîy soluble in water. Techniques to ,..repare suitable polyoxyalkyleneamine rea~a, lls are known in the art, and include reacting a hydroxyl group containing initiator with ethylene oxide and/or propylene oxide, followed by conversion of the resulting terminal 1~ hydroxyl group(s) to amine(s). Illustrative of the polyoxyalkyleneamine reacLanls employed in the invention are the Jeffamine (Reg. TM) brand of polyoxyalkyleneamines available from Texaco Chemical Company, Bellaire, Texas.
The polyoxyalkyleneamines of this invention have the structural 20 formula R,-O-R2-CH2CH(R3)-NH2 wherein ~WOg5/01387 ~ ia!~ 21664~4 PCTluS94/06770 R, designates a monovalent organic radical selected from the group consisling of C, to C,2 aliphatic, alicyclic or aro",dlic h~ oca~bons, and R2 represents a polyoxyalkylene chain having the structural formula:
(cH2-cH2-o).-(cH2-cH(R4)-o)b wherein R4 is a monovalent organic radical selected from the group consisting of C, to C4 aliphatic hydrocarbons, 'a' designates a number of ethoxy groups (CH2-CH2-O), 'b' designates a number of monosl ~bstituted ethoxy groups (CH2-CH(R4)-O) where the substitution of one monos~ ~hstitl Ited ethoxy group is independent from the substitution of any other monos~ Ihstituted ethoxy group in the polyoxyalkylene chain, the sum of 'a' and 'b' is equal to or greater than 10 butless than or equal to 200, and where the sequence of ethoxy and monosl Ihstituted ethoxy groups within a polyoxyalkylene chain may be completely random and/or there may be blocks of ethoxy and/or monosl ~hstituted ethoxy groups, and R3 designates H or a monovalent organic radical selected from the group consisting of C, to C4 aliphatic hyd, ocarbons.
P~erer,ed polyoxyalkyleneamines have R" R3 and R4 each equal to methyl, and either (i) a ratio of 'a' and 'b' of about 4:1, wherein the ethoxy and iso-propoxy groups are arranged in random blocks and the molecular weight of the polyoxyalkyleneamine is less than about 4,000, or (ii) a block of 5 ethoxy groups joined to a random sequence of ethoxy and iso-propoxy WO 95/01387 ~ a ~ 6 6 4 1 4 PCT/US94/06770 groups wherein the ratio of 'a' and 'b' in the random sequence is about 7:3 and the molecular weight of the polyoxyalkyleneamine is less than about 4 000 or (iii) a ratio of 'a' and 'b' of about 95:5 wherein the ethoxy and iso-propoxy groups are arranged sl ~l,sl~nLially in two blocks and the molecular weight of the polyoxyalkyleneamine is less than about 6 000 or (iv) a ratio of 'a' and 'b' of about 7:3 wherein the ethoxy and iso-~ ropoxy groups are present in random sequence and the molecular weight of the polyoxyalkyleneamine is less than about 4 000 or (v) a ratio of 'a' and 'b' of about 4:1 wherein the ethoxy and iso-p,upoxy groups are prese"l in ra,-dor"
sequence and the molecular weight of the polyoxyalkyleneamine is less than about 4 000.
The most preferred polyoxyalkyleneamine is Jeffamine (Reg. TM) M-2070 from Texaco Chemical Con,,~a,)y Bellaire Texas. Accordi,)g to Texaco this polyoxyalkyleneamine is ,~repared by reacting methanol with ethylene oxide and propylene oxide followed by conversion of the resulting terl"inal hydroxyl group to an amine. The most pr are"ad polyoxyalkyleneamine has an approximate molecular weight of 2 000 and a mole ratio of propylene oxide to ethylene oxide of 10/32.
The AliPhatic PolYePoxide The aliphatic polyepoxide reactant comprises one or more compounds each having a plurality of epoxide functional groups. The aliphatic polyepoxide reactanl has at least 2 epoxide groups present in the molecule and may have as many as 6 epoxide groups present in the molecule.
~WO 95/013$7 ,;~ S 2 1 6 6 4 1 4 PCT/US94/06770 , Techniques to prepare suitable polyepoxide compounds are known in the art, and include reacting compounds having a plurality of hydroxyl groups with epichlorohydrin in the presence of a suitable catalyst. Suitable aliphatic polyepoxide cor"pounds are commercially available from Henkel CorporaliG,), 5 Ambler Pennsylvania underthe lrddelna,ks "Capcures Reg. TM" or "Pl ,olo"~ers Reg. TM"
One representative class of aliphatic polyepoxide reactant according to the invention has the structural formula:
D ~D -H~ ~D ~H -"H-"H `
'~5~'6 Jc~ 2 ~' ~' 2Jd wherein Rs designates a linear, branched or cyclic aliphatic or alicyclic organic radical having a valency equal to the sum of 'c' and 'd', where the sum of 'c' 15 and 'd' is equal to or ~,ealer than 2 but no more than or equal to 6 and where 'd' is equal to or greater than 2 but less than or equal to 6. When the sum of 'c' and 'd' equals two (2), R5 designates a linear, branched or cyclic aliphatic or alicyclic divalent organic radical having from 2 to 14 carbon atoms, and specifically includes the hydrocarbon portions of the dihydric alcohols 20 ethylene glycol, butylene glycol, hexylene glycol, decanediol and dodecanediol which remain after the hydroxyl groups have been removed, and when the sum of 'c' and 'd' equals three (3), Rs designates a linear, branchecl or cyclic aliphatic or alicyclic trivalent organic radical having from 3 to 14 carbon atoms, and specifically includes the hycl,ocarbon portions of the WO 95101387 -i I i ?. ~ ~ 2 1 6 6 4 1 4 PCT/US94/06770 ~
trihydric alcohols glycerol, 1,1,1-tris(hydroxymethyl)ethane, and 2-ethyl-2-(hydroxymethyl)-1,3-propanediol which remain after the hydroxyl groups have been removed, and when the sum of 'c' and 'd' equals four (4), R5 designates a linear, branched or cyclic aliphatic or alicyclic tetravalent organic radical 5 having from 5 to 30 carbon atoms, and specifically includes the hydrocarbon ~,o, liol) of the tetrahydric alcohol pentaerythritol which remains after the hydroxyl groups have been removed, and when the sum of 'c' and 'd' equals five (5), R5 designates a linear, branched or cyclic aliphatic or alicyclic pentavalent organic radical having from 6 to 30 carbon atoms, and when the 10 sum of 'c' and 'd' equals six (6), R5 designates a linear, branched or cyclic aliphatic or alicyclic hexavalent organic radical having from 8 to 30 carbon atoms, and specifically includes the hyd,ocarbon portion of the hexahydric alcohol dipentaerythritol which remains after the hydroxyl groups have been removed, and R6 represel,ls a divalent polyoxyalkylene chain having the structural formula:
-O-(CH2-CH2-O).-(CH2-CH(R7)-O)f wherein R, is a monovalent organic radical selected from the 20 group consisting of Cl to C~ aliphatic hydrocarl,ons, 'e' designates a number of ethoxy groups (CH2-CH2-O), 'f' designates a number of monosubstituted ethoxy groups (CH2-CH(R7)-0) where the substitution of one monosubstituted ethoxy group is independent from the substitution of any other monosubstituted ~0 95/01387 ~ 2 1 6 6 4 1 4 PCT/US94/06770 ethoxy group in the poiyoxyalkylene chain, the sum of 'e' and 'f' is equal to or y(ea~er than 0 but less than or equal to 10, and where the sequence of ethoxy and monos~ ~hstituted ethoxy groups within a polyoxyalkylene chain may be completely random and/or there may be blocks of ethoxy and/or mo"osuhstituted ethoxy groups.
The most prefer,ed aliphatic polyepoxide compound is the reaction product of pentaerythritol, propylene oxide and epichlorohydrin, having an epoxide equivalent weight (EEW) of about 230.
The E~oxy Resin The epoxy resin used in the practice of this invention comprises one or more polyglycidyl ethers of polyhydric phenols having two (2) or more epoxide groups and o~e (1 ) or more six-carbon aromatized rings present in the molecule, as represented by the structural formula:
R8(CH2-CH2)o \ /
wherein R8 represents a '9' valent C6-Cso organic radical co"~risins~ at least one six-car60n aron,ali~ed ring (e.g. when g is 2, Rs can be -CH2 - O -0-C(CH3)2-0-0-CH2- or Rs can be -CH2 - 0 -0-CH2-0-0-CH2- wherein 0 represents a phenyl group), and 'g' is equal to or greater than 2 but less than or equal to 6.
Cross-Rerere"ce to Related APPlications This application is a continuation-in-part of U.S. Serial No. 08/086,288, filed June 30, 1993, the ~lisclosllre of which is incorporated by reference herein.
Field Of The Invention The present invention relates to coating compositions made from aqueous epoxy dispersions. More specifically, this invention relates to self-dispersing curable epoxy resins, and to aqueo! ~s dispersions and coating 5 compositions comprising the same.
WO 95/01387 ~ 2 1 6 6 ~ 1 4 PCT/US94/06770 ~
Back~round of the Invention Epoxy resins have come into widespread use as components in coating compositions. Coatings which comprise cured epoxy resins are valued for their durability, chemical resislance, and excellent adhesion to a 5 broad range of substrates. Particularly desitable 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 directed to the development of aq~ ~eo~ ~s dispersions and emulsions of epoxy resins.
One class of ~l leo! ls epoxy dispersions employs one or more additives, also known as dispersanls or emulsifiers or su, rac~anls, which are necess~y to stabilize the epoxy resin in the dispersion or emulsion form.
Represenlalive examples include an a~ueo~ ~s epoxy dispersion as described in U.S. Patent No. 3,301,804 (employing the reaction product of a boric acid 15 ester derived from boric acid with both an alkylene glycol and a beta-dialkyl-substituted aminoalkanol as an emulsifier), U.S. Patent No. 3,634,348 (employing a phosphate ester as an emulsifying agent), U.S. Patent No.
3,249,412 (employing in combination a cationic emulsifying agent selected from the group consisling of imidazolines and amides and a non-ionic 20 emulsifying agent), and Specialty Chemicals Bulletin SC-021 titled "Water-Reducible Coatings via Epoxy Resin Modification with Jeffamine (Reg. TM) ED-2001 and Jeffamine (Reg. TM) M-1000" available from Texaco Chemical Company, Bellaire, Texas. Another example comes from the technical literature of Synthron Inc., Morgantown, North Carolina, which discloses the ~WO 95/01387 ~ '~ 2 1 6 6 4 1 4 PCT/US94/06770 use ol' PROX-E-141, a diglycidyl ether of Pluronic (Reg. TM) F88 diol (an ethylene oxide - propylene oxide - ethylene oxide block copolymer available from E3ASF Pe, ror",a,lce Chemicals, Par~i,upany, New Jersey) as a reactive dispersant for epoxy resins. PROX-E-141 can act as a dispersant for epoxy 5 resin Dn water, but then will react along with the epoxy resin when exrosed to an amine functional curing agent.
The use of an additive to provide stability to an aqueous epoxy dispersion is preferably avoided as such additives add additional cost, formulation complexity, and may potentially interfere with the performance of 10 a coating derived from the ~queous epoxy dispersion.
It is known to prepare aqueous epoxy dispersions from self-emulsifying epoxy resins. For example, U.S. Patent No. 4,315,044 describes a stable epoxy dispersion co",posilion comprising (1) an ~ eo~s medium; and (2) between about 50-70 weight peroenl of self-emulsifying epoxy resin which is 15 the addition product of r~acta, ll~ coi "~., ising (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 by weight of diglycidyl ether of polyoxyalkylene glycol, where~in the molecular weight of the epoxy resin is in the range between about 500-20,000. The dispersion can also contain 1-25 weight percent 20 based on resin solids of a water-immiscible C8-C20 aliphatic monoepoxide reactive diluent.
U.S. Patent No. 4,608,406 describes stable aqueous epoxy resin dispel~ions comprised of (1) an aqueous medium; and (2) between about 50 to about 70 weight percent of self-emulsifying epoxy resin which is the WO 95/01387 ~ t ~ 2 1 6 6 4 1 4 PCT/US94/06770 ~
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 epoxy resin is in the range of about 1000 to about 20 000. The stable dispersions can be modified by the addition of about 1 to about 25 weight per~nt of an aliphatic ",o"oepoxide reactive diluent.
In an allelllpt to improve freeze-thaw stability, the stable aqueous ~epoxy resin dispersions can be modified by the addition of about 5-20 weight percent based on resin solids weight, of a water-miscible solvent which, prererably, is a 2 to 8 carbon glycol or glycol ether.
There remains a need for further improvements in terms of the freeze-thaw r~sisLa"ce of aqueous epoxy resin dispersions and in terms of the cor, osio"
~sislance and ~;I ,er"ical resislance of coalings derived from aqueous epoxy resin dispersions which are adapted for application as industrial maintenance coating systems.
Accordingly, it is a primary object of this invention to provide a self-dispersing curable epoxy resin which may be dispersed in water without the necessity for an additive to stabilize the epoxy dispersion.
Another object of this invention is to provide ~ eous dispersions of self-dispersing curable epoxy resins which exhibit long term stability under ambient storage conditions.
~O 95/01387 .~ . a t~ ~ 2 1 6 6 4 1 4 PCT/US94/06770 Yet another object of this invention is to provide coating compositions incorporating a self-disper~ing curabie epoxy resin, where the coating composition exhibits excellent properties when cured.
Other objects and advanlages of the present invention shall become 5 apparent from the accor"~,anying des~ri~tion and examples.
SummarY of the Invention It has been found that a self-dispersing curable epoxy composition can be prepared upon conlacting (a) 1.0 reactive equivalents of an epoxy resin, (b) from about 0.01 to 1.0 reactive equivalents of a polyhydric phenol, and (c) from about 0.005 to 0.5 reactive equivalents of an amine-epoxy ~dd~ ~ct, wherein the amine-epoxy ~dd~ ~ct is formed upon conlacling 1.0 equivalents of an aliphatic polyepoxide and from about 0.3 and 0.9 reactive equivalents of a polyoxyalkyleneamine.
The self-disper-~;ing curable epoxy resin of the invention forms an ~queQu-s disper~ion upon mixing with water. When cured, films of the self-dispersing curable epoxy resin are useful as a coating composition.
Detailed Desc, i~lion of the Invention The self-dispersing curable epoxy resin formulation of the invention is prepared upon co"lacling (a) 1.0 reactive equivalents of an epoxy resin, (b) from about 0.01 to 1.0 reactive equivalents, preferably from about 0.4 to 0.6 reactive equivalents of a polyhydric phenol, and (c) from about 0.005 to 0.5 reactive equivalents (typically from about 0.005 to 0.05 reactive equivalents, WO 95/01387 i m ~ 2 1 6 6 4 1 4 PCT/US94/06770 ~
more typically from about 0.005 to 0.025 reactive equivalents, and preferably from about 0.005 to 0.015 reactive equivalents) of an amine-epoxy adduct, wherein the amine-epoxy adduct is formed upon conlcicti,-9 1.0 equivalents of an aliphatic polyepoxide and from about 0.3 to 0.9 reactive equivalents, 5 preferaL,ly from about 0.6 and 0.8 reactive equivalents of a poîyoxyalkyle"ean ,ine.
The PolYoxYalkvleneamine The polyoxyalkyleneamine reactant com,c rises one or more amino-compounds where the amino-compound comprises both an amine group and 10 a s~ Ihst~ntially water-soluble polyether chain. The polyoxyalkyleneamine reactanl is soluble or at least partialîy soluble in water. Techniques to ,..repare suitable polyoxyalkyleneamine rea~a, lls are known in the art, and include reacting a hydroxyl group containing initiator with ethylene oxide and/or propylene oxide, followed by conversion of the resulting terminal 1~ hydroxyl group(s) to amine(s). Illustrative of the polyoxyalkyleneamine reacLanls employed in the invention are the Jeffamine (Reg. TM) brand of polyoxyalkyleneamines available from Texaco Chemical Company, Bellaire, Texas.
The polyoxyalkyleneamines of this invention have the structural 20 formula R,-O-R2-CH2CH(R3)-NH2 wherein ~WOg5/01387 ~ ia!~ 21664~4 PCTluS94/06770 R, designates a monovalent organic radical selected from the group consisling of C, to C,2 aliphatic, alicyclic or aro",dlic h~ oca~bons, and R2 represents a polyoxyalkylene chain having the structural formula:
(cH2-cH2-o).-(cH2-cH(R4)-o)b wherein R4 is a monovalent organic radical selected from the group consisting of C, to C4 aliphatic hydrocarbons, 'a' designates a number of ethoxy groups (CH2-CH2-O), 'b' designates a number of monosl ~bstituted ethoxy groups (CH2-CH(R4)-O) where the substitution of one monos~ ~hstitl Ited ethoxy group is independent from the substitution of any other monos~ Ihstituted ethoxy group in the polyoxyalkylene chain, the sum of 'a' and 'b' is equal to or greater than 10 butless than or equal to 200, and where the sequence of ethoxy and monosl Ihstituted ethoxy groups within a polyoxyalkylene chain may be completely random and/or there may be blocks of ethoxy and/or monosl ~hstituted ethoxy groups, and R3 designates H or a monovalent organic radical selected from the group consisting of C, to C4 aliphatic hyd, ocarbons.
P~erer,ed polyoxyalkyleneamines have R" R3 and R4 each equal to methyl, and either (i) a ratio of 'a' and 'b' of about 4:1, wherein the ethoxy and iso-propoxy groups are arranged in random blocks and the molecular weight of the polyoxyalkyleneamine is less than about 4,000, or (ii) a block of 5 ethoxy groups joined to a random sequence of ethoxy and iso-propoxy WO 95/01387 ~ a ~ 6 6 4 1 4 PCT/US94/06770 groups wherein the ratio of 'a' and 'b' in the random sequence is about 7:3 and the molecular weight of the polyoxyalkyleneamine is less than about 4 000 or (iii) a ratio of 'a' and 'b' of about 95:5 wherein the ethoxy and iso-propoxy groups are arranged sl ~l,sl~nLially in two blocks and the molecular weight of the polyoxyalkyleneamine is less than about 6 000 or (iv) a ratio of 'a' and 'b' of about 7:3 wherein the ethoxy and iso-~ ropoxy groups are present in random sequence and the molecular weight of the polyoxyalkyleneamine is less than about 4 000 or (v) a ratio of 'a' and 'b' of about 4:1 wherein the ethoxy and iso-p,upoxy groups are prese"l in ra,-dor"
sequence and the molecular weight of the polyoxyalkyleneamine is less than about 4 000.
The most preferred polyoxyalkyleneamine is Jeffamine (Reg. TM) M-2070 from Texaco Chemical Con,,~a,)y Bellaire Texas. Accordi,)g to Texaco this polyoxyalkyleneamine is ,~repared by reacting methanol with ethylene oxide and propylene oxide followed by conversion of the resulting terl"inal hydroxyl group to an amine. The most pr are"ad polyoxyalkyleneamine has an approximate molecular weight of 2 000 and a mole ratio of propylene oxide to ethylene oxide of 10/32.
The AliPhatic PolYePoxide The aliphatic polyepoxide reactant comprises one or more compounds each having a plurality of epoxide functional groups. The aliphatic polyepoxide reactanl has at least 2 epoxide groups present in the molecule and may have as many as 6 epoxide groups present in the molecule.
~WO 95/013$7 ,;~ S 2 1 6 6 4 1 4 PCT/US94/06770 , Techniques to prepare suitable polyepoxide compounds are known in the art, and include reacting compounds having a plurality of hydroxyl groups with epichlorohydrin in the presence of a suitable catalyst. Suitable aliphatic polyepoxide cor"pounds are commercially available from Henkel CorporaliG,), 5 Ambler Pennsylvania underthe lrddelna,ks "Capcures Reg. TM" or "Pl ,olo"~ers Reg. TM"
One representative class of aliphatic polyepoxide reactant according to the invention has the structural formula:
D ~D -H~ ~D ~H -"H-"H `
'~5~'6 Jc~ 2 ~' ~' 2Jd wherein Rs designates a linear, branched or cyclic aliphatic or alicyclic organic radical having a valency equal to the sum of 'c' and 'd', where the sum of 'c' 15 and 'd' is equal to or ~,ealer than 2 but no more than or equal to 6 and where 'd' is equal to or greater than 2 but less than or equal to 6. When the sum of 'c' and 'd' equals two (2), R5 designates a linear, branched or cyclic aliphatic or alicyclic divalent organic radical having from 2 to 14 carbon atoms, and specifically includes the hydrocarbon portions of the dihydric alcohols 20 ethylene glycol, butylene glycol, hexylene glycol, decanediol and dodecanediol which remain after the hydroxyl groups have been removed, and when the sum of 'c' and 'd' equals three (3), Rs designates a linear, branchecl or cyclic aliphatic or alicyclic trivalent organic radical having from 3 to 14 carbon atoms, and specifically includes the hycl,ocarbon portions of the WO 95101387 -i I i ?. ~ ~ 2 1 6 6 4 1 4 PCT/US94/06770 ~
trihydric alcohols glycerol, 1,1,1-tris(hydroxymethyl)ethane, and 2-ethyl-2-(hydroxymethyl)-1,3-propanediol which remain after the hydroxyl groups have been removed, and when the sum of 'c' and 'd' equals four (4), R5 designates a linear, branched or cyclic aliphatic or alicyclic tetravalent organic radical 5 having from 5 to 30 carbon atoms, and specifically includes the hydrocarbon ~,o, liol) of the tetrahydric alcohol pentaerythritol which remains after the hydroxyl groups have been removed, and when the sum of 'c' and 'd' equals five (5), R5 designates a linear, branched or cyclic aliphatic or alicyclic pentavalent organic radical having from 6 to 30 carbon atoms, and when the 10 sum of 'c' and 'd' equals six (6), R5 designates a linear, branched or cyclic aliphatic or alicyclic hexavalent organic radical having from 8 to 30 carbon atoms, and specifically includes the hyd,ocarbon portion of the hexahydric alcohol dipentaerythritol which remains after the hydroxyl groups have been removed, and R6 represel,ls a divalent polyoxyalkylene chain having the structural formula:
-O-(CH2-CH2-O).-(CH2-CH(R7)-O)f wherein R, is a monovalent organic radical selected from the 20 group consisting of Cl to C~ aliphatic hydrocarl,ons, 'e' designates a number of ethoxy groups (CH2-CH2-O), 'f' designates a number of monosubstituted ethoxy groups (CH2-CH(R7)-0) where the substitution of one monosubstituted ethoxy group is independent from the substitution of any other monosubstituted ~0 95/01387 ~ 2 1 6 6 4 1 4 PCT/US94/06770 ethoxy group in the poiyoxyalkylene chain, the sum of 'e' and 'f' is equal to or y(ea~er than 0 but less than or equal to 10, and where the sequence of ethoxy and monos~ ~hstituted ethoxy groups within a polyoxyalkylene chain may be completely random and/or there may be blocks of ethoxy and/or mo"osuhstituted ethoxy groups.
The most prefer,ed aliphatic polyepoxide compound is the reaction product of pentaerythritol, propylene oxide and epichlorohydrin, having an epoxide equivalent weight (EEW) of about 230.
The E~oxy Resin The epoxy resin used in the practice of this invention comprises one or more polyglycidyl ethers of polyhydric phenols having two (2) or more epoxide groups and o~e (1 ) or more six-carbon aromatized rings present in the molecule, as represented by the structural formula:
R8(CH2-CH2)o \ /
wherein R8 represents a '9' valent C6-Cso organic radical co"~risins~ at least one six-car60n aron,ali~ed ring (e.g. when g is 2, Rs can be -CH2 - O -0-C(CH3)2-0-0-CH2- or Rs can be -CH2 - 0 -0-CH2-0-0-CH2- wherein 0 represents a phenyl group), and 'g' is equal to or greater than 2 but less than or equal to 6.
2 1 6 6 4 1 4 PCT/US94/06770 ~
Techniques to prepare such epoxy resins are known in the art, and include reacting compounds having 2 or more hydroxyl groups with epichlorohydrin in the presence of a suitable catalyst. Suitable epoxy resins are commercially available from a variety of sources and include EPON (Reg.
TM) epoxy resins from Shell Chemical CGr"pa, Iy, Houston, Texas, and DER
(Reg. TM) or DEN (Reg. TM) epoxy resins from Dow Ci)er"ical Co",,.any, Midland, Michigan.
Examples of suitable epoxy resins are:
I) Polyglycidyl and poly(beta-methylglycidyl) esters obtainable by reacting a compound having at least two carboxy groups in the molecule with epichlorohydrin or beta-methyl-epichlorohydrin, respectively. The reaction is adva"ldgeously carried out in the presence of bases. Examples of ar~l"dlic polycarboxylic acids which may be used include, for example, phthalic acid, isophll,alic acid or tere~chlhalic acid.
Il) Polyglycidyl or poly(beta-methylglycidyl) ethers obtainable by re~cting a compound having at least two free phenolic hydroxy groups with epichlorohydrin or beta-methyl-epichlorohydrin, respectively, under alkaline conditions, or in the presence of an acid catalyst and with sl ~hseq! lent alkali lr~aln,ent.
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, bis(4-hydroxyphenyl)methane, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)sulfone~ 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-~0 95~01387 ~ a ~ ~ ~ 2 1 6 6 4 1 4 PCTIUSg4/06770 dibrorno-4-hydroxyphenyl) pro~a"e, and from novolacs obtainable by conder,salion of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfuraldehyde, with phenols, such as phenol, or with phenols that are substituted in the nucle~ ~s by halide atoms or C,-C,8 (~ rererably C,- Cg) alkyl 5 groups, such as, for example, 4-chlorophenol, 2-methylphenol or 4-tert-butylphenol, or by conde"salio" with bisphenols, in the ma""er described above.
There are preferably used epoxy resins that have an epoxy conlenl of from 2 to 10 equivalents/mole and that are glycidyl ethers or glycidyl esters of 10 aro"~alic or alkylarol"d~ic corl,pounds. Especially prefer,ed epoxy resins are polyglycidyl ethers of bisphenols, such as, for example, of 2,2-bis(4-hydroxyphenyl)propane (bispl ,enol A) or bis(4-hydroxyphenyl)methane (bisphenol F), or novolacs formed by reacliny formaldehyde with a phenol.
For reasons of cost and availability, the most preferred epoxy resins are 15 polyglycidyl ethers based on bisphenol A.
P~ efel, ed epoxy resins have an epoxide equivalent weight of less than about 400 grams/squivalent, e.g. from about 100 grams/equivalent to about 350 grams/equivalent, more ,l~referably from about 150 grams/equivalent to about 225 grams/equivalent, e.g. DER 331 available from Dow Chemical at 20 about 182 grams/equivalent.
The PolYhYdric Phenol The polyhydric phenol reactanl comprises one or more compounds each having a plurality of hydroxyl groups covalently bonded to one or more WO 95/01387 , ~ 2 1 ~ ~ 4 1 4 PCT/US94/06770 ~
six-carbon aromali~ed rings. The polyhydric phenol reactant may contain substituents such as alkyl, aryl, sulfido, sulfonyl, halo, and the like. The polyhydric phenol is represented by the structural formula:
R~(OH)h 5 wherein R9 represents an 'h' valent C6-Cso organic radical co",prisi"g at least one six-carbon aro",~ ed ring, and 'h' represents a number of phenolic hydroxyl groups where 'h' is equal to or greater than 2 but less than or equal to6.
Techniques to prepare suitable polyhydric phenol compounds are known in the art. Suitable polyhydric phenol compounds are commercially available from Dow Chemical Coi"pally, Midland Michigan, and Shell Chemical Compa,-y, Houston, Texas.
Illustrative of suitable polyhydric phenols are 2,2-bis(4-hydroxyphenyl)pro,t~ane, 2,2-bis(3-bromo4-hydroxyphenyl)-propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)-methane, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, resorcinol, hydroquinone, phenol-formaldehyde novolac resins, and the like. The most 20 prefer,ed dihydric phenols are 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) and bis(4-hydroxyphenyl)methane (bisphenol F) for reasons of cost and availability.
~O 95/0L387 ~ C; 2 1 6 6 4 1 4 PCT/US94/06770 The Amine-Epoxy Adduct The preparation of the self-dispersing curable epoxy resins of the invenl:ion may proceed through an amine-epoxy ~ld~ ~ct, where the amine-epoxy ~dduct is s' ~hseq! ~ently reacted with a polyhydric phenol and an epoxy 5 resin. The structure of the amine-epoxy ~dduct is dependant on the structQ-res of the polyoxyalkyleneamine and the aliphatic polyepoxide used in the preparalion of the amine-epoxy ~dduct, as well as the relative ratio of the r ~a.:l~" ItS.
A represenlali-/e amine-epoxy adduct has the structural formula:
10((CH2-CH-R6)(d "(H-R6)CR5R6-CH(OH)CH2-N-\ / I
O R,-O-R2-CH2CH(R3) [cH2cH(oH)-R6-Rs(-R6-cH-cH2)(d-2)(-R6-H)c-F~6-cH(oH) O
CH2-N]jCH2CH(OH)-R6-Rs(-R6-cH2cH-cH2)(d 1)(-R6-H)c) \ /
20(R3)CHCH2-R2-O-R, O
wherein 'i' indiG~tes a number of repetitive units where 'i' is equal to or greater than zero (0) but less than or equal to about fifty.
- The Self-DisPersin~ Curable EPOXY Resin 25The self-dispersing curable epoxy resins of the invention may be prepared by reacting an amine-epoxy adduct with a polyhydric phenol and an WO 95/01387 ~ ' 2 1 ~ 6 4 1 4 PCT/US94/06770 epoxy resin. 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 epoxy resin, the identity of the polyhydric phenol and the relative ratio of the reac~a"~s.
The products of the above reactiGn are envisioned to be an extremely com,cl_x mixture of polymeric malel ials cc ,n~, ising two cl;slinct groups. A
simplified structure for each group of reaction products can be shown if it is assumed that the phenolic cGr"p~nenl is dihydric and the epoxy component is a diepoxide.
Structure rll (CH2-CH-R8-CH(OH)-CH20-[R~,-OCH2-CH(OH)-R8-CH(OH)-CH20-]J-O
R9o-cH2-cH(oH)-R8-cH-cH2) wherein 'j' in-licAles a number of repealir~9 units, and is equal to or greater than zero (0) but less than or equal to twenty (20).
20 Structure rlll [(GE)(d-1)(R6-H)cR5-R6-cH2-cH(oH)-cH2-N-R,-O-R2-CH2CH(R3) [CH2cH(oH)-R6-R~(GE)(d-2)(R6-H)cR6-cH(oH)cH2-N]i-R2-CH2CH(R3) 2 1 6 6 ~ 1 4 ~0 95/01387 ~ t .5 ~ i, PCT/US94/06770 CH2cH(oH)-R6-Rs(GE)(d~ H) wherein 'GE' is defined as -R6-cH(oH)cH2-o-[R9-o-cH2cH(oH)-R8-cH(oH)cH2-o]
CH2CH(OH)-R8-CH-CH2 \ I
and all other variables are as defined above.
Orqanic Cosolvents The self-dispersing curable epoxy resin of the present invention may 10 be combined with a non-reactive, water-miscible, organic cosolvent. The cosolvent serves to reduce the viscosity of the self-dispersing curable epoxy resin. rl erer, ed organic cosolvents include the alkyl ethers of monohydric and dihydric alcohols, where the alkyl group comprises C,-C8 linear or branched aliphatic or alicyclic chains. The choice of cosolvent can affect the 15 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 (Easl",an Chemicals) with one of the following cosolvents (the greater increase being obtained in order): 1-methoxy-2-propyl ~cet:~te, methyl n-amyl ketone, or dipropylene glycol n-butyl ether.
20 Reactive Diluents The ~refe" ed stable a~ ~eo~ Is epoxy resin dispersions of the present invention are those which contain a water-immiscible C8-C20 aliphatic r ~ 2 1 6 6 4 1 4 WO 95/01387 - ' PCT/US94/06770 monoepoxide reactive diluent. The said monoepoxide component can contain alicyclic and aromatic structures as well as halogen sulfur p hos~l ,orus, and other such heteroalor"s. Suitable reactive diluents are available from CVC Specialty Chemicals Inc., Cherry Hill, New Jersey.
Illustrative of monoepoxide reactive diluents are epoxidized unsaturated hydrocarbons such as decene and cyclohexene; glycidyl ethers of monohydric alcohols such as 2-ethylhexanol doclec~nol and eicosa, lol;
glycidyl esters of ",onocarboxylic acids such as hexanoic acid; ~cet~ls of glycidaldehyde; and the like. The preferred reactive diluent is glycidyl ether of monohydric C8-C10 aliphatic alcohols.
The presence of a water-immiscible C8-C20 aliphatic monoepoxide reactive diluent in an aqueous epoxy resin dispersion has significant beneficial effects in addiliGn to modifying the viscosity of the dispersion. Forexample, the said water-i"""iscit~le reactive diluent appears to coat the particles of epoxy resin solids and thereby. provide the aqueous dispersion with improved shear, freeze-thaw resislance shelf viscosity stability, and paint gloss.
Also, since the reactive diluent is epoxy functional it becomes chemically bonded into the film which is formed during the subsequent room temperature curing of the aqueous dispersion composition after it has been blended with a curing agent and coated on a surface. The total quantity of reactive diluent contributes to the calcl ll~ted proportion of non-volatiles in the dispersion composition.
. ~ ~ 21 6641 4 ~0 95/01387 ~ S PCT/US94/06770 Preparation of the Self-DisPersinq Curable EpoxY Resin In pl eparing the self-dispersing curable epoxy resins of this invention, an arnine-epoxy addud is first ~.repared by combining the polyoxyalkyleneamine reactal)t and the aliphatic polyepoxide reaclanl, healing the mixture slowly to about 130 C, holding the mixture at temperature for about 2.5 hours, and then discl ,aryi"y the amine-epoxy ~dd~ lc.t from the reactor. The self-dispersing epoxy resin is prepared by c~"lbir,ing the amine-epoxy ~dduct, 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 exoLl1er",ic reaction will then occur, and cooling is applied to maintain the reaction temperature at about 150-160 C. The mixture is mainlained at about 160 C for about one hour s~ ~hse~ ~ent to the conclusion of the exoll ,er",ic reaction, followed by heating to 190 C. The reaction is maintained at 190 C for about 15 minutes in order to drive the reaction to completion, then cooled to about 160 C whereupon a small amount of a water-soluble organic solvent is added prior to cooling and discharging the self-dispersing curable epoxy resin from the reactor.
Preparation of an Aqueous DisPersion of the Self-DisPersinq Curable EPOXY
Resin The aqueous epoxy dispersion of the invention is prepared by charging the sel~-dispersing curable epoxy resin to a reaction vessel, then heating the resin to about 50-100 C with stirring. Water is gradually added d ~ ~ ~
WO 95/01387 2 1 ~ 6 4 1 4 PCT/US94/06770 ~ .
to the self-dispersing curabie epoxy resin while the temperature is allowed to drop to about 50 C. During this period, the water in oil dispersion is formed and then inverts to an oil in water disper~ion. After inversion, additional water may be added as well as reactive diluent in the form of a C8-C10 alcohol 5 mono~lycidyl ether.
The particle size of the oil phase in the aqueous disper~ion can be modified by physical techniques to reduce the particle size. The particle size red~ ~ction is ,ureferably acco""~lished by subjecting an ~q~ ~eo! ~s dispersion of the precipit~e to high shear, e.g. in a hor"ogenizer such as that disclosed in U.S. Patent No. 4,533,254 (Cook et al.), the ~isclos~re of which is i, ,cor,uordled herein be reference, and commercially available as MICROFLUIDIZERTM from Microfluidics Cc: r~,oralion, Newton, Massachusett~
Homogenizers are ~iscussed in W. C. Griffin, "Emulsions", EncycloPedia of Chemical Technolo~Y. Vol. 8, pp. 900-930 (Kirk-Othmer, eds., John Wiley &
Sons, Inc., New York, New York, 3d ed., 1979), the disclosure of which is incorporated herein by reference.
The aqueous dispersion of self-dispersing resin will typically exhibit excellent chemical and physical stability over an extended shelf-life, e.g. of from five to six months. As an example of the chemical stability, the epoxide 20 equivalent weight (EEW) of the aq~ ~eo~ ~s dispersion of self-dispersing resin should remain essentially co"sla"l, e.g. should show no trend of increasing molecular weight, over a period of at least one month from the preparation of the aqueous dispersion.
~0 95/01387 . ~ PCT/US94/06770 Epoxide equivalent weight can be determined by dirrere, llial titration with perchloric acid using crystal violet as an indicator (e.g. a first sample is titrated with 0.1 N perchloric acid to an endpoint that shows the first sight of green color form the crystal violet indicator, the amine equivalent weight of 5 the dispersion is calcul~te:l from this titration, a second sample is mixed with ~xcess tetraethylan""Gnium bromide and titrated with 0.1 N perchloric acid to a green endpoint that persists for at least 30 seconds, total epoxide and amine equivalents are ~Icl ~ted from this titration, and the epoxide equivalent weight is calculated as the difference).
As an example of physical stability, the resin should not display layer for" ,ation for a period of at least one month from the prepal aLion of the :~ueous dispersion, i.e. there should be no for",alion of a macro-observable water phase as a layer separate from the dispersed resin phase.
Coatin~ ComPositions ComPrisinq an Aqueous Dispersion of the Self-15 DisPersin~ Curable EPOXY Resin The coating composition of the invention is ~repared by combining the aqueous epoxy dispersion with a suitable hardening agent. The coatings are tack free after 45 minutes and have excellent film properties. An aqueous epoxy resin paint composition of the present invention may further contain 20 additives conventionally employed in coating technology, such as organic piglllents, inorganic pigments, surfactants, thickeners, and the like.
A room tempera~LIre curable water-borne coating composition is prepared by admixing a stable epoxy dispersion composition as described Ij,r~,a~,~ 2l66414 above with an epoxy-interacting curing vehicle, such as a polyamine curing agent. The ratio of active amino hydrogens to epoxy groups in the admixture is in the range of from 0.5:1 to 2:1 and, preferably, is in the range between about 0.8:1 to 1.5:1. For purposes of industrial maintenance paint com~osilions, the amino hyd~oge"s must be sufficiently reactive to effect crosslinking inlera~lion with the epoxy groups at ambient temperatures.
Suitable polyamine curing agents are those which are soluble or dispersible in water and which co"lain more than 2 active hydrogen atoms per molecule. Examples of such curing agents are alkylene polyamines represented by the formula:
H2N-T-(NH-T)uNH2 wherein r is an alkylene radical containing 2 to 6 carbon atoms and 'u' is equal to or yl ealer than zero (0) but less than or equal to five (5). Such alkylene polyamines include ethylene diamine, diethylene triamine, triethylene teLra"~ e, tel,aelllylene penla",ine, pentaethylene hexamine, propylene diamine, dibutylene triamine, hexamethylene diamine, and the like.
Other polyamine curing agents that can be employed in the practice of this invention are the polyamido amines, which are reaction products of alkylene polyamines and fatty acids. Such polyamidoamines are well known in the art and are described in U.S. Pat. Nos. 2,705,223, 2,811,495 and 2,899,397, which patents are hereby incorporated by reference. Other polyamine curing agents are the ~ddl lctc of polyamines and epoxy compounds such as those described in U.S. Pat. Nos. 2,651,589, 2,864,775 ~VO 95/01387 ` ~ 2 1 6 6 4 1 4 PCT/U~i94/06770 and 4,116,900, which patents are hereby incorporated by reference.
Examples of useful curing agents also include those disclosed in U.S.
patent application Serial No. 08/08~,861, filed June 30, 1993, entitled "Curing Agents for Aq~ '90US Epoxy Resins", by Jason Chou et al., the disclosure of 5 which is incor~ oralecJ herein by reference. These epoxy curing agents cor"prise the reaction product of ~eacla"ts consisling essentially of an alkylene polyamine having less than about 12 carl,Gn atoms, an ~rc,l"dlic mono-glycidyl ether having less than.about 18 carbon atoms, and a diglycidyl ether of an aromalic diol having an average degree of oligomerization of less 10 than about 3.5, wherein the ratio of primary amine equivalents of said alkylene polyamine to the total epoxide equivalents of said aromatic glycidyl ether and said diglycidyl ether of an aro",alic diol is not essentially less than one, and the ratio of epoxide equivalents of said aro,nalic mono-glycidyl ether to epoxide equivalents of said diglycidyl ether of an aromalic diol is greater than one.
In addition to the amine curing agent, a curing accelerator can be included in the coating composition. Such an accelerator will serve to reduce the time for the coaling to become tack-free. Useful accelerators for amine curing agents include tertiary amines, e.g. N,N'-bis(dil"ell,yl-amino-propyl) 20 urea.
Other curing agents can be used in the composition of this invention, particularly when the coatings made from the compositions are heated to effec~ a cure. Examples of such additional curing agents are the aminoplast and phenolplast resins. Suitable aminoplast resins are the reaction products WO 95/01387 ~ , iiJ ,~ ti 2 ~ 6 6 4 1 4 PCT/US94/06770 of ureas and melamines with aidehydes further etherified in some cases with an alcohol. Examples of aminopiast resin components are urea, ethylene urea, thiourea, melamine, benzoguana",ine and acetogu~"a")i,le. Aldehydes include formaldehyde, acetaldel "/de and propionaldehyde. The ami"oplast resins can be used in the alkylol form but, preferably, are utilized in the ether form wherein the etherifying agent is a mGUOI "~dric alcohol containing from 1 to 8 carbon atoms. Examples of suitable ar"i"oplast resins are methylol urea, cli,nell ,oxymethylol urea, butylated polymeric urea-formaldehyde resins, hexamell)oxymethyl melamine, methylated polymeric melamine-formaldehyde resins and butylated polymeric melamine-formaldehyde resins.
Phenolplast resins are the reaction products of phenols and aldehydes which conlai., reactive methylol groups. These co",positions can be ,nGr,G",eric or polymeric in nature depending on the molar ratio of phenol to aldehyde used in the initial condensation reaction. Examples of suitable phenols are phenol, o, m or p-cresol, 2,4-xylenol, 3,4-xylenol, 2,~-xylenol, cardanol, p-tert-butyl phenol, and the like. Useful 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.
Other epoxy resin curing agents may also be useful, e.g. catalytic curing agenls; Lewis bases (such as tertiary amines), Lewis acids (such as boron trifluoride), cationic curing agents (such as aryldiazonium salts, diaryliodinium salts, onium salts of Group Vla elements, especially sulfur) and reactive curing agents: mercaptans, isocyanates, carboxylic acids, and acid ~/O 95101387 ~\ t J~ S 2 1 ~ 6 4 1 4 PCT/US94/06770 anhydrides. Curing agents for epoxy resins in general are discussed in the EncvcloPedia of Polymer Science and Enqineerin~, vol. 6, pp. 340-361 (John Wiiey & Sons, Inc., N.Y., N.Y., 1986), the disclosure of which is incorporated by r~3ference.
The following examples are further illustrative of the presenl invention.
The reactants and other specific ingredients are presented as being typical, and various modifications can be derived in view of the foregoing disclosure within the scope of the invention.
EXAMPLES
ExamPie 1 r, e~aralion of Amine-ePoxide Adduct (66% CaPPed) Into a one liter reaction flask eql lipped with a stirrer, heating mantle, nitrogen line, cooling co"5~e,)ser, and thermometer is charged 485 grams (0.4 equivalents) Jerr~"lir~e 2000. (Texaco Chemical ComPanY. Houston, Texas) and 142.2 grams (0.61 equivalents) of polyepoxide of propoxylated (5PO) pel ,laerythritol (Henkel Cor~ oralion, Ambler, PA). The reaction mixture is heated slowly to 125-130C with stirring and held at this temperature for about 2.5 hours. The reaction mixture is then cooled to 70C and analyzed for epoxide and amine conlenl. The product amine polyepoxide adduct has 0.4 rneq./gm of total amine and 0.33 meq./gm of epoxide which indicates that ~- ~ ; à ~ t ~ 2 1 664 1 4 WO 95/01387 ` PCT/US94/06770 about 66% of the initial free epoxide groups have been reacted with the amine.
ExamPle 1A
Amine-ecoxide adduct (50% caPped) Example 1 was repealed except 75.0 gm (0.063 equivalent) of polyethoxy amine* and 35.5 gm (0.126 equivalent) polyepoxide of ~.ropoxylated (5P0) pentaerythritol were re~cterl The resulting adduct yielded a product containing 0.34 me*/gm of total amine and 0.54 me/gm of epoxid~ which represents 50% of the original epoxide moiety capped with the 1 0 amine.
* TEXACO's Jerra"~i,)e M-2070 * me (milliequivalent) ExamPle 1 B
Amine-ePoxide adduct (7g% cacPed) Example 1 was repeated except 75 gm (0.063 equivalent) of polyethoxy amine* and 23.6 gm (0.083 equivalent) polyepoxide of ~.ropoxylated (5PO) pentaerythritol were re~cte~ The resulting adduct yielded a product containing 0.4 me/gm of total amine and 0.26 me/gm of epoxide which represents about 75% of the initial epoxide capped with the amine.
* TEXACO's Jeffamine M-2070 S..~ a~
~O 95/01387 2 1 6 6 4 1 4 PCT/US94/06770 ExamPle 1C
Amine-ePoxide adduct (66% capped) Example 1 was repeated except S0.0 gm polyethoxy amine~ (0.0831 equivalent) and 35.0 gm (0.1245 equivalent) polyepoxide of propoxylated (5PO~ pentaerythritol were reActed The resulting Add~lct contained 0.61 me/gm of total amine and 0.37 me/gm of epoxi~le which re~,rese"ls about 66% of the initial epoxide capped with the amine.
TEXACO s Jeffamine M-1000 ExamPle 1 D
Example 1 was repeated except 150.0 gm (0.102 equivalent) of polyethoxy amine~ and 41.6 gm (0.153 equivalent) polyepoxide of propoxylated (5PO) penlae,ythritol were reActe~ The resulting A~d~lct ccnW,)ed 0.32 me/gm of total amine and 0.31 me/gm of epoxide which represents about 66% of the initial epoxide capped with the amine.
~ TEXACO s Expe, i" ,ental amine No. 6940-29 (MW 3 000) ExamPle 2 rle~aralion of Self-DisPersin~ Resin.
Into a 250 mL reaction flask equipped with heating mantle nitrogen line cooling condenser lher",G,neter and stirring means is charged 66.4 grams (0.348 equivalents) of the diglycidyl ether of bis-phenol A and 19.6 2~66414 WO95/01387 ~ ~ 3d ~ ~ PCT/US94/06770 grams (0.172 equivaients) of bis-phenol A. The reactants are heated to 95C
and then 12.0 grams (0.004 equivalents) of the amine-epoxide adduct prepared above (Example 1 ) is added with 0.15 grams triphenyl phosphine.
The reaction mixture is heated slowly to 150C with stirring whereupon an exothermic reaction is observed. Cooling is immedi~tely applied to maintain the reaction temperature between 1 50C and 1 60C. After the exothermic reaction s~hsides, the reaction mixture is maintained at 160C for an additional hour followed by a 15 minute period at 1 90C. The reaction mixture is then cooled to 160C and 14 grams of propyl cellosolve is added which immediately begins refluxing. The reaction mixture is cooled to 100C
and analyzed. The resultant self-dispersing resin, present at 87.5% solids in propyl cellosolve, has 0.07 meq./gm total amine and an epoxide equivalent weight of 552 based on resin solids.
ExamPle 2A
ExamPle of a Lar~er Scale PreParation of Self-DisPersin~ Resin.
Into a 5 I. reaction flask equipped with heating mantle, nitrogen line, cooling co"denser, thermometer and stirrer, is charged 1716 grams (8.99 equivalents) of the diglycidyl ether of bis-phenol A, and 506.4 grams (4.44 equivalents) of bis-phenol A. The reactants were heated to 95 C and then 413.4 grams (0.138 equivalents) of the amine-epoxide adduct prepared according to Example 1 along with 2.1 grams of triphenyl phosphene is added. The reaction mixture is heated carefully to about 150 C with stirring whereupon an exothermic reaction is noted. Cooling is immediately applied ~O 95/01387 ~ 2 1 6 6 4 1 4 PCT/US94106770 to maintain the temperature between 150 C and 160 C. After the exotherrn subsides, the reaction mixture is maintained at 160 C for an additional hour followed by a 15 minute period at 190 C. The reaction mixture is then cooled to about 160 C and 362.1 grams of propyl cellosolve is ~dded Cooling is 5 continued to about 100 C .when it is sampled and analyzed for epoxide equivalent weight. The resulting self-dispersing resin has an epoxide equivalent weight of 550 based on resin solids.
ExamPle 3 P(el~aralion of Water-Borne DisPersion.
Into a 500 mL reaction flask e~l lippPd with a stirrer, heating mantle, nil, o0en line, cooling conde, Iser and lherlllometer is charged 112 grams of the self-dispersing resin (SDR) prepared accGrding to Example 2. The resin is heated to 100C whereupon 16.5 grams water are added gradually with stirring over a thirty minute period while the temperature drops to about 55C.
15 Then an additional 48 grams of water is added as the temperature is brought to 70C over twenty minutes. At 70C there is added 2 grams of water, followed by stirring for twenty minutes and then by 3 grams of water. The resulting water in oil dispersion is stirred for 45 minutes while it cools to 45C~ and therearler is in the form of an oil in water dispersion. After the 20 inversion is complete, 2.0 grams of C8-C,0 alcohol mono-glycidyl ether from CVC Specialty Chemicals Corp is added as a reactive diluent. Then 36.3 grams water is added at 50C over a one hour period. The resulting water-WO 95/01387 i ~ a ~ ~ 2 1 ~ 6 4 1 4 PCT/US94/06770 borne dispersion contains 56% resin solids in water/propyl cellosolve (82/18) solvent.
ExamPle 3A
P~erjaralion of Water-Borne Dis~ersion on a Laraer Scale.
Into a 1 liter reaction flask equipped with a stirrer, heating mantle, nil,ogen line, cooling condenser and thermu,,,eter is charged 494 grams of the SDR prepared accordin~ to example 2A. The resin is heated to 60 C to 65 C and 130.3 grams of water is added over one hour. The temperature is then lowered to 50 C over about 30 minutes whereupon the water in oil emulsion formed inverted to an oil in water emulsion. After inversion is complete, 8.8 grams of C8-C,0 alcohol mono-glycidyl ether is added. After mixing for 10 minutes, 159.3 grams of water was added at 50 C over one hour. The resulting water borne dispersion contains 56% resin solids.
Example 3B
Example 3 was repeated except the SDR con~ai"ed the amine epoxide adduct from Example 1A.
ExamPle 3C
Example 3 was repeated except the SDR contained the amine epoxide adduct from Example 1 B.
ExamPle 3D
~o gS/01387 j ~ 1 6 6 4 1 4 PCTfUS94/06770 Example 3 was repeated except the SDR contained the amine epoxide adduct from Example 1 C.
ExamPle 3E
Example 3 was repeaLed except the SDR contained the amine epoxide S ~dd~lct from Example 1 D.
Example 3F
Example 3 was repeated except the amine-epoxide ~ld~ ~ct of Example 1 A was post-added, i.e. added to the reaction product of the diglycidyl ether of Bis-phenol A and Bis-phenol A.
ExamPle 3G
Example 3 was repeated except the amine-epoxide ~ Jct from Exarnple 1 B was Dost-added after the reaction of the diglycidyl ether of Bis-phenol A and Bis-phenol A.
The properties of these dispersions are given in the following table:
PROPERTIES OF DISPERSIONS
Viscosity Stability at Particle DisPersion CPS/25C 50/4 weeks Size (Microns) Film 3 250 S 1.4 P
3B 900 U 3.2 P
3C 850 S 2.0 P
3D 800 S 1.2 P
3E 850 S 1.6 P
3F 100 U 4.0 P
WO 95/01387 ~ 2 1 6 6 4 ~ 4 PCTIUS94/06770 *
3G 200 U 3.7 P
Note:
1. Inthe abovetable P=Passed S=Stable and U=Unstable.
2. 3B prod~ ~ced an unstable dispersion and large particle size be~ se the amine-epoxy adduct at 50% cappi"g was ineffective. 3F and 3G
produced unstable dispersions and large particle size he~ ~se the amine-epoxy adduct was post added to the resin. Film properties were acceptable for the dispersions tested.
ExamPle 4 Preparation of Coatino ComPosition.
Into a 25 mL plastic cup is charged 12.4 gm (56% solids) of the water-borne dispe, ~io" ~repared accordi"g to Example 3 followed by an equal equivalent amount (2 gm) of epoxy curing agent available as 8290 by HiTech 15 (a modified diethylene triamine with a hydrogen equivalent weight of 163).
Sufficient water is then added to bring the mixture to a spreadable co, Isisle, ,cy. The epoxy disperaiol ,/curing agent blend is aged for 10 minutes then a film casting is prod~ ~ced by drawing the blend down on pre-sanded TRU COLD cold rolled steel panel (3 x 6 x 0.32 inches) using a #34 wire 20 wound steel rod. The film was tack free after 45 minutes. The physical properties of the coating composition were measured after the film had air dried at room temperature for 28 days.
The principles, preferred embodi",ents and modes of operation of the 25 present invention have been described in the foregoing specification. The ~O 95/01387 PCT/US94/06770 invention which is intended to be ~, otet;led herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be re~2srded as illustrative rather than resl, icli./e. Variations and changes may be made by those skilled in the art without clepa, ling from the spirit of the 5 invention.
Techniques to prepare such epoxy resins are known in the art, and include reacting compounds having 2 or more hydroxyl groups with epichlorohydrin in the presence of a suitable catalyst. Suitable epoxy resins are commercially available from a variety of sources and include EPON (Reg.
TM) epoxy resins from Shell Chemical CGr"pa, Iy, Houston, Texas, and DER
(Reg. TM) or DEN (Reg. TM) epoxy resins from Dow Ci)er"ical Co",,.any, Midland, Michigan.
Examples of suitable epoxy resins are:
I) Polyglycidyl and poly(beta-methylglycidyl) esters obtainable by reacting a compound having at least two carboxy groups in the molecule with epichlorohydrin or beta-methyl-epichlorohydrin, respectively. The reaction is adva"ldgeously carried out in the presence of bases. Examples of ar~l"dlic polycarboxylic acids which may be used include, for example, phthalic acid, isophll,alic acid or tere~chlhalic acid.
Il) Polyglycidyl or poly(beta-methylglycidyl) ethers obtainable by re~cting a compound having at least two free phenolic hydroxy groups with epichlorohydrin or beta-methyl-epichlorohydrin, respectively, under alkaline conditions, or in the presence of an acid catalyst and with sl ~hseq! lent alkali lr~aln,ent.
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, bis(4-hydroxyphenyl)methane, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)sulfone~ 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-~0 95~01387 ~ a ~ ~ ~ 2 1 6 6 4 1 4 PCTIUSg4/06770 dibrorno-4-hydroxyphenyl) pro~a"e, and from novolacs obtainable by conder,salion of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfuraldehyde, with phenols, such as phenol, or with phenols that are substituted in the nucle~ ~s by halide atoms or C,-C,8 (~ rererably C,- Cg) alkyl 5 groups, such as, for example, 4-chlorophenol, 2-methylphenol or 4-tert-butylphenol, or by conde"salio" with bisphenols, in the ma""er described above.
There are preferably used epoxy resins that have an epoxy conlenl of from 2 to 10 equivalents/mole and that are glycidyl ethers or glycidyl esters of 10 aro"~alic or alkylarol"d~ic corl,pounds. Especially prefer,ed epoxy resins are polyglycidyl ethers of bisphenols, such as, for example, of 2,2-bis(4-hydroxyphenyl)propane (bispl ,enol A) or bis(4-hydroxyphenyl)methane (bisphenol F), or novolacs formed by reacliny formaldehyde with a phenol.
For reasons of cost and availability, the most preferred epoxy resins are 15 polyglycidyl ethers based on bisphenol A.
P~ efel, ed epoxy resins have an epoxide equivalent weight of less than about 400 grams/squivalent, e.g. from about 100 grams/equivalent to about 350 grams/equivalent, more ,l~referably from about 150 grams/equivalent to about 225 grams/equivalent, e.g. DER 331 available from Dow Chemical at 20 about 182 grams/equivalent.
The PolYhYdric Phenol The polyhydric phenol reactanl comprises one or more compounds each having a plurality of hydroxyl groups covalently bonded to one or more WO 95/01387 , ~ 2 1 ~ ~ 4 1 4 PCT/US94/06770 ~
six-carbon aromali~ed rings. The polyhydric phenol reactant may contain substituents such as alkyl, aryl, sulfido, sulfonyl, halo, and the like. The polyhydric phenol is represented by the structural formula:
R~(OH)h 5 wherein R9 represents an 'h' valent C6-Cso organic radical co",prisi"g at least one six-carbon aro",~ ed ring, and 'h' represents a number of phenolic hydroxyl groups where 'h' is equal to or greater than 2 but less than or equal to6.
Techniques to prepare suitable polyhydric phenol compounds are known in the art. Suitable polyhydric phenol compounds are commercially available from Dow Chemical Coi"pally, Midland Michigan, and Shell Chemical Compa,-y, Houston, Texas.
Illustrative of suitable polyhydric phenols are 2,2-bis(4-hydroxyphenyl)pro,t~ane, 2,2-bis(3-bromo4-hydroxyphenyl)-propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)-methane, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, resorcinol, hydroquinone, phenol-formaldehyde novolac resins, and the like. The most 20 prefer,ed dihydric phenols are 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) and bis(4-hydroxyphenyl)methane (bisphenol F) for reasons of cost and availability.
~O 95/0L387 ~ C; 2 1 6 6 4 1 4 PCT/US94/06770 The Amine-Epoxy Adduct The preparation of the self-dispersing curable epoxy resins of the invenl:ion may proceed through an amine-epoxy ~ld~ ~ct, where the amine-epoxy ~dduct is s' ~hseq! ~ently reacted with a polyhydric phenol and an epoxy 5 resin. The structure of the amine-epoxy ~dduct is dependant on the structQ-res of the polyoxyalkyleneamine and the aliphatic polyepoxide used in the preparalion of the amine-epoxy ~dduct, as well as the relative ratio of the r ~a.:l~" ItS.
A represenlali-/e amine-epoxy adduct has the structural formula:
10((CH2-CH-R6)(d "(H-R6)CR5R6-CH(OH)CH2-N-\ / I
O R,-O-R2-CH2CH(R3) [cH2cH(oH)-R6-Rs(-R6-cH-cH2)(d-2)(-R6-H)c-F~6-cH(oH) O
CH2-N]jCH2CH(OH)-R6-Rs(-R6-cH2cH-cH2)(d 1)(-R6-H)c) \ /
20(R3)CHCH2-R2-O-R, O
wherein 'i' indiG~tes a number of repetitive units where 'i' is equal to or greater than zero (0) but less than or equal to about fifty.
- The Self-DisPersin~ Curable EPOXY Resin 25The self-dispersing curable epoxy resins of the invention may be prepared by reacting an amine-epoxy adduct with a polyhydric phenol and an WO 95/01387 ~ ' 2 1 ~ 6 4 1 4 PCT/US94/06770 epoxy resin. 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 epoxy resin, the identity of the polyhydric phenol and the relative ratio of the reac~a"~s.
The products of the above reactiGn are envisioned to be an extremely com,cl_x mixture of polymeric malel ials cc ,n~, ising two cl;slinct groups. A
simplified structure for each group of reaction products can be shown if it is assumed that the phenolic cGr"p~nenl is dihydric and the epoxy component is a diepoxide.
Structure rll (CH2-CH-R8-CH(OH)-CH20-[R~,-OCH2-CH(OH)-R8-CH(OH)-CH20-]J-O
R9o-cH2-cH(oH)-R8-cH-cH2) wherein 'j' in-licAles a number of repealir~9 units, and is equal to or greater than zero (0) but less than or equal to twenty (20).
20 Structure rlll [(GE)(d-1)(R6-H)cR5-R6-cH2-cH(oH)-cH2-N-R,-O-R2-CH2CH(R3) [CH2cH(oH)-R6-R~(GE)(d-2)(R6-H)cR6-cH(oH)cH2-N]i-R2-CH2CH(R3) 2 1 6 6 ~ 1 4 ~0 95/01387 ~ t .5 ~ i, PCT/US94/06770 CH2cH(oH)-R6-Rs(GE)(d~ H) wherein 'GE' is defined as -R6-cH(oH)cH2-o-[R9-o-cH2cH(oH)-R8-cH(oH)cH2-o]
CH2CH(OH)-R8-CH-CH2 \ I
and all other variables are as defined above.
Orqanic Cosolvents The self-dispersing curable epoxy resin of the present invention may 10 be combined with a non-reactive, water-miscible, organic cosolvent. The cosolvent serves to reduce the viscosity of the self-dispersing curable epoxy resin. rl erer, ed organic cosolvents include the alkyl ethers of monohydric and dihydric alcohols, where the alkyl group comprises C,-C8 linear or branched aliphatic or alicyclic chains. The choice of cosolvent can affect the 15 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 (Easl",an Chemicals) with one of the following cosolvents (the greater increase being obtained in order): 1-methoxy-2-propyl ~cet:~te, methyl n-amyl ketone, or dipropylene glycol n-butyl ether.
20 Reactive Diluents The ~refe" ed stable a~ ~eo~ Is epoxy resin dispersions of the present invention are those which contain a water-immiscible C8-C20 aliphatic r ~ 2 1 6 6 4 1 4 WO 95/01387 - ' PCT/US94/06770 monoepoxide reactive diluent. The said monoepoxide component can contain alicyclic and aromatic structures as well as halogen sulfur p hos~l ,orus, and other such heteroalor"s. Suitable reactive diluents are available from CVC Specialty Chemicals Inc., Cherry Hill, New Jersey.
Illustrative of monoepoxide reactive diluents are epoxidized unsaturated hydrocarbons such as decene and cyclohexene; glycidyl ethers of monohydric alcohols such as 2-ethylhexanol doclec~nol and eicosa, lol;
glycidyl esters of ",onocarboxylic acids such as hexanoic acid; ~cet~ls of glycidaldehyde; and the like. The preferred reactive diluent is glycidyl ether of monohydric C8-C10 aliphatic alcohols.
The presence of a water-immiscible C8-C20 aliphatic monoepoxide reactive diluent in an aqueous epoxy resin dispersion has significant beneficial effects in addiliGn to modifying the viscosity of the dispersion. Forexample, the said water-i"""iscit~le reactive diluent appears to coat the particles of epoxy resin solids and thereby. provide the aqueous dispersion with improved shear, freeze-thaw resislance shelf viscosity stability, and paint gloss.
Also, since the reactive diluent is epoxy functional it becomes chemically bonded into the film which is formed during the subsequent room temperature curing of the aqueous dispersion composition after it has been blended with a curing agent and coated on a surface. The total quantity of reactive diluent contributes to the calcl ll~ted proportion of non-volatiles in the dispersion composition.
. ~ ~ 21 6641 4 ~0 95/01387 ~ S PCT/US94/06770 Preparation of the Self-DisPersinq Curable EpoxY Resin In pl eparing the self-dispersing curable epoxy resins of this invention, an arnine-epoxy addud is first ~.repared by combining the polyoxyalkyleneamine reactal)t and the aliphatic polyepoxide reaclanl, healing the mixture slowly to about 130 C, holding the mixture at temperature for about 2.5 hours, and then discl ,aryi"y the amine-epoxy ~dd~ lc.t from the reactor. The self-dispersing epoxy resin is prepared by c~"lbir,ing the amine-epoxy ~dduct, 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 exoLl1er",ic reaction will then occur, and cooling is applied to maintain the reaction temperature at about 150-160 C. The mixture is mainlained at about 160 C for about one hour s~ ~hse~ ~ent to the conclusion of the exoll ,er",ic reaction, followed by heating to 190 C. The reaction is maintained at 190 C for about 15 minutes in order to drive the reaction to completion, then cooled to about 160 C whereupon a small amount of a water-soluble organic solvent is added prior to cooling and discharging the self-dispersing curable epoxy resin from the reactor.
Preparation of an Aqueous DisPersion of the Self-DisPersinq Curable EPOXY
Resin The aqueous epoxy dispersion of the invention is prepared by charging the sel~-dispersing curable epoxy resin to a reaction vessel, then heating the resin to about 50-100 C with stirring. Water is gradually added d ~ ~ ~
WO 95/01387 2 1 ~ 6 4 1 4 PCT/US94/06770 ~ .
to the self-dispersing curabie epoxy resin while the temperature is allowed to drop to about 50 C. During this period, the water in oil dispersion is formed and then inverts to an oil in water disper~ion. After inversion, additional water may be added as well as reactive diluent in the form of a C8-C10 alcohol 5 mono~lycidyl ether.
The particle size of the oil phase in the aqueous disper~ion can be modified by physical techniques to reduce the particle size. The particle size red~ ~ction is ,ureferably acco""~lished by subjecting an ~q~ ~eo! ~s dispersion of the precipit~e to high shear, e.g. in a hor"ogenizer such as that disclosed in U.S. Patent No. 4,533,254 (Cook et al.), the ~isclos~re of which is i, ,cor,uordled herein be reference, and commercially available as MICROFLUIDIZERTM from Microfluidics Cc: r~,oralion, Newton, Massachusett~
Homogenizers are ~iscussed in W. C. Griffin, "Emulsions", EncycloPedia of Chemical Technolo~Y. Vol. 8, pp. 900-930 (Kirk-Othmer, eds., John Wiley &
Sons, Inc., New York, New York, 3d ed., 1979), the disclosure of which is incorporated herein by reference.
The aqueous dispersion of self-dispersing resin will typically exhibit excellent chemical and physical stability over an extended shelf-life, e.g. of from five to six months. As an example of the chemical stability, the epoxide 20 equivalent weight (EEW) of the aq~ ~eo~ ~s dispersion of self-dispersing resin should remain essentially co"sla"l, e.g. should show no trend of increasing molecular weight, over a period of at least one month from the preparation of the aqueous dispersion.
~0 95/01387 . ~ PCT/US94/06770 Epoxide equivalent weight can be determined by dirrere, llial titration with perchloric acid using crystal violet as an indicator (e.g. a first sample is titrated with 0.1 N perchloric acid to an endpoint that shows the first sight of green color form the crystal violet indicator, the amine equivalent weight of 5 the dispersion is calcul~te:l from this titration, a second sample is mixed with ~xcess tetraethylan""Gnium bromide and titrated with 0.1 N perchloric acid to a green endpoint that persists for at least 30 seconds, total epoxide and amine equivalents are ~Icl ~ted from this titration, and the epoxide equivalent weight is calculated as the difference).
As an example of physical stability, the resin should not display layer for" ,ation for a period of at least one month from the prepal aLion of the :~ueous dispersion, i.e. there should be no for",alion of a macro-observable water phase as a layer separate from the dispersed resin phase.
Coatin~ ComPositions ComPrisinq an Aqueous Dispersion of the Self-15 DisPersin~ Curable EPOXY Resin The coating composition of the invention is ~repared by combining the aqueous epoxy dispersion with a suitable hardening agent. The coatings are tack free after 45 minutes and have excellent film properties. An aqueous epoxy resin paint composition of the present invention may further contain 20 additives conventionally employed in coating technology, such as organic piglllents, inorganic pigments, surfactants, thickeners, and the like.
A room tempera~LIre curable water-borne coating composition is prepared by admixing a stable epoxy dispersion composition as described Ij,r~,a~,~ 2l66414 above with an epoxy-interacting curing vehicle, such as a polyamine curing agent. The ratio of active amino hydrogens to epoxy groups in the admixture is in the range of from 0.5:1 to 2:1 and, preferably, is in the range between about 0.8:1 to 1.5:1. For purposes of industrial maintenance paint com~osilions, the amino hyd~oge"s must be sufficiently reactive to effect crosslinking inlera~lion with the epoxy groups at ambient temperatures.
Suitable polyamine curing agents are those which are soluble or dispersible in water and which co"lain more than 2 active hydrogen atoms per molecule. Examples of such curing agents are alkylene polyamines represented by the formula:
H2N-T-(NH-T)uNH2 wherein r is an alkylene radical containing 2 to 6 carbon atoms and 'u' is equal to or yl ealer than zero (0) but less than or equal to five (5). Such alkylene polyamines include ethylene diamine, diethylene triamine, triethylene teLra"~ e, tel,aelllylene penla",ine, pentaethylene hexamine, propylene diamine, dibutylene triamine, hexamethylene diamine, and the like.
Other polyamine curing agents that can be employed in the practice of this invention are the polyamido amines, which are reaction products of alkylene polyamines and fatty acids. Such polyamidoamines are well known in the art and are described in U.S. Pat. Nos. 2,705,223, 2,811,495 and 2,899,397, which patents are hereby incorporated by reference. Other polyamine curing agents are the ~ddl lctc of polyamines and epoxy compounds such as those described in U.S. Pat. Nos. 2,651,589, 2,864,775 ~VO 95/01387 ` ~ 2 1 6 6 4 1 4 PCT/U~i94/06770 and 4,116,900, which patents are hereby incorporated by reference.
Examples of useful curing agents also include those disclosed in U.S.
patent application Serial No. 08/08~,861, filed June 30, 1993, entitled "Curing Agents for Aq~ '90US Epoxy Resins", by Jason Chou et al., the disclosure of 5 which is incor~ oralecJ herein by reference. These epoxy curing agents cor"prise the reaction product of ~eacla"ts consisling essentially of an alkylene polyamine having less than about 12 carl,Gn atoms, an ~rc,l"dlic mono-glycidyl ether having less than.about 18 carbon atoms, and a diglycidyl ether of an aromalic diol having an average degree of oligomerization of less 10 than about 3.5, wherein the ratio of primary amine equivalents of said alkylene polyamine to the total epoxide equivalents of said aromatic glycidyl ether and said diglycidyl ether of an aro",alic diol is not essentially less than one, and the ratio of epoxide equivalents of said aro,nalic mono-glycidyl ether to epoxide equivalents of said diglycidyl ether of an aromalic diol is greater than one.
In addition to the amine curing agent, a curing accelerator can be included in the coating composition. Such an accelerator will serve to reduce the time for the coaling to become tack-free. Useful accelerators for amine curing agents include tertiary amines, e.g. N,N'-bis(dil"ell,yl-amino-propyl) 20 urea.
Other curing agents can be used in the composition of this invention, particularly when the coatings made from the compositions are heated to effec~ a cure. Examples of such additional curing agents are the aminoplast and phenolplast resins. Suitable aminoplast resins are the reaction products WO 95/01387 ~ , iiJ ,~ ti 2 ~ 6 6 4 1 4 PCT/US94/06770 of ureas and melamines with aidehydes further etherified in some cases with an alcohol. Examples of aminopiast resin components are urea, ethylene urea, thiourea, melamine, benzoguana",ine and acetogu~"a")i,le. Aldehydes include formaldehyde, acetaldel "/de and propionaldehyde. The ami"oplast resins can be used in the alkylol form but, preferably, are utilized in the ether form wherein the etherifying agent is a mGUOI "~dric alcohol containing from 1 to 8 carbon atoms. Examples of suitable ar"i"oplast resins are methylol urea, cli,nell ,oxymethylol urea, butylated polymeric urea-formaldehyde resins, hexamell)oxymethyl melamine, methylated polymeric melamine-formaldehyde resins and butylated polymeric melamine-formaldehyde resins.
Phenolplast resins are the reaction products of phenols and aldehydes which conlai., reactive methylol groups. These co",positions can be ,nGr,G",eric or polymeric in nature depending on the molar ratio of phenol to aldehyde used in the initial condensation reaction. Examples of suitable phenols are phenol, o, m or p-cresol, 2,4-xylenol, 3,4-xylenol, 2,~-xylenol, cardanol, p-tert-butyl phenol, and the like. Useful 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.
Other epoxy resin curing agents may also be useful, e.g. catalytic curing agenls; Lewis bases (such as tertiary amines), Lewis acids (such as boron trifluoride), cationic curing agents (such as aryldiazonium salts, diaryliodinium salts, onium salts of Group Vla elements, especially sulfur) and reactive curing agents: mercaptans, isocyanates, carboxylic acids, and acid ~/O 95101387 ~\ t J~ S 2 1 ~ 6 4 1 4 PCT/US94/06770 anhydrides. Curing agents for epoxy resins in general are discussed in the EncvcloPedia of Polymer Science and Enqineerin~, vol. 6, pp. 340-361 (John Wiiey & Sons, Inc., N.Y., N.Y., 1986), the disclosure of which is incorporated by r~3ference.
The following examples are further illustrative of the presenl invention.
The reactants and other specific ingredients are presented as being typical, and various modifications can be derived in view of the foregoing disclosure within the scope of the invention.
EXAMPLES
ExamPie 1 r, e~aralion of Amine-ePoxide Adduct (66% CaPPed) Into a one liter reaction flask eql lipped with a stirrer, heating mantle, nitrogen line, cooling co"5~e,)ser, and thermometer is charged 485 grams (0.4 equivalents) Jerr~"lir~e 2000. (Texaco Chemical ComPanY. Houston, Texas) and 142.2 grams (0.61 equivalents) of polyepoxide of propoxylated (5PO) pel ,laerythritol (Henkel Cor~ oralion, Ambler, PA). The reaction mixture is heated slowly to 125-130C with stirring and held at this temperature for about 2.5 hours. The reaction mixture is then cooled to 70C and analyzed for epoxide and amine conlenl. The product amine polyepoxide adduct has 0.4 rneq./gm of total amine and 0.33 meq./gm of epoxide which indicates that ~- ~ ; à ~ t ~ 2 1 664 1 4 WO 95/01387 ` PCT/US94/06770 about 66% of the initial free epoxide groups have been reacted with the amine.
ExamPle 1A
Amine-ecoxide adduct (50% caPped) Example 1 was repealed except 75.0 gm (0.063 equivalent) of polyethoxy amine* and 35.5 gm (0.126 equivalent) polyepoxide of ~.ropoxylated (5P0) pentaerythritol were re~cterl The resulting adduct yielded a product containing 0.34 me*/gm of total amine and 0.54 me/gm of epoxid~ which represents 50% of the original epoxide moiety capped with the 1 0 amine.
* TEXACO's Jerra"~i,)e M-2070 * me (milliequivalent) ExamPle 1 B
Amine-ePoxide adduct (7g% cacPed) Example 1 was repeated except 75 gm (0.063 equivalent) of polyethoxy amine* and 23.6 gm (0.083 equivalent) polyepoxide of ~.ropoxylated (5PO) pentaerythritol were re~cte~ The resulting adduct yielded a product containing 0.4 me/gm of total amine and 0.26 me/gm of epoxide which represents about 75% of the initial epoxide capped with the amine.
* TEXACO's Jeffamine M-2070 S..~ a~
~O 95/01387 2 1 6 6 4 1 4 PCT/US94/06770 ExamPle 1C
Amine-ePoxide adduct (66% capped) Example 1 was repeated except S0.0 gm polyethoxy amine~ (0.0831 equivalent) and 35.0 gm (0.1245 equivalent) polyepoxide of propoxylated (5PO~ pentaerythritol were reActed The resulting Add~lct contained 0.61 me/gm of total amine and 0.37 me/gm of epoxi~le which re~,rese"ls about 66% of the initial epoxide capped with the amine.
TEXACO s Jeffamine M-1000 ExamPle 1 D
Example 1 was repeated except 150.0 gm (0.102 equivalent) of polyethoxy amine~ and 41.6 gm (0.153 equivalent) polyepoxide of propoxylated (5PO) penlae,ythritol were reActe~ The resulting A~d~lct ccnW,)ed 0.32 me/gm of total amine and 0.31 me/gm of epoxide which represents about 66% of the initial epoxide capped with the amine.
~ TEXACO s Expe, i" ,ental amine No. 6940-29 (MW 3 000) ExamPle 2 rle~aralion of Self-DisPersin~ Resin.
Into a 250 mL reaction flask equipped with heating mantle nitrogen line cooling condenser lher",G,neter and stirring means is charged 66.4 grams (0.348 equivalents) of the diglycidyl ether of bis-phenol A and 19.6 2~66414 WO95/01387 ~ ~ 3d ~ ~ PCT/US94/06770 grams (0.172 equivaients) of bis-phenol A. The reactants are heated to 95C
and then 12.0 grams (0.004 equivalents) of the amine-epoxide adduct prepared above (Example 1 ) is added with 0.15 grams triphenyl phosphine.
The reaction mixture is heated slowly to 150C with stirring whereupon an exothermic reaction is observed. Cooling is immedi~tely applied to maintain the reaction temperature between 1 50C and 1 60C. After the exothermic reaction s~hsides, the reaction mixture is maintained at 160C for an additional hour followed by a 15 minute period at 1 90C. The reaction mixture is then cooled to 160C and 14 grams of propyl cellosolve is added which immediately begins refluxing. The reaction mixture is cooled to 100C
and analyzed. The resultant self-dispersing resin, present at 87.5% solids in propyl cellosolve, has 0.07 meq./gm total amine and an epoxide equivalent weight of 552 based on resin solids.
ExamPle 2A
ExamPle of a Lar~er Scale PreParation of Self-DisPersin~ Resin.
Into a 5 I. reaction flask equipped with heating mantle, nitrogen line, cooling co"denser, thermometer and stirrer, is charged 1716 grams (8.99 equivalents) of the diglycidyl ether of bis-phenol A, and 506.4 grams (4.44 equivalents) of bis-phenol A. The reactants were heated to 95 C and then 413.4 grams (0.138 equivalents) of the amine-epoxide adduct prepared according to Example 1 along with 2.1 grams of triphenyl phosphene is added. The reaction mixture is heated carefully to about 150 C with stirring whereupon an exothermic reaction is noted. Cooling is immediately applied ~O 95/01387 ~ 2 1 6 6 4 1 4 PCT/US94106770 to maintain the temperature between 150 C and 160 C. After the exotherrn subsides, the reaction mixture is maintained at 160 C for an additional hour followed by a 15 minute period at 190 C. The reaction mixture is then cooled to about 160 C and 362.1 grams of propyl cellosolve is ~dded Cooling is 5 continued to about 100 C .when it is sampled and analyzed for epoxide equivalent weight. The resulting self-dispersing resin has an epoxide equivalent weight of 550 based on resin solids.
ExamPle 3 P(el~aralion of Water-Borne DisPersion.
Into a 500 mL reaction flask e~l lippPd with a stirrer, heating mantle, nil, o0en line, cooling conde, Iser and lherlllometer is charged 112 grams of the self-dispersing resin (SDR) prepared accGrding to Example 2. The resin is heated to 100C whereupon 16.5 grams water are added gradually with stirring over a thirty minute period while the temperature drops to about 55C.
15 Then an additional 48 grams of water is added as the temperature is brought to 70C over twenty minutes. At 70C there is added 2 grams of water, followed by stirring for twenty minutes and then by 3 grams of water. The resulting water in oil dispersion is stirred for 45 minutes while it cools to 45C~ and therearler is in the form of an oil in water dispersion. After the 20 inversion is complete, 2.0 grams of C8-C,0 alcohol mono-glycidyl ether from CVC Specialty Chemicals Corp is added as a reactive diluent. Then 36.3 grams water is added at 50C over a one hour period. The resulting water-WO 95/01387 i ~ a ~ ~ 2 1 ~ 6 4 1 4 PCT/US94/06770 borne dispersion contains 56% resin solids in water/propyl cellosolve (82/18) solvent.
ExamPle 3A
P~erjaralion of Water-Borne Dis~ersion on a Laraer Scale.
Into a 1 liter reaction flask equipped with a stirrer, heating mantle, nil,ogen line, cooling condenser and thermu,,,eter is charged 494 grams of the SDR prepared accordin~ to example 2A. The resin is heated to 60 C to 65 C and 130.3 grams of water is added over one hour. The temperature is then lowered to 50 C over about 30 minutes whereupon the water in oil emulsion formed inverted to an oil in water emulsion. After inversion is complete, 8.8 grams of C8-C,0 alcohol mono-glycidyl ether is added. After mixing for 10 minutes, 159.3 grams of water was added at 50 C over one hour. The resulting water borne dispersion contains 56% resin solids.
Example 3B
Example 3 was repeated except the SDR con~ai"ed the amine epoxide adduct from Example 1A.
ExamPle 3C
Example 3 was repeated except the SDR contained the amine epoxide adduct from Example 1 B.
ExamPle 3D
~o gS/01387 j ~ 1 6 6 4 1 4 PCTfUS94/06770 Example 3 was repeated except the SDR contained the amine epoxide adduct from Example 1 C.
ExamPle 3E
Example 3 was repeaLed except the SDR contained the amine epoxide S ~dd~lct from Example 1 D.
Example 3F
Example 3 was repeated except the amine-epoxide ~ld~ ~ct of Example 1 A was post-added, i.e. added to the reaction product of the diglycidyl ether of Bis-phenol A and Bis-phenol A.
ExamPle 3G
Example 3 was repeated except the amine-epoxide ~ Jct from Exarnple 1 B was Dost-added after the reaction of the diglycidyl ether of Bis-phenol A and Bis-phenol A.
The properties of these dispersions are given in the following table:
PROPERTIES OF DISPERSIONS
Viscosity Stability at Particle DisPersion CPS/25C 50/4 weeks Size (Microns) Film 3 250 S 1.4 P
3B 900 U 3.2 P
3C 850 S 2.0 P
3D 800 S 1.2 P
3E 850 S 1.6 P
3F 100 U 4.0 P
WO 95/01387 ~ 2 1 6 6 4 ~ 4 PCTIUS94/06770 *
3G 200 U 3.7 P
Note:
1. Inthe abovetable P=Passed S=Stable and U=Unstable.
2. 3B prod~ ~ced an unstable dispersion and large particle size be~ se the amine-epoxy adduct at 50% cappi"g was ineffective. 3F and 3G
produced unstable dispersions and large particle size he~ ~se the amine-epoxy adduct was post added to the resin. Film properties were acceptable for the dispersions tested.
ExamPle 4 Preparation of Coatino ComPosition.
Into a 25 mL plastic cup is charged 12.4 gm (56% solids) of the water-borne dispe, ~io" ~repared accordi"g to Example 3 followed by an equal equivalent amount (2 gm) of epoxy curing agent available as 8290 by HiTech 15 (a modified diethylene triamine with a hydrogen equivalent weight of 163).
Sufficient water is then added to bring the mixture to a spreadable co, Isisle, ,cy. The epoxy disperaiol ,/curing agent blend is aged for 10 minutes then a film casting is prod~ ~ced by drawing the blend down on pre-sanded TRU COLD cold rolled steel panel (3 x 6 x 0.32 inches) using a #34 wire 20 wound steel rod. The film was tack free after 45 minutes. The physical properties of the coating composition were measured after the film had air dried at room temperature for 28 days.
The principles, preferred embodi",ents and modes of operation of the 25 present invention have been described in the foregoing specification. The ~O 95/01387 PCT/US94/06770 invention which is intended to be ~, otet;led herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be re~2srded as illustrative rather than resl, icli./e. Variations and changes may be made by those skilled in the art without clepa, ling from the spirit of the 5 invention.
Claims (7)
1. An amine-epoxy adduct useful in the preparation of a self-dispersing curable epoxy resin, the adduct comprising the addition product of reactants comprising 1.0 reactive equivalent of an aliphatic polyepoxide and from about 0.3 to 0.9 reactive equivalents of a polyoxyalkyleneamine.
2. An amine-epoxy adduct according to claim 1 wherein said adduct is prepared by the process of reacting 1.0 equivalent of an aliphatic polyepoxide and from about 0.3 to 0.9 reactive equivalents of a polyoxyalkyleneamine.
3. A self-dispersing curable epoxy resin composition comprising the addition product of reactants comprising (a) 1.0 reactive equivalents of an epoxy resin, (b) from about 0.01 to 1.0 reactive equivalents of a polyhydric phenol, and (c) from about 0.005 to 0.025 reactive equivalents of an amine-epoxy adduct according to claim 1.
4. A self-dispersing curable epoxy resin composition prepared by the process of reacting (a) 1.0 reactive equivalents of an epoxy resin, (b) from about 0.01 to 1.0 reactive equivalents of a polyhydric phenol, and (c) from about 0.005 to 0.025 reactive equivalents of an amine-epoxy adduct according to claim 1.
5. An aqueous dispersion comprising a self-dispersing epoxy resin as defined in claim 3, wherein the self-dispersing epoxy resin is prepared by the steps comprising:
(a) preparing an amine-epoxy adduct by contacting a polyoxyalkyleneamine and a polyepoxide, where the ratio of the reactive equivalents of the polyoxyalkyleneamine and the polyepoxide is in the range from about 0.3:1 to 0.9:1, and (b) contacting the amine-epoxy adduct with a polyhydric phenol and an epoxy resin, where the ratio of the reactive equivalents of the polyhydric phenol and the polyglycidyl ether of a polyhydric phenol is in the range from about 0.01:1 to about 1.0:1, and where the ratio of the reactive equivalents of the amine-epoxy adduct and the polyglycidyl ether of the polyhydric phenol is in the range from about 0.005:1 to about 0.025:1.
(a) preparing an amine-epoxy adduct by contacting a polyoxyalkyleneamine and a polyepoxide, where the ratio of the reactive equivalents of the polyoxyalkyleneamine and the polyepoxide is in the range from about 0.3:1 to 0.9:1, and (b) contacting the amine-epoxy adduct with a polyhydric phenol and an epoxy resin, where the ratio of the reactive equivalents of the polyhydric phenol and the polyglycidyl ether of a polyhydric phenol is in the range from about 0.01:1 to about 1.0:1, and where the ratio of the reactive equivalents of the amine-epoxy adduct and the polyglycidyl ether of the polyhydric phenol is in the range from about 0.005:1 to about 0.025:1.
6. A stable epoxy dispersion composition as defined in claim 5 comprising (1) between about 20-80 weight percent of a solvent phase comprising between 50 and 100 weight percent water and between 0 and 50 weight percent of a water-soluble organic cosolvent, and (2) between about 80-20 weight percent of a self-dispersing curable epoxy dispersion composition comprising the addition product of reactants comprising 1.0 reactive equivalents of an epoxy resin, between about 0.01 and 1.0 reactive equivalents of a polyhydric phenol, and between about 0.005 and 0.025 reactive equivalents of an amine-epoxy adduct, wherein the amine-epoxy adduct comprises the addition product of reactants comprising 1.0 equivalents of a polyepoxide and between 0.3 and 0.9 reactive equivalents of a polyoxyalkyleneamine.
7. A coating composition comprising a cured self-dispersing epoxy resin as defined in claim 3.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8628893A | 1993-06-30 | 1993-06-30 | |
| US08/086,288 | 1993-06-30 | ||
| US08/255,732 | 1994-06-14 | ||
| US08/255,732 US5565505A (en) | 1993-06-30 | 1994-06-14 | Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom |
| PCT/US1994/006770 WO1995001387A1 (en) | 1993-06-30 | 1994-06-22 | Self-dispersing curable epoxy resins and coatings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2166414A1 true CA2166414A1 (en) | 1995-01-12 |
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ID=26774579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002166414A Abandoned CA2166414A1 (en) | 1993-06-30 | 1994-06-22 | Self-dispersing curable epoxy resins and coatings |
Country Status (11)
| Country | Link |
|---|---|
| US (3) | US5565505A (en) |
| EP (1) | EP0707610B1 (en) |
| JP (1) | JPH08512080A (en) |
| AU (1) | AU7314294A (en) |
| CA (1) | CA2166414A1 (en) |
| DE (1) | DE69433207T2 (en) |
| MY (1) | MY111005A (en) |
| PH (1) | PH31436A (en) |
| SG (1) | SG54235A1 (en) |
| TW (1) | TW254963B (en) |
| WO (1) | WO1995001387A1 (en) |
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| WO1996020970A1 (en) * | 1994-12-29 | 1996-07-11 | Henkel Corporation | Aqueous self-dispersible epoxy resin based on epoxy-amine adducts |
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| US5719210A (en) * | 1996-11-26 | 1998-02-17 | Henkel Corporation | Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom |
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1994
- 1994-06-14 US US08/255,732 patent/US5565505A/en not_active Expired - Lifetime
- 1994-06-19 PH PH48538A patent/PH31436A/en unknown
- 1994-06-22 JP JP7503528A patent/JPH08512080A/en active Pending
- 1994-06-22 EP EP94923202A patent/EP0707610B1/en not_active Expired - Lifetime
- 1994-06-22 DE DE69433207T patent/DE69433207T2/en not_active Expired - Fee Related
- 1994-06-22 CA CA002166414A patent/CA2166414A1/en not_active Abandoned
- 1994-06-22 WO PCT/US1994/006770 patent/WO1995001387A1/en active IP Right Grant
- 1994-06-22 AU AU73142/94A patent/AU7314294A/en not_active Abandoned
- 1994-06-22 SG SG1996005356A patent/SG54235A1/en unknown
- 1994-06-28 MY MYPI94001680A patent/MY111005A/en unknown
- 1994-07-16 TW TW083106511A patent/TW254963B/zh active
-
1995
- 1995-06-06 US US08/470,391 patent/US5652323A/en not_active Expired - Lifetime
-
1996
- 1996-09-26 US US08/721,163 patent/US5763506A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08512080A (en) | 1996-12-17 |
| EP0707610B1 (en) | 2003-10-01 |
| TW254963B (en) | 1995-08-21 |
| US5763506A (en) | 1998-06-09 |
| DE69433207T2 (en) | 2004-07-29 |
| SG54235A1 (en) | 1998-11-16 |
| US5565505A (en) | 1996-10-15 |
| AU7314294A (en) | 1995-01-24 |
| US5652323A (en) | 1997-07-29 |
| PH31436A (en) | 1998-11-03 |
| EP0707610A1 (en) | 1996-04-24 |
| MY111005A (en) | 1999-07-31 |
| DE69433207D1 (en) | 2003-11-06 |
| WO1995001387A1 (en) | 1995-01-12 |
| EP0707610A4 (en) | 1997-11-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |