CA1161985A - Stable aqueous epoxy dispersions - Google Patents
Stable aqueous epoxy dispersionsInfo
- Publication number
- CA1161985A CA1161985A CA000388550A CA388550A CA1161985A CA 1161985 A CA1161985 A CA 1161985A CA 000388550 A CA000388550 A CA 000388550A CA 388550 A CA388550 A CA 388550A CA 1161985 A CA1161985 A CA 1161985A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- diglycidyl ether
- epoxy
- parts
- glycol
- 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.)
- Expired
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/145—Compounds containing one epoxy group
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Abstract
ABSTRACT OF THE DISCLOSURE
This invention provides a stable epoxy dispersion composition which contains a self-emulsifying epoxy resin film-forming component. The self-emulsifying property is achieved by the incorporation in the epoxy resin of a diglycidyl ether of polyoxyalkylene glycol constituent.
A preferred epoxy dispersion composition of the present invention additionally contains a monoepoxide reactive diluent component.
The epoxy dispersion composition exhibits excellent shear, freeze-thaw resistance and shelf viscosity stability properties, and can be coated on a substrate and cured to a thermoset protective film with a polyamine curing agent at room temperature.
This invention provides a stable epoxy dispersion composition which contains a self-emulsifying epoxy resin film-forming component. The self-emulsifying property is achieved by the incorporation in the epoxy resin of a diglycidyl ether of polyoxyalkylene glycol constituent.
A preferred epoxy dispersion composition of the present invention additionally contains a monoepoxide reactive diluent component.
The epoxy dispersion composition exhibits excellent shear, freeze-thaw resistance and shelf viscosity stability properties, and can be coated on a substrate and cured to a thermoset protective film with a polyamine curing agent at room temperature.
Description
`3 I, .
, BACKGROUND OF THE INVENTION
The need to reduce air pollution hazards caused by volatile organic solvents has increased the importance of water-borne resin coating systems.
~ As described in United States patents 4,048,179 and 4,073,762, various resins have been developed for aqueous paint compositions, and epoxy resins are o~ten employed when such ~coating properties as rust prevention and chemical resistance ilare regarded as essential for particular applications.
1l~ U.S. 3,238,170 describes an aqueous epoxy resin ¦¦composition comprising (1) a polyepoxy resin and t2) a copolymer of an alkyl ester of an ~ ethylenically unsaturated monocarboxylic acid and an alkyl half ester of itaconic acid, ~ which is an aqueous coating composition having good alkali resistance, adhesion and storage stability.
An aqueous emulsion comprising an epoxy resin and a ! protein acting as protective colloid, and an emulsion comprising a mixture of an amine-epoxy resin condensate and an epoxy resin, are disclosed in U.S. 3,020,250 and U.S. 3,449,281.
, Further, attention has been directed to various emulsifiers which are adapted for emulsification of epoxy resins in water. For example, an aqueous emulsion of an epoxy resin , in which a reaction product of a boric acid ester derived from boric acid with both an alkylene glycol and a ~-dialkyl-substituted aminoalkanol is employed as an emulsifier is described ¦lin U.S. 3,301,804. A polyepoxide emulsion or electrodeposition l~in which a polyepoxide is emulsifiecl with an emulsifying agent of the phosphate ester type is described in U.S. 3,634,348. An epoxy resin emulsion for sizing glass fibers in which a catIonic emulsifying agent selected frorn the group consisting of i', , ~imidazolines and amides and a non-ionic emulsifying agent are used in combination in U.S. 3,249,412.
! Also, various curing agents for epoxy resin emulsion Illcompositions are known in the art. For example, curing agents ¦~for epoxy resin compositions include a polyamide reaction product derived from a polymeric fatty acid and an aliphatic polyamine ~containing terminal amino groups (U.S. 2,811,495 and U.S.
1 2,899,397), a salted amine derived from a carboxylic acid having ~ 8 carbon atoms and a tertiary amine (U.S. 3,640,926), a ¦¦polyamide derived from a diamine and a dicarboxylic acid (U.S. 3,355,409~, a phenol modified polyamine (U.S. 3,383,347), an amino-containing polyamide prepared by reacting a polyamine j,with a polymerized fatty acid (U.S. 3,324,041), and the like.
j In most cases a bisphenol type of epoxy resin is ,employed as a film-forming component of an aqueous epoxy resin paint composition. However, a bisphenol type of epoxy resin as an aqueous dispersion component normally has the disadvantage that lt tends to crystallize and settle out when the aqueous dispersion 1,is stored for three months or longer under ambient conditions.
Destruction of emulsion particles usually occurs with advance of crystallization, and thereafter it is impossible to restore the original state even by heating. Thus, an aqueous epoxy r~sin paint has the disadvantage that if crystallization loccurs the crystallized paint cannot be used for coating purposes.
1 Some recent developments relate to the production o water-borne epoxy resin systems which exhibit improved properties under ambient condit.ons.
, U.S. 4,048,179 describes a process for preparing water-dilutable, heat-curing coating compositions comprising (~) reacting ~an aromatic polyglycidyl ether with a polyethylene glycol in the ;
, BACKGROUND OF THE INVENTION
The need to reduce air pollution hazards caused by volatile organic solvents has increased the importance of water-borne resin coating systems.
~ As described in United States patents 4,048,179 and 4,073,762, various resins have been developed for aqueous paint compositions, and epoxy resins are o~ten employed when such ~coating properties as rust prevention and chemical resistance ilare regarded as essential for particular applications.
1l~ U.S. 3,238,170 describes an aqueous epoxy resin ¦¦composition comprising (1) a polyepoxy resin and t2) a copolymer of an alkyl ester of an ~ ethylenically unsaturated monocarboxylic acid and an alkyl half ester of itaconic acid, ~ which is an aqueous coating composition having good alkali resistance, adhesion and storage stability.
An aqueous emulsion comprising an epoxy resin and a ! protein acting as protective colloid, and an emulsion comprising a mixture of an amine-epoxy resin condensate and an epoxy resin, are disclosed in U.S. 3,020,250 and U.S. 3,449,281.
, Further, attention has been directed to various emulsifiers which are adapted for emulsification of epoxy resins in water. For example, an aqueous emulsion of an epoxy resin , in which a reaction product of a boric acid ester derived from boric acid with both an alkylene glycol and a ~-dialkyl-substituted aminoalkanol is employed as an emulsifier is described ¦lin U.S. 3,301,804. A polyepoxide emulsion or electrodeposition l~in which a polyepoxide is emulsifiecl with an emulsifying agent of the phosphate ester type is described in U.S. 3,634,348. An epoxy resin emulsion for sizing glass fibers in which a catIonic emulsifying agent selected frorn the group consisting of i', , ~imidazolines and amides and a non-ionic emulsifying agent are used in combination in U.S. 3,249,412.
! Also, various curing agents for epoxy resin emulsion Illcompositions are known in the art. For example, curing agents ¦~for epoxy resin compositions include a polyamide reaction product derived from a polymeric fatty acid and an aliphatic polyamine ~containing terminal amino groups (U.S. 2,811,495 and U.S.
1 2,899,397), a salted amine derived from a carboxylic acid having ~ 8 carbon atoms and a tertiary amine (U.S. 3,640,926), a ¦¦polyamide derived from a diamine and a dicarboxylic acid (U.S. 3,355,409~, a phenol modified polyamine (U.S. 3,383,347), an amino-containing polyamide prepared by reacting a polyamine j,with a polymerized fatty acid (U.S. 3,324,041), and the like.
j In most cases a bisphenol type of epoxy resin is ,employed as a film-forming component of an aqueous epoxy resin paint composition. However, a bisphenol type of epoxy resin as an aqueous dispersion component normally has the disadvantage that lt tends to crystallize and settle out when the aqueous dispersion 1,is stored for three months or longer under ambient conditions.
Destruction of emulsion particles usually occurs with advance of crystallization, and thereafter it is impossible to restore the original state even by heating. Thus, an aqueous epoxy r~sin paint has the disadvantage that if crystallization loccurs the crystallized paint cannot be used for coating purposes.
1 Some recent developments relate to the production o water-borne epoxy resin systems which exhibit improved properties under ambient condit.ons.
, U.S. 4,048,179 describes a process for preparing water-dilutable, heat-curing coating compositions comprising (~) reacting ~an aromatic polyglycidyl ether with a polyethylene glycol in the ;
2 --presence of 0 to 20% of a polyhydric phenol, (b~ adding an aminoplast curing agent, and (c) diluting with water to give a stable aqueous composition.
U.S. 4,073,762 describes an aqueous epoxy resin paint composition comprising an epoxy resin emulsion formed by emulsifying in water (a) 98 to 50% by weight of a bisphenol type ¦epoxy resin and (b) 2 to 50% by weight novolak type epoxy resins, ¦Iwith a non-ionic surface active agent, and a curing agent jlincorporated in said epoxy resin emulsion.
ll There remains a need for improved stable aqueous epoxy ~Iresin dispersions which are adapted for application as industrial ¦¦maintenance coating systems.
ll Accordingly, it is an object of this invention to ¦Iprovide an aqueous dispersion o~ a bisphenol A type epoxy resin, ,,which exhibits long term stability under ambient storage !~ conditions.
!~ It is another object of this invention to provide a freeze-thaw resistant water-borne paint composition containing l,self-emulsifying epoxy resin, which paint composition can be , applied as a coating that cures at room temperature to form a ,continuous thermoset film.
Other objects and advantages of the present invention shall become apparent from the accompanying description and l examples.
~ DESCRIPTION OF THE INVENTION
I~ One or more objects of the present invention are I acco~plished by the provision o~ A stable epoxy dispersion composition comprising (1) an a~ueous medium; and (2) between about S0-70 weight percent of self-emulsifying epoxy resin which is the addition product of reactants comprising (a) 40-90 parts ~3L9~35 by weight of diglycidyl ether of dihydric phenol, (b) 5-35 pax~s j by weight of dihydric phenol, and (c) 2-15 parts by weiyht of I diglycidyl ether of polyoxyalkylene glycol, wherein the ~ molecular weight of the epoxy resin is in the range between ¦ about 500-20,000.
¦~ In one embodiment, this invention provides a stable epoxy dispersion composition comprising (1) an aqueous medium;
1l(2) between about 50-70 weight percent of self-emulsifying epoxy ¦Iresin which is the addition product of reactants comprising - ¦
'(a) 40-90 parts by weight of diglycidyl ether of dihydric phenol, ~ (b) 5-35 parts by weight of dihydric phenol, and (c) 2-15 parts ,iby weight of diglycidyl ether of polyoxyalkylene glycol, wherein jthe molecular weight of the epoxy resin is in the range between ,'about 500-20,000; and (3) 1-25 weight percent, based on resin l.solids weight, of water-immiscible C8-C20 aliphatic monoepoxide reactive diluent.
In another embodiment, this invention provides a l,freeze-thaw resistant epoxy dispersion composition comprising '~ (1) an aqueous medium; (2) between about 50-70 weight percent of self-emulsifying epoxy resin which is the addition product of j reactants comprising (a) 40-90 parts by weight of diglycidyl I
ether of dihydric phenol,. (b) 5-35 parts by weight of dihydric .
phenol and (c) 2-15 parts by weight of diglycidyl ether of polyoxyalklyene glycol, wherein the molecular weight of the epoxy :
~ resin is in the range between about 500-20,000; (3) 1-25 weight '~percent, based on resin solids weight, of water-immiscible ~C8-C~ aliphatic monoepoxide reactive diluent; and (4) 5-20 weight~
percent, based on resin solids weight, of water-miscible solvent selected from C2-C10 glycols and glycol ethers~
In a further embodiment, this invention provides a .. -- 4 --'.
;
~water-borne paint composition comprising (1) an aqueous medium;
(2) between about 50-70 weight percent of self-emulsi~ying epoxy resin which is the addition product of reactants comprising ll(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 I by weight of diglycidyl ether of polyoxyalkylene glycol, wherein the average molecular weight of the epoxy resin is in ;the range between about 500-20,000; and (3) polyarnine curing '~agent, wherein the ratio of active amino hydrogens to epoxy llgroups is in the range between about 0.5-2:1. j I Dihydric Phenol And Glycidyl Ether Components j, . ....................................................... I
The dihydric phenol component and the diglycidyl ether of dihydric phenol component of the epoxy resin may contain other llsubstituents such as alkyl, aryl, sulfido, sulfonyl, halo, and !. the like.
I Illustrative of suitable dihydric phenols are 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-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, and the like. The preferred dihydric ~phenols are 2,2-bis(4-hydroxyphenvl)propane (bisphenol A) and bis(4-hydroxyphenyl)methane for reasons of cost and availability.
The diglycidyl ether derivatives are prepared by the reaction of a dihydric phenol with a halogen-containing epoxide I~or dihalohydrin in the presence of an alkaline medium. By varying the ratios of the dihydric phenol and epichlorohydrin reactants, different molecular weight products can be obtained - as described in United States Patents 2,582,985; 2,615,007; and ~,633,458.
l l ~
For puxposes of the present invention, op~ionally at least a portion of the diglycidyl ether OL dihydric phenol component can be replaced with a diglycidyl ether of a hydro-lgenated dihydric phenol derivative. For example, the said lldiglycidyl etner of dihydric phenol can have up to essentiallylO0 percent of its weight substituted by a diglycidyl alicyclic ether such as 2,2-bis(4-hydroxycyclohexyl)propane or ibis~4-hydroxycyclohexyl)methane.
~, Glycol Glycidyl Ether Component 1 An important feature of the stable aqueous dispersions lof the present invention is the incorporation of a diglycidyl ¦lether of polyoxyalkylene glycol component into the curable epoxy resin vehiclè of the aqueous systems.
The preferred diglycidyl ether of polyoxyalkylene Iglycol derivatives are those having a molecular weight in the range between about 4000-20,000. The said glycol ethers are conveniently prepared by reacting epichlorohydrin with a selected '~olyoxyalkylene glycol, in a molar proportion which provides substantially a diglycidyl ether reaction product.
, The polyoxyalkylene glycol reactant usually is soluble `or at least partially soluble in water. Polyalkylene glycol type compcunds are prepared conveniently by the condensation of an alkylene oxide with a suitable polyhydric alcoholO Illustrative of al'~ylene oxides are ethylene oxide and propylene oxide and mixtures thereof~ Illustrative of polyhydric alcohols are aliphatic alcohols such as ethylene ylycol, 1,3~propylene glycol, 1,2-pro-pylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-buty-'lene glycol, 1,5-pentandiol,1,4,-pentandiol, 1,3-pentandiol, l1,6-hexandiol, l,~-heptandiol, glycerol, 1,1,1 trimethylolpropane, l,l,l-trimethylolethane, hexan-1,2,6-triol, pentaerythritol, !l sorbitol, 2,2-bis(4-hydroxycyclohexyl)propane, and the like~
Preferred polyoxyalkylene glycols are those prepared llby the reaction of ethylene oxide and/or propylene oxide ¦,with a dihydric aliphatic alcohol, e.g., ethylene glycol.
'' ~jIllustrative of polyoxyalkylene ylycols are commercial Pluronic (BASF-Wyandotte) type products which are block copolymers of ethylene oxide and propylene oxide of about 5000-1(),000 molecular ¦Iweight, containing from about 50 to about 90 weight percent ¦;ethylene oxide and about lO to about 50 weight percent propylene lloxide.
Reactive D _ en~ Component l l il The highly preferred stable aqueous epoxy resin dispersions of the present invention are those which contain a l~water-immiscible C8-C20 aliphatic monoepoxide reactive diluent ¦Icomponent. The said monoepoxide component can contain alicyclic and aromatic structures, as well as halogen, sulfur, phosphorus, and other such heteroato~s.
Illustrative of monoepoxide reactive diluents are 'epoxidized unsaturated hydrocarbons such as decene and cyclohexene;
~glycidyl ethers of monohydric alcohols such as 2-ethylhexanol, dodecanol and eicosanol; glycidyl esters of monocarboxylic acids such as hexanoic acid; acetals of glycidaldehyde; and the like.
The preferred reactive diluent is glycidyl ether of monohydric C8-C17 aliphatic alcohols.
~ The presence of a water-immiscible C8-C20 aliphatic ~monoepoxide reactive diluent in an aqueous epoxy resin dispersion ,has a significant beneficial effect on the properties of the aqueous dispersion. The said water-immiscible reactive diluent appears to function by coating khe particles of epoxy resin solids and thereby providing the aqueous dispersion with improved shear, Il.
!
freeze-thaw resistance, shelf viscosity stability, and paint gloss.
Also, since the reactive diluent is epoxy functional, it I becomes incorporated into the film-forming substrate during the ~ subsequent room temperature curing of the aqueous dispersion com- I
position after it has been blended with a curing agent and coated ¦
on a surface. The total quantity o~ reactive diluent contributes ¦
to the calculated proportion of non-volatiles in the dispersion ' composition.
~ Curing Agent , A room temperature curable water-borne coating compo- ¦
;Isition is prepared by admixing a stable epoxy dispersion compo-sition as described above wlth an epoxy-interacting curing vehicle, I such as a polyamine curing agent. The ratio of active amino !Ihydrogens to epoxy groups in the admixture is in the range of , 0.5-2:1 and, preferably, is in the range between about 0.8-1.5:1. ¦
For purposes of industrial maintenance paint compositions, the amino hydrogens must be sufficiently reactive to effect cross- i , linking interaction with the epoxy groups at ambient temperatures. !
I Suitable polyamine curing agents are those which are soluble or dispersible in water and which contain more than 2 active hydrogen atoms per molecule. Examples of such curing agents are alkylene polyamines represented by the formula , H2N R(NH R)XNH2 wherein R is an alkylene radical containing 2 to 4 carbon atoms and X has the value of 0 to 5. Such alkylene polyamines are ethylene diamine, dlethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, propylene l diamine, dibutylene triamine, and the like. Other polyamine curing agents are the polyamido amines, which are reaction products 1~ 35 - of alkylene polyamines and fatty acids. Such polyamido-amines are well kno~l in the art and are described in United States 2,705,223, 2,811,495 and 2,899,397. Other polyamine curing agents are the adducts of polyamines and epoxy compounds such as those described in United States 2,651,589, 2,864,775 and 4,116,900.
Other curing agents can be used in the composi-tion of this inventlon, particularly when the coatings made from the compositions are heated to effect a cure.
Examples of such additional curing agents are the aminoplast and phonolplast resins. Suitable aminoplast resins are the reaction products of ureas and melamines with aldehydes fur-ther etherified in some cases with an alcohol. Examples of aminoplast resin components are urea, ethylene urea, thio-urea, melamine~ benzoguanamine and acetoguanamine. Alde-hydes include formaldehyde, acetaldehyde and propionalde-; hyde. The aminoplast resins can be used in the alkylol form but, preferably, are utilized in the ether form wherein the etherifying agent is a monohydric alcohol containing from 1 to 8 carbon atoms. Examples of suitable ami.noplast resins are methylol urea, dimethoxymethylol urea, butylated poly-meric urea-formaldehyde resins, hexamethoxymethyl melamine~
methylated polymeric melamine-formaldehyde resins and butyl-ated polymeric melamine-formaldehyde resins.
Phenolplast resins are the reaction products of phenols and aldehydes which contain reactive methylol groups.
These compositions can be monomeric or polymeric in nature depending on the molar ratio of phcnol to aldehyde used in the initial condensation react:ion. Examples of suitable phenols are phenol, o, m or p-cresol, 2,4-xylenol, 3,4-xylenol, 2,5-xylenol, cardanol, _ 9 _ - ~ ;
11~ 35 !
p-tert-butyl phenol, and the like. Useful aldehydes are formaldehyde, acetaldehyde and proplonaldehyde. Particularly useful phenolplast resins are polymethylol phenolg wherein the llphenolic group is etherified with an alkyl, e.g., methyl or jlethylr group.
I! An aqueous epoxy resin paint composition of the present jlinvention may further contain addi.tives conventionally employed in coating technology, such as organic pigments, inorganic !Ipigments, surfactants, thickeners, and the like.
l In normal usage, after a water-borne paint composition is prepared using a polyamine curing agent, it is coat2d on a substrate by roller, spray, dip, doctor blade, or similar I application means. The film-forma~ion and curing is accomplished 1~ by air-drying under ambient temperature conditions.
As a further embodiment, the present invention provides water-borne epoxy compositions which have properties suitable for use as a one-package coating system. This type of coating system is prepared by blending a stable epoxy dispersion ; composit~on as described above with a crosslinking agent which is substantially unreactive with the epoxy groups at room temperature. In this type of system, crosslinking is accomplished by baking an applied coating at an elevated temperature.
In addition to the aminoplast and phenolplast curing agents described hereinbefore, other crosslinking agents suitable i ' for the one-package coating systems are novolacs, dibasic car-j, boxylic acids, carboxyl phthalocyanines, dimer and trimer fatty ~l acids, aliphatic and aromatic polycarboxylic acids; and their acid containing acrylic resins such as polyacrylic and poly-methacrylic acids, anhydrides, amide~ and miscellaneous nitrogen , compounds such as dicyandiamide and hydrazides. The various l l i , ~ 9B5 ,i , icuring agents useful with epoxy resins are discussed in Lee and Neville's "~andbook of Epoxy Resins", McGraw-Hill (1967).
Il A present invention one-package coating system as I described above can be cured by heatlng a coated article at a 'temperature between about 90-250C. for a period of time between about 5 minutes and two hours sufficient to effect a ¦thermosetting cure. I
1~ The following examples are further illustrative of the ¦~present 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 llthe invention. Parts and percentages unless otherwise specified llare parts and percentages by weight.
EXAMPLE A
15 ,, This example illustrates a general method for preparing stable epoxy dispersion compositions in accordance with the present invention.
The following components are admixed and heated to 240-, 280F. with stirring under a nitrogen atmosphere:
l, 617 g Epi Rez 510 (Celanese)( ) 179 g Bisphenol A( ) 2.1 g Triphenylphosphine 51 g Novepox Tan 141 (Synthron, Inc.) (3) '' At rnaximum exotherm the temperature rises to 335-385F.
The temperature is maintained at 310-330F. for about an hour, ! then the heating and the 1OW of nitrogen are terminated.
ll l I ~ A 0 to 250 gram quantity of ethylene glycol monoethyl ether is added to the reaction mixture, followed by the slow addition of 100 to 500 milliliters of deionized water as the temperature of the reaction mixture gradually decreases to about ' .
8~
, l130-160~. A dispersion of resin solids is formed which has a "maximum particle size of about 3 microns. The reaction product ', can then be diluted with additional deionized water.
¦I The resin solids generallyconst,i~,ute 50-60 weight l'percent of the a~ueous dispersion and the dispersion has a ¦¦viscosity of 1000 to 10,000 cps (Brookfield, Model RV Spindle I No. 5, 20 RPM).
No settling of resin solids is o~served in a pint llsample after centrifuging at 1000 RPM for 30 minutes. No I settling of resin solids occurs after 6 months of storage at room !; temperature and after 4 weeks at 125F.
~(1) Diglycidyl ether of ~isphenol A; epoxide equivalent weight , of 190.
1'(2) 2,2-Bis(p-hydroxyphenyl)propane.
, (3) Diglycidyl ether of Pluronic F 88 (BASF-Wyandotte)( ).
(4) Block copolymer of ethylene oxide and propylene oxide with , the polyoxypropylene block in t,he middle and with terminal i' !
po'lyoxyethylene blocks. The copolymer contains 80 weight ,' percent ethylene and 20 ~eight percent propylene, and the I~ !
'' average molecular weight is 10,800.
' Example I
'l, The following components'are admixed and heated to 280F.
with stirring under a nitrogen atmosphere:
617 g Epi Rez 510 j~ 179 g Bisphenol A
¦~ 2.1 g Triphenylphosphine ¦' ~ 51 g Novepox Tan 141 When the 280F. temperature is attained, heating is discontinued , and the temperature rises to 355F. d~le to t,he exothermic reaction.
The temperature then drops to 320F. and is held at 315-320F.
1, - 12 -1, for about one hour, after which time the heat source is removed and the flow of nitrogen is terminated.
An 85 gram quantity of ethylene glycol monoethyl ether ¦lis added to the reaction mixture, followed by the slow addition ¦lof 200 milliliters of deionized water as the temperature of the ¦¦reaction mixture gradually decreases to 150F. A dispersion of ! resin solids is formed which has a maximum particle size of 3 microns. The reaction product is then diluted with an additional ;j208 grams of deionized water.
The resin solids of the a~ueous dispersion are 56.5 weight percent and the viscosity of the dispersion is 2000 cps.
~Brookfield, Spindle No. 5, 20 RPM).
I No settling of resin solids is observed in a pint ¦,sample after centrifuying at 1000 RPM for 30 minutes. No settling~
1 15 l of resin solids occurs after 6 months at room temperature.
! I EXP*IPLE II
`.
Employing a similar procedure of component addition and l'heating as in Example I, an epoxy dispersion is prepared from the il Ilfollowing ingredients:
l 617 g Epi Rez 510 (Celanese) ; g Bisphenol A
2.1 g Triphenylphosphine il 70 g Novepox Tan 117 (Synthron, Inc.)( ) , 70 g ~thylene glycol monoethyl ether 813 g Deionized water i~ Viscosity, 7800 cps (Brookfield, Spindle No. 5, 20 RPM).
Solids, 51.3~. .
' No settling after 43 minutes at 1000 RPM.
No settling aft~r 6 months at room temperature.
` - 13 -- ¦ I
l ~
(1) Diglycidyl ether of Pluronic F 38 (BASF~Wyandotte)( );
epoxide equivalent weight of 4760..
l~ (2) Block copolymer of ethylene oxide and propylene oxide ¦¦ having an average molecular weight o 5000.
l ¦ EXAMPLE I I I
In a similar manner to that previously described, an epoxy dispersion is prepared from the following components;
617 g Epi Rez 510 (Celanese) l179 g Bisphenol A
ll2.1 g Triphenylphosphine 70 g Novepox Tan141 (Synthron, Incs) jl70 g Ethylene glycol monoethyl ether ¦638 g Deionized water jl Viscosity, 7500 cps (Brookfield, Spindle No. 5, 20 RPM) 1, Solids, 56.4%.
j No settling after 30 minutes at 1000 RPM.
¦I No settling after 5 months at room temperature 20 ij l: . I
"
25 1l jl -- I
I' I
I!
, EXAMPLE IV
¦ This Example illustrates khe preparation of a stable ~I water-borne paint composi-tion.
j An epoxy dispersion is prepared in the manner li previously described: j 617 g Epi Rez 510 (Celanese) Bisphenol A
2.1 g Triphenylphosphine 1 33 g Novepox Tan141 (Synthron, Inc.~
ll 83 g Ethylene glycol monoethyl ether ¦. 471 g Deionized water ¦l Viscosity, 4200 cps (Brookfield, Spindle No. 5, ll 20 RPM).
¦I Solids, 60.2%
' No settling after 30 minutes at 1000 RPM.
. No settling after 5 months at room temperature.
A paint composition is formulated with the following , components:
1! 381 g Epoxy dispersion described above "
20 ~ I. 250 g Titanium di.o~ide 252 g Water II. 165 g Epi Cure CT 60-8534 (Celanese)( ) i !
11 ' ' 1, i. _ . i ! I
. . .
- 15 - ;
i' 31~ ' The group I components are ground with a high speed i dispersator. Then I and II are blended, and the resultant paint ¦Icomposition is drawn down (3 mil) on steel when it is freshly ¦¦prepared, and also 2, 4 and 6 hours after preparation. The 1¦ Pencil Hardness and Gloss are checked after drying overnight, ~and at intervals at room temperature, as listed below. Pencil IlHardness is conducted according to ASTM D3363-74. Gloss is ¦ determined at 60 angle according to ASTM D523-8.
¦l(l) 60 Weight percent solution of a polyamido-amine in a I solvent mixture of 60 weight percent ethylene glycol ¦ monobutyl ether, 2 0 weight percent ethylene glycol monoethyl ether and 20 weight percent toluene.
I The polyamido-amine has an equivalent weight of 380-385 15 ; on a solids basis.
HardnessFresh 2 hours 4 hours6 hours Overnight2B 2B 2B 2B
¦, 2 days 2B 2B 2B 2B
¦ 3 days B B B B
~' 8 days B B B ~B
, 15 days B B B HB
I' .
Gloss Overnight 81 62 64 45 11 1 week 74 58 52 40 -1 2 weeks 78 66 54 46 ~, , EXAMPI,E V
' This Example illustrates a preparation of a high gloss paint formulation~
~ An epoxy dispersion is prepared wikh the following ~components; the Epoxide 7 component is added af-ter the addition llof the ethylene glycol monoethyl ether and after enough water i5 ¦ladded to allow the formation of an oil in water emulsion.
il617 g Epi Rez 510 (Celanese) ~ g Bisphenol A ~
1 1152 g Novepox Tan l-Drl (Synthron, Inc.) 0 3 g Triphenylphosphine ¦ 121 g Ethylene glycol monoethylether 209 g Deionized water (1) ll17 g Epoxide 7 (Procter & Gamble) ll Viscosity 7,600 cps (Brookfield, Model RV, Spindle No. 5 and 20 RPM).
Solids, 54.7%.
, No settling after 30 minutes at 1000 RPM.
I No settling after 8 months at RT.
jl No settling after 4 weeks at 120F.
I No settling after 2 Freeze and thaw cycles (ASTM
¦` D2243-68).
,` _ i !
i'l i , ,, i - 17 -ll i "
``` 3L~6~
I, .
i .
¦l In a manner similar -to that previously described, paint i compositions are prepared with the following components.
I. 367 g Epoxy dispersion described above I' 77 g Water l¦ 148 g Epi Cure CT-60-8534 (Celanese) ¦, 2.7 g Glacial Acetic Acid II. 250 g Titanium Dioxide 30 g Hydrite UF (Georgia Kaolin Co.)( ) 190 g Water Ii , , Hardness Fresh 2 hours 6 hours ` 3 days 2B B 2B
!. 1 week HB HB HB
' 2 weeks HB HB HB
.
I Gloss , 3 days 99 99 95 ; 1 week 99 99 94 . 2 weeks 98 97 92 .
., '. (1) Glycidyl ether of C8 and C10 alcohol having an epoxide l, equivalent weight of 220-235.
(2) China Clay - Aluminum Silicate.
, .~ .
~L1619135 ii XAMPI,E VI
This is another example of a high gloss paint formulation made from the epoxy resin emulsion in Example V.
~The fllm hardness and gloss are determined by ~,he same methods 5 11 as de-scribed in Example V.
¦, I. 367 g Epoxy dispersion described in Example V
13 g Benzyl Alcohol 5 g Triton X-100 (Rohm & Haas Co.)( ) I, 5 g Tamoi 731 ~Rchm & Haas Co.)( ) ¦l 250 g Titanium Dioxide I' 262 g Water ', '.
I II. 148 g Epi Cure CT-60-8534 (Celanese) .Hardness Fresh 6 Hours ' l day 4B 4B
¦, 2 days 2B 2B
l week HB HB
2 weeks HB HB
Gloss ' 1 day 100 100 , l week 100 100 ,~ 2 weeks 100 100 :
(l) Octyl phenoxy polyethoxy ethanol.
l (2) Sodium salt of polymeric carboxylic acid.
, . - 19 -.
.` ~.
1619B~
The principles, preferred embodiments and modes of ; operation of the present inventlon have been described in the foregoing specification. The invention which is intended to be I protffcted herein, however, is not to be construed as limited to 5 l¦ the particular forms disclosed, since these are to be regarded , as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.
i, , ,' :
i - 20 -
U.S. 4,073,762 describes an aqueous epoxy resin paint composition comprising an epoxy resin emulsion formed by emulsifying in water (a) 98 to 50% by weight of a bisphenol type ¦epoxy resin and (b) 2 to 50% by weight novolak type epoxy resins, ¦Iwith a non-ionic surface active agent, and a curing agent jlincorporated in said epoxy resin emulsion.
ll There remains a need for improved stable aqueous epoxy ~Iresin dispersions which are adapted for application as industrial ¦¦maintenance coating systems.
ll Accordingly, it is an object of this invention to ¦Iprovide an aqueous dispersion o~ a bisphenol A type epoxy resin, ,,which exhibits long term stability under ambient storage !~ conditions.
!~ It is another object of this invention to provide a freeze-thaw resistant water-borne paint composition containing l,self-emulsifying epoxy resin, which paint composition can be , applied as a coating that cures at room temperature to form a ,continuous thermoset film.
Other objects and advantages of the present invention shall become apparent from the accompanying description and l examples.
~ DESCRIPTION OF THE INVENTION
I~ One or more objects of the present invention are I acco~plished by the provision o~ A stable epoxy dispersion composition comprising (1) an a~ueous medium; and (2) between about S0-70 weight percent of self-emulsifying epoxy resin which is the addition product of reactants comprising (a) 40-90 parts ~3L9~35 by weight of diglycidyl ether of dihydric phenol, (b) 5-35 pax~s j by weight of dihydric phenol, and (c) 2-15 parts by weiyht of I diglycidyl ether of polyoxyalkylene glycol, wherein the ~ molecular weight of the epoxy resin is in the range between ¦ about 500-20,000.
¦~ In one embodiment, this invention provides a stable epoxy dispersion composition comprising (1) an aqueous medium;
1l(2) between about 50-70 weight percent of self-emulsifying epoxy ¦Iresin which is the addition product of reactants comprising - ¦
'(a) 40-90 parts by weight of diglycidyl ether of dihydric phenol, ~ (b) 5-35 parts by weight of dihydric phenol, and (c) 2-15 parts ,iby weight of diglycidyl ether of polyoxyalkylene glycol, wherein jthe molecular weight of the epoxy resin is in the range between ,'about 500-20,000; and (3) 1-25 weight percent, based on resin l.solids weight, of water-immiscible C8-C20 aliphatic monoepoxide reactive diluent.
In another embodiment, this invention provides a l,freeze-thaw resistant epoxy dispersion composition comprising '~ (1) an aqueous medium; (2) between about 50-70 weight percent of self-emulsifying epoxy resin which is the addition product of j reactants comprising (a) 40-90 parts by weight of diglycidyl I
ether of dihydric phenol,. (b) 5-35 parts by weight of dihydric .
phenol and (c) 2-15 parts by weight of diglycidyl ether of polyoxyalklyene glycol, wherein the molecular weight of the epoxy :
~ resin is in the range between about 500-20,000; (3) 1-25 weight '~percent, based on resin solids weight, of water-immiscible ~C8-C~ aliphatic monoepoxide reactive diluent; and (4) 5-20 weight~
percent, based on resin solids weight, of water-miscible solvent selected from C2-C10 glycols and glycol ethers~
In a further embodiment, this invention provides a .. -- 4 --'.
;
~water-borne paint composition comprising (1) an aqueous medium;
(2) between about 50-70 weight percent of self-emulsi~ying epoxy resin which is the addition product of reactants comprising ll(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 I by weight of diglycidyl ether of polyoxyalkylene glycol, wherein the average molecular weight of the epoxy resin is in ;the range between about 500-20,000; and (3) polyarnine curing '~agent, wherein the ratio of active amino hydrogens to epoxy llgroups is in the range between about 0.5-2:1. j I Dihydric Phenol And Glycidyl Ether Components j, . ....................................................... I
The dihydric phenol component and the diglycidyl ether of dihydric phenol component of the epoxy resin may contain other llsubstituents such as alkyl, aryl, sulfido, sulfonyl, halo, and !. the like.
I Illustrative of suitable dihydric phenols are 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-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, and the like. The preferred dihydric ~phenols are 2,2-bis(4-hydroxyphenvl)propane (bisphenol A) and bis(4-hydroxyphenyl)methane for reasons of cost and availability.
The diglycidyl ether derivatives are prepared by the reaction of a dihydric phenol with a halogen-containing epoxide I~or dihalohydrin in the presence of an alkaline medium. By varying the ratios of the dihydric phenol and epichlorohydrin reactants, different molecular weight products can be obtained - as described in United States Patents 2,582,985; 2,615,007; and ~,633,458.
l l ~
For puxposes of the present invention, op~ionally at least a portion of the diglycidyl ether OL dihydric phenol component can be replaced with a diglycidyl ether of a hydro-lgenated dihydric phenol derivative. For example, the said lldiglycidyl etner of dihydric phenol can have up to essentiallylO0 percent of its weight substituted by a diglycidyl alicyclic ether such as 2,2-bis(4-hydroxycyclohexyl)propane or ibis~4-hydroxycyclohexyl)methane.
~, Glycol Glycidyl Ether Component 1 An important feature of the stable aqueous dispersions lof the present invention is the incorporation of a diglycidyl ¦lether of polyoxyalkylene glycol component into the curable epoxy resin vehiclè of the aqueous systems.
The preferred diglycidyl ether of polyoxyalkylene Iglycol derivatives are those having a molecular weight in the range between about 4000-20,000. The said glycol ethers are conveniently prepared by reacting epichlorohydrin with a selected '~olyoxyalkylene glycol, in a molar proportion which provides substantially a diglycidyl ether reaction product.
, The polyoxyalkylene glycol reactant usually is soluble `or at least partially soluble in water. Polyalkylene glycol type compcunds are prepared conveniently by the condensation of an alkylene oxide with a suitable polyhydric alcoholO Illustrative of al'~ylene oxides are ethylene oxide and propylene oxide and mixtures thereof~ Illustrative of polyhydric alcohols are aliphatic alcohols such as ethylene ylycol, 1,3~propylene glycol, 1,2-pro-pylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-buty-'lene glycol, 1,5-pentandiol,1,4,-pentandiol, 1,3-pentandiol, l1,6-hexandiol, l,~-heptandiol, glycerol, 1,1,1 trimethylolpropane, l,l,l-trimethylolethane, hexan-1,2,6-triol, pentaerythritol, !l sorbitol, 2,2-bis(4-hydroxycyclohexyl)propane, and the like~
Preferred polyoxyalkylene glycols are those prepared llby the reaction of ethylene oxide and/or propylene oxide ¦,with a dihydric aliphatic alcohol, e.g., ethylene glycol.
'' ~jIllustrative of polyoxyalkylene ylycols are commercial Pluronic (BASF-Wyandotte) type products which are block copolymers of ethylene oxide and propylene oxide of about 5000-1(),000 molecular ¦Iweight, containing from about 50 to about 90 weight percent ¦;ethylene oxide and about lO to about 50 weight percent propylene lloxide.
Reactive D _ en~ Component l l il The highly preferred stable aqueous epoxy resin dispersions of the present invention are those which contain a l~water-immiscible C8-C20 aliphatic monoepoxide reactive diluent ¦Icomponent. The said monoepoxide component can contain alicyclic and aromatic structures, as well as halogen, sulfur, phosphorus, and other such heteroato~s.
Illustrative of monoepoxide reactive diluents are 'epoxidized unsaturated hydrocarbons such as decene and cyclohexene;
~glycidyl ethers of monohydric alcohols such as 2-ethylhexanol, dodecanol and eicosanol; glycidyl esters of monocarboxylic acids such as hexanoic acid; acetals of glycidaldehyde; and the like.
The preferred reactive diluent is glycidyl ether of monohydric C8-C17 aliphatic alcohols.
~ The presence of a water-immiscible C8-C20 aliphatic ~monoepoxide reactive diluent in an aqueous epoxy resin dispersion ,has a significant beneficial effect on the properties of the aqueous dispersion. The said water-immiscible reactive diluent appears to function by coating khe particles of epoxy resin solids and thereby providing the aqueous dispersion with improved shear, Il.
!
freeze-thaw resistance, shelf viscosity stability, and paint gloss.
Also, since the reactive diluent is epoxy functional, it I becomes incorporated into the film-forming substrate during the ~ subsequent room temperature curing of the aqueous dispersion com- I
position after it has been blended with a curing agent and coated ¦
on a surface. The total quantity o~ reactive diluent contributes ¦
to the calculated proportion of non-volatiles in the dispersion ' composition.
~ Curing Agent , A room temperature curable water-borne coating compo- ¦
;Isition is prepared by admixing a stable epoxy dispersion compo-sition as described above wlth an epoxy-interacting curing vehicle, I such as a polyamine curing agent. The ratio of active amino !Ihydrogens to epoxy groups in the admixture is in the range of , 0.5-2:1 and, preferably, is in the range between about 0.8-1.5:1. ¦
For purposes of industrial maintenance paint compositions, the amino hydrogens must be sufficiently reactive to effect cross- i , linking interaction with the epoxy groups at ambient temperatures. !
I Suitable polyamine curing agents are those which are soluble or dispersible in water and which contain more than 2 active hydrogen atoms per molecule. Examples of such curing agents are alkylene polyamines represented by the formula , H2N R(NH R)XNH2 wherein R is an alkylene radical containing 2 to 4 carbon atoms and X has the value of 0 to 5. Such alkylene polyamines are ethylene diamine, dlethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, propylene l diamine, dibutylene triamine, and the like. Other polyamine curing agents are the polyamido amines, which are reaction products 1~ 35 - of alkylene polyamines and fatty acids. Such polyamido-amines are well kno~l in the art and are described in United States 2,705,223, 2,811,495 and 2,899,397. Other polyamine curing agents are the adducts of polyamines and epoxy compounds such as those described in United States 2,651,589, 2,864,775 and 4,116,900.
Other curing agents can be used in the composi-tion of this inventlon, particularly when the coatings made from the compositions are heated to effect a cure.
Examples of such additional curing agents are the aminoplast and phonolplast resins. Suitable aminoplast resins are the reaction products of ureas and melamines with aldehydes fur-ther etherified in some cases with an alcohol. Examples of aminoplast resin components are urea, ethylene urea, thio-urea, melamine~ benzoguanamine and acetoguanamine. Alde-hydes include formaldehyde, acetaldehyde and propionalde-; hyde. The aminoplast resins can be used in the alkylol form but, preferably, are utilized in the ether form wherein the etherifying agent is a monohydric alcohol containing from 1 to 8 carbon atoms. Examples of suitable ami.noplast resins are methylol urea, dimethoxymethylol urea, butylated poly-meric urea-formaldehyde resins, hexamethoxymethyl melamine~
methylated polymeric melamine-formaldehyde resins and butyl-ated polymeric melamine-formaldehyde resins.
Phenolplast resins are the reaction products of phenols and aldehydes which contain reactive methylol groups.
These compositions can be monomeric or polymeric in nature depending on the molar ratio of phcnol to aldehyde used in the initial condensation react:ion. Examples of suitable phenols are phenol, o, m or p-cresol, 2,4-xylenol, 3,4-xylenol, 2,5-xylenol, cardanol, _ 9 _ - ~ ;
11~ 35 !
p-tert-butyl phenol, and the like. Useful aldehydes are formaldehyde, acetaldehyde and proplonaldehyde. Particularly useful phenolplast resins are polymethylol phenolg wherein the llphenolic group is etherified with an alkyl, e.g., methyl or jlethylr group.
I! An aqueous epoxy resin paint composition of the present jlinvention may further contain addi.tives conventionally employed in coating technology, such as organic pigments, inorganic !Ipigments, surfactants, thickeners, and the like.
l In normal usage, after a water-borne paint composition is prepared using a polyamine curing agent, it is coat2d on a substrate by roller, spray, dip, doctor blade, or similar I application means. The film-forma~ion and curing is accomplished 1~ by air-drying under ambient temperature conditions.
As a further embodiment, the present invention provides water-borne epoxy compositions which have properties suitable for use as a one-package coating system. This type of coating system is prepared by blending a stable epoxy dispersion ; composit~on as described above with a crosslinking agent which is substantially unreactive with the epoxy groups at room temperature. In this type of system, crosslinking is accomplished by baking an applied coating at an elevated temperature.
In addition to the aminoplast and phenolplast curing agents described hereinbefore, other crosslinking agents suitable i ' for the one-package coating systems are novolacs, dibasic car-j, boxylic acids, carboxyl phthalocyanines, dimer and trimer fatty ~l acids, aliphatic and aromatic polycarboxylic acids; and their acid containing acrylic resins such as polyacrylic and poly-methacrylic acids, anhydrides, amide~ and miscellaneous nitrogen , compounds such as dicyandiamide and hydrazides. The various l l i , ~ 9B5 ,i , icuring agents useful with epoxy resins are discussed in Lee and Neville's "~andbook of Epoxy Resins", McGraw-Hill (1967).
Il A present invention one-package coating system as I described above can be cured by heatlng a coated article at a 'temperature between about 90-250C. for a period of time between about 5 minutes and two hours sufficient to effect a ¦thermosetting cure. I
1~ The following examples are further illustrative of the ¦~present 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 llthe invention. Parts and percentages unless otherwise specified llare parts and percentages by weight.
EXAMPLE A
15 ,, This example illustrates a general method for preparing stable epoxy dispersion compositions in accordance with the present invention.
The following components are admixed and heated to 240-, 280F. with stirring under a nitrogen atmosphere:
l, 617 g Epi Rez 510 (Celanese)( ) 179 g Bisphenol A( ) 2.1 g Triphenylphosphine 51 g Novepox Tan 141 (Synthron, Inc.) (3) '' At rnaximum exotherm the temperature rises to 335-385F.
The temperature is maintained at 310-330F. for about an hour, ! then the heating and the 1OW of nitrogen are terminated.
ll l I ~ A 0 to 250 gram quantity of ethylene glycol monoethyl ether is added to the reaction mixture, followed by the slow addition of 100 to 500 milliliters of deionized water as the temperature of the reaction mixture gradually decreases to about ' .
8~
, l130-160~. A dispersion of resin solids is formed which has a "maximum particle size of about 3 microns. The reaction product ', can then be diluted with additional deionized water.
¦I The resin solids generallyconst,i~,ute 50-60 weight l'percent of the a~ueous dispersion and the dispersion has a ¦¦viscosity of 1000 to 10,000 cps (Brookfield, Model RV Spindle I No. 5, 20 RPM).
No settling of resin solids is o~served in a pint llsample after centrifuging at 1000 RPM for 30 minutes. No I settling of resin solids occurs after 6 months of storage at room !; temperature and after 4 weeks at 125F.
~(1) Diglycidyl ether of ~isphenol A; epoxide equivalent weight , of 190.
1'(2) 2,2-Bis(p-hydroxyphenyl)propane.
, (3) Diglycidyl ether of Pluronic F 88 (BASF-Wyandotte)( ).
(4) Block copolymer of ethylene oxide and propylene oxide with , the polyoxypropylene block in t,he middle and with terminal i' !
po'lyoxyethylene blocks. The copolymer contains 80 weight ,' percent ethylene and 20 ~eight percent propylene, and the I~ !
'' average molecular weight is 10,800.
' Example I
'l, The following components'are admixed and heated to 280F.
with stirring under a nitrogen atmosphere:
617 g Epi Rez 510 j~ 179 g Bisphenol A
¦~ 2.1 g Triphenylphosphine ¦' ~ 51 g Novepox Tan 141 When the 280F. temperature is attained, heating is discontinued , and the temperature rises to 355F. d~le to t,he exothermic reaction.
The temperature then drops to 320F. and is held at 315-320F.
1, - 12 -1, for about one hour, after which time the heat source is removed and the flow of nitrogen is terminated.
An 85 gram quantity of ethylene glycol monoethyl ether ¦lis added to the reaction mixture, followed by the slow addition ¦lof 200 milliliters of deionized water as the temperature of the ¦¦reaction mixture gradually decreases to 150F. A dispersion of ! resin solids is formed which has a maximum particle size of 3 microns. The reaction product is then diluted with an additional ;j208 grams of deionized water.
The resin solids of the a~ueous dispersion are 56.5 weight percent and the viscosity of the dispersion is 2000 cps.
~Brookfield, Spindle No. 5, 20 RPM).
I No settling of resin solids is observed in a pint ¦,sample after centrifuying at 1000 RPM for 30 minutes. No settling~
1 15 l of resin solids occurs after 6 months at room temperature.
! I EXP*IPLE II
`.
Employing a similar procedure of component addition and l'heating as in Example I, an epoxy dispersion is prepared from the il Ilfollowing ingredients:
l 617 g Epi Rez 510 (Celanese) ; g Bisphenol A
2.1 g Triphenylphosphine il 70 g Novepox Tan 117 (Synthron, Inc.)( ) , 70 g ~thylene glycol monoethyl ether 813 g Deionized water i~ Viscosity, 7800 cps (Brookfield, Spindle No. 5, 20 RPM).
Solids, 51.3~. .
' No settling after 43 minutes at 1000 RPM.
No settling aft~r 6 months at room temperature.
` - 13 -- ¦ I
l ~
(1) Diglycidyl ether of Pluronic F 38 (BASF~Wyandotte)( );
epoxide equivalent weight of 4760..
l~ (2) Block copolymer of ethylene oxide and propylene oxide ¦¦ having an average molecular weight o 5000.
l ¦ EXAMPLE I I I
In a similar manner to that previously described, an epoxy dispersion is prepared from the following components;
617 g Epi Rez 510 (Celanese) l179 g Bisphenol A
ll2.1 g Triphenylphosphine 70 g Novepox Tan141 (Synthron, Incs) jl70 g Ethylene glycol monoethyl ether ¦638 g Deionized water jl Viscosity, 7500 cps (Brookfield, Spindle No. 5, 20 RPM) 1, Solids, 56.4%.
j No settling after 30 minutes at 1000 RPM.
¦I No settling after 5 months at room temperature 20 ij l: . I
"
25 1l jl -- I
I' I
I!
, EXAMPLE IV
¦ This Example illustrates khe preparation of a stable ~I water-borne paint composi-tion.
j An epoxy dispersion is prepared in the manner li previously described: j 617 g Epi Rez 510 (Celanese) Bisphenol A
2.1 g Triphenylphosphine 1 33 g Novepox Tan141 (Synthron, Inc.~
ll 83 g Ethylene glycol monoethyl ether ¦. 471 g Deionized water ¦l Viscosity, 4200 cps (Brookfield, Spindle No. 5, ll 20 RPM).
¦I Solids, 60.2%
' No settling after 30 minutes at 1000 RPM.
. No settling after 5 months at room temperature.
A paint composition is formulated with the following , components:
1! 381 g Epoxy dispersion described above "
20 ~ I. 250 g Titanium di.o~ide 252 g Water II. 165 g Epi Cure CT 60-8534 (Celanese)( ) i !
11 ' ' 1, i. _ . i ! I
. . .
- 15 - ;
i' 31~ ' The group I components are ground with a high speed i dispersator. Then I and II are blended, and the resultant paint ¦Icomposition is drawn down (3 mil) on steel when it is freshly ¦¦prepared, and also 2, 4 and 6 hours after preparation. The 1¦ Pencil Hardness and Gloss are checked after drying overnight, ~and at intervals at room temperature, as listed below. Pencil IlHardness is conducted according to ASTM D3363-74. Gloss is ¦ determined at 60 angle according to ASTM D523-8.
¦l(l) 60 Weight percent solution of a polyamido-amine in a I solvent mixture of 60 weight percent ethylene glycol ¦ monobutyl ether, 2 0 weight percent ethylene glycol monoethyl ether and 20 weight percent toluene.
I The polyamido-amine has an equivalent weight of 380-385 15 ; on a solids basis.
HardnessFresh 2 hours 4 hours6 hours Overnight2B 2B 2B 2B
¦, 2 days 2B 2B 2B 2B
¦ 3 days B B B B
~' 8 days B B B ~B
, 15 days B B B HB
I' .
Gloss Overnight 81 62 64 45 11 1 week 74 58 52 40 -1 2 weeks 78 66 54 46 ~, , EXAMPI,E V
' This Example illustrates a preparation of a high gloss paint formulation~
~ An epoxy dispersion is prepared wikh the following ~components; the Epoxide 7 component is added af-ter the addition llof the ethylene glycol monoethyl ether and after enough water i5 ¦ladded to allow the formation of an oil in water emulsion.
il617 g Epi Rez 510 (Celanese) ~ g Bisphenol A ~
1 1152 g Novepox Tan l-Drl (Synthron, Inc.) 0 3 g Triphenylphosphine ¦ 121 g Ethylene glycol monoethylether 209 g Deionized water (1) ll17 g Epoxide 7 (Procter & Gamble) ll Viscosity 7,600 cps (Brookfield, Model RV, Spindle No. 5 and 20 RPM).
Solids, 54.7%.
, No settling after 30 minutes at 1000 RPM.
I No settling after 8 months at RT.
jl No settling after 4 weeks at 120F.
I No settling after 2 Freeze and thaw cycles (ASTM
¦` D2243-68).
,` _ i !
i'l i , ,, i - 17 -ll i "
``` 3L~6~
I, .
i .
¦l In a manner similar -to that previously described, paint i compositions are prepared with the following components.
I. 367 g Epoxy dispersion described above I' 77 g Water l¦ 148 g Epi Cure CT-60-8534 (Celanese) ¦, 2.7 g Glacial Acetic Acid II. 250 g Titanium Dioxide 30 g Hydrite UF (Georgia Kaolin Co.)( ) 190 g Water Ii , , Hardness Fresh 2 hours 6 hours ` 3 days 2B B 2B
!. 1 week HB HB HB
' 2 weeks HB HB HB
.
I Gloss , 3 days 99 99 95 ; 1 week 99 99 94 . 2 weeks 98 97 92 .
., '. (1) Glycidyl ether of C8 and C10 alcohol having an epoxide l, equivalent weight of 220-235.
(2) China Clay - Aluminum Silicate.
, .~ .
~L1619135 ii XAMPI,E VI
This is another example of a high gloss paint formulation made from the epoxy resin emulsion in Example V.
~The fllm hardness and gloss are determined by ~,he same methods 5 11 as de-scribed in Example V.
¦, I. 367 g Epoxy dispersion described in Example V
13 g Benzyl Alcohol 5 g Triton X-100 (Rohm & Haas Co.)( ) I, 5 g Tamoi 731 ~Rchm & Haas Co.)( ) ¦l 250 g Titanium Dioxide I' 262 g Water ', '.
I II. 148 g Epi Cure CT-60-8534 (Celanese) .Hardness Fresh 6 Hours ' l day 4B 4B
¦, 2 days 2B 2B
l week HB HB
2 weeks HB HB
Gloss ' 1 day 100 100 , l week 100 100 ,~ 2 weeks 100 100 :
(l) Octyl phenoxy polyethoxy ethanol.
l (2) Sodium salt of polymeric carboxylic acid.
, . - 19 -.
.` ~.
1619B~
The principles, preferred embodiments and modes of ; operation of the present inventlon have been described in the foregoing specification. The invention which is intended to be I protffcted herein, however, is not to be construed as limited to 5 l¦ the particular forms disclosed, since these are to be regarded , as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.
i, , ,' :
i - 20 -
Claims (19)
1. A stable epoxy dispersion composition comprising (1) an aqueous medium; and (2) between about 50-70 weight percent of self-emulsifying epoxy resin which is the addition product of reactants comprising (a) 40-90 parts by weight of diglycidyl ether of dihydric phenol, (b) 5-35 parts by weight of dihydric phenol, and (c) 2-15 parts by weight of diglycidyl ether of polyoxy-alkylene glycol, wherein the molecular weight of the epoxy resin is in the range between about 500-20,000.
2. An epoxy dispersion in accordance with claim 1 wherein the diglycidyl ether of dihydric phenol in (a) is diglycidyl ether of bisphenol A.
3. An epoxy dispersion in accordance with claim 1 wherein at least a portion of the diglycidyl ether of dihydric phenol in (a) is replaced with diglycidyl ether of 2,2-bis(4-hydroxycyclohexyl)propane.
4. An epoxy dispersion in accordance with claim 1 wherein the dihydric phenol in (b) is bisphenol A.
5. An epoxy dispersion in accordance with claim 1 wherein the diglycidyl ether of polyoxyalkylene glycol in (3) is diglycidyl ether of polyoxyethylene glycol.
6. An epoxy dispersion in accordance with claim 1 wherein the diglycidyl ether of polyoxyalkylene glycol in (3) is diglycidyl ether of polyoxypropylene glycol.
7. An epoxy dispersion in accordance with claim 1 wherein the diglycidyl ether of polyoxyalkylene glycol in (3) is diglycidyl ether of polyoxyethylene-propylene glycol.
8. An epoxy dispersion in accordance with claim 1 wherein the diglycidyl ether of polyoxyalkylene glycol in (3) has a molecular weight in the range between about 4,000-20,000.
9. A stable epoxy dispersion composition comprising (1) an aqueous medium; (2) between about 50-70 weight percent of self-emulsifying epoxy resin which is the addition product of reactants comprising (a) 40-90 parts by weight of diglycidyl ether of dihydric phenol, (b) 5-35 parts by weight of dihydric phenol, and (c) 2-15 parts by weight of diglycidyl ether of polyoxyalkylene glycol, wherein the molecular weight of the epoxy resin is in the range between about 500-20,000; and (3) 1-25 weight percent, based on resin solids weight, of water-immiscuble C8-C80 aliphatic monoepoxide reactive diluent.
10. An epoxy dispersion in accordance with claim 9 wherein the monoepoxide diluent in (3) is glycidyl ether of monohydrie C8-C17 aliphatie alcohol.
11. A freeze-thaw resistant epoxy dispersion composition comprising (1) an aqueous medium; (2) between about 50-70 weight percent of self-emulsifying epoxy resin which is the addition product of reactants comprising (a) 40-90 parts by weight of diglycidyl ether of dihydric phenol, (b) 5-35 parts by weight of dihydric phenol and (c) 2-15 parts by weight of diglycidyl ether of polyoxyalkylene glycol, wherein the molecular weight of the epoxy resin is in the range between about 500-20,000;
(3) 1-25 weight percent, based on resin solids weight, of water-immiscible C8-C20 aliphatic monoepoxide reactive diluent; and (4) 5-20 weight percent, based on resin solids weight, of water-miscible solvent selected from C2-C10 glycols and glycol ethers.
(3) 1-25 weight percent, based on resin solids weight, of water-immiscible C8-C20 aliphatic monoepoxide reactive diluent; and (4) 5-20 weight percent, based on resin solids weight, of water-miscible solvent selected from C2-C10 glycols and glycol ethers.
12. An epoxy dispersion in accordance with claim 11 wherein the solvent in (4) is ethylene glycol or ethylene glycol alkyl ether.
13. An epoxy dispersion in accordance with claim 11 wherein the solvent in (4) is diethylene glycol or diethylene glycol alkyl ether.
14. An epoxy dispersion in accordance with claim 11 wherein the solvent in (4) is propylene glycol or propylene glycol alkyl ether.
15. An epoxy dispersion in accordance with claim 11 wherein the solvent in (4) is dipropylene glycol or dipropylene glycol alkyl ether.
16. A water-borne paint composition comprising (1) an aqueous medium; (2) between about 50-70 weight percent of self-emulsifying epoxy resin which is the addition product of reactants comprising (a) 40-90 parts by weight of dihycidyl 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, wherein the average molecular weight of the epoxy resin is in the range between about 500-20,000;
and (3) polyamine curing agent, wherein the ratio of active amino hydrogens to epoxy groups is in the range between about 0.5-2:1.
and (3) polyamine curing agent, wherein the ratio of active amino hydrogens to epoxy groups is in the range between about 0.5-2:1.
17. A water-borne paint composition in accordance with claim 16 which contains pigment.
18. A process for providing a substrate surface with a protective coating which comprises applying a water-borne paint composition in accordance with claim 16 to the substrate surface, and thereafter allowing the substrate coating to cure under ambient conditions to form a continuous thermoset film.
19. A one-package water-borne epoxy coating composition comprising (1) an aqueous medium; (2) between about 50-70 weight percent of self-emulsifying epoxy resin which is the addition product of reactants comprising (a) 40-90 parts by weight of diglycidyl ether of dihydric phenol, (b) 5-35 parts by weight of dihydric phenol, and (c) 2-15 parts by weight of diglycidyl ether of polyoxyalkylene glycol, wherein the average molecular weight of the epoxy resin is in the range between about 500-20,000; and (3) a curing agent which is substantially unreactive with epoxy groups at ambient temperature, and which is epoxy-interacting and thermosetting at a temperature in the range between about 90°-250°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/204,101 US4315044A (en) | 1980-11-05 | 1980-11-05 | Stable aqueous epoxy dispersions |
| US204,101 | 1988-06-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1161985A true CA1161985A (en) | 1984-02-07 |
Family
ID=22756618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000388550A Expired CA1161985A (en) | 1980-11-05 | 1981-10-22 | Stable aqueous epoxy dispersions |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4315044A (en) |
| EP (1) | EP0051483B1 (en) |
| JP (1) | JPS57108150A (en) |
| AU (1) | AU541592B2 (en) |
| CA (1) | CA1161985A (en) |
| DE (1) | DE3168394D1 (en) |
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-
1980
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-
1981
- 1981-10-22 CA CA000388550A patent/CA1161985A/en not_active Expired
- 1981-11-02 DE DE8181305209T patent/DE3168394D1/en not_active Expired
- 1981-11-02 EP EP81305209A patent/EP0051483B1/en not_active Expired
- 1981-11-03 AU AU77058/81A patent/AU541592B2/en not_active Expired
- 1981-11-05 JP JP56176582A patent/JPS57108150A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| AU7705881A (en) | 1982-09-09 |
| DE3168394D1 (en) | 1985-02-28 |
| JPH0227368B2 (en) | 1990-06-15 |
| JPS57108150A (en) | 1982-07-06 |
| EP0051483A1 (en) | 1982-05-12 |
| US4315044A (en) | 1982-02-09 |
| EP0051483B1 (en) | 1985-01-16 |
| AU541592B2 (en) | 1985-01-10 |
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