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Timestamp: 2013-05-25 22:29:27
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Patente US5998508 - Aqueous dispersions of polyamide-amine derived from aminoalkylpiperazine ... - Google PatentesB�squeda Im�genes Maps Play YouTube Noticias Gmail Drive M�s » B�squeda avanzada de patentes | Historial web | Iniciar sesi�n B�squeda avanzada de patentesPatentesAn epoxy resin composition containing a) an epoxy resin, b) a liquid amine terminated polyamine curing agent prepared by condensing an aminoalkylpiperazine and a dicarboxylic acid, and (c) water. An aqueous dispersion of the amine terminated polyamine curing agent used in this invention is useful as...http://www.google.es/patents/US5998508?utm_source=gb-gplus-sharePatente US5998508 - Aqueous dispersions of polyamide-amine derived from aminoalkylpiperazine with epoxy resin N�mero de publicaci�nUS5998508 ATipo de publicaci�nConcesi�n N�mero de solicitud08/978,073 Fecha de publicaci�n7 Dic 1999 Fecha de presentaci�n25 Nov 1997 Fecha de prioridad16 Nov 1995Tambi�n publicado comoUS5962629US6013757 InventoresLarry Steven CorleyDerek Scott KincaidGlenda Carole Young Cesionario originalShell Oil Company Clasificaci�n de EE.UU.523/414524/608524/607528/289 Clasificaci�n internacionalC08G69/26C08L63/00C08G59/54C08G59/50C08L77/00C08G69/34C09D163/00C08J3/24 Clasificaci�n cooperativaC08J2363/00C08J3/24C09D163/00C08G69/265C08G69/34C08G69/26C08G59/54 Clasificaci�n europeaC08J3/24C09D163/00C08G69/26KC08G59/54C08G69/34C08G69/26ReferenciasCitas de patentes (30) Citada por (6)Enlaces externosUSPTO Cesi�n de USPTO EspacenetAqueous dispersions of polyamide-amine derived from aminoalkylpiperazine with epoxy resinUS 5998508 A Resumen An epoxy resin composition containing a) an epoxy resin, b) a liquid amine terminated polyamine curing agent prepared by condensing an aminoalkylpiperazine and a dicarboxylic acid, and (c) water. An aqueous dispersion of the amine terminated polyamine curing agent used in this invention is useful as a curing agent for water borne applications.
We claim: 1. A curable epoxy resin composition comprising: (a) an epoxy resin having at least 1.5 epoxy groups per molecule; (b) a liquid amine terminated polyamide prepared by reacting at least one C.sub.18-50 dicarboxylic acid, dicarboxylic acid ester or dicarboxylic acid chloride and an amine compound consisting of an aminoalkylpiperazine; and (c) water; wherein said polyamide is mixed with water to provide an oil-in-water emulsion when preparing said composition.
2. The composition of claim 1 wherein the ratio of moles of aminoalkylpiperazine to equivalents of carboxyl groups in the acid is greater than 0.75:1.
3. The composition of claim 1 wherein the mole ratio of the epoxy resin to liquid amine terminated polyamide is from about 3:1 to about 1:3.
4. The composition of claim 1 wherein the aminoalkylpiperazine is selected from the group consisting of N-(2-aminoethyl)piperazine, N,N'-bis(2-aminoethyl)piperazine and N,N'-bis(3-aminopropyl)piperazine.
5. The composition of claim 4 wherein the dicarboxylic acid is selected from the group consisting of adducts of acrylic and methacrylic acids with unsaturated fatty acids and dimerized unsaturated fatty acids.
6. The composition of claim 4 wherein the dicarboxylic acid is a dimerized unsaturated fatty acid.
7. The composition of claim 1 wherein the liquid amine terminated polyamide component (b) is prepared by reacting (i) a C.sub.18-50 dicarboxylic acid, (ii) at least one other dicarboxylic acid and (iii) an aminoalkylpiperazine.
8. The composition of claim 1 further comprising an accelerator.
This is a division of application Ser. No. 08/558,357, filed Nov. 16, 1995, allowed.
BACKGROUND OF THE INVENTION A typical commercial ambient cure epoxy coating contains condensates of dimer acids with polyethylene polyamines containing more than 4 amine hydrogen atoms as a curing agent and a solution of a solid epoxy resin. This epoxy coating system has excellent flexibility adhesion to many substrates, and resistance to water and many types of solvents. However, a problem with this system is that a solvent content of almost 50% is necessary in order to obtain a "sprayable" (Gardner D or lower) viscosity. A large fraction of such solvent evaporates from a coating, or other exposed layer of epoxy resins during cure, and thereby behaves as a volatile organic compound (VOC). Environmentally it is desirable to have low VOC content. However, it is difficult to provide a stable zero VOC aqueous dispersion of polyamine based curing agents having good cured product properties.
Solvent requirements can be reduced considerably by using a system based on liquid epoxy resin with the above polyethylene polyamine curing agent. However, even this approach still requires a system solvent level of about 30% in order to obtain a Gardner "D", or sprayable, viscosity. One way to obtain very low, or in some cases even zero, VOC content is to use a waterborne system. Standard curing agents for waterborne systems, however, are water-soluble or nearly water-soluble adducts of polyamines with epoxy resins, or else Mannich base-type amine curing agents. These materials tend to yield cured films with considerably lower flexibility and impact resistance than those provided by standard solvent-borne epoxy systems cured with polyamide-amine curing agents.
The aminoalkylpiperazine-based amine terminated polyamide can be produced by reacting long-chain dicarboxylic acids such as dimerized fatty acids ("dimer acids") or adducts of acrylic and methacrylic acid with unsaturated fatty acids ("adduct acids") with aminoalkylpiperazines under conditions effective to produce a liquid amine terminated polyamide. The resultant polyamines have a number-average amine hydrogen functionality of above 1.7 and up to 4. Preferably the polyamide has an amine plus acid number greater than about 250 and has an excess of amine groups over acid groups.
The aminoalkylpiperazine-based amine terminated polyamide may be prepared by thermal condensation of the aminoalkylpiperazine, preferably in excess, with one or more long-chain dicarboxylic acids or their esters under conditions effective to produce a liquid aminoalkylpiperazine-based amine terminated polyamide. Generally the reaction is carried out at a temperature gradually climbing to a level of above about 200 preferably at a final temperature within the range of from about 220 liquid reaction product, followed by distillation, preferably under vacuum, to remove excess unreacted amine, as well as water and/or alcohol reaction product. (The water or alcohol reaction product generally distills at atmospheric pressure before vacuum is applied.) The term "liquid" refers to compositions which have a melting point, or ring and ball softening point (ASTM E28-67) of below room temperature (typically 25 polyamides are low molecular weight oligomers, typically having number average molecular weight within the range from about 400, preferably from about 700, to about 3000, preferably to about 2000. Alternatively, the amine may be reacted with a chloride of the dicarboxylic acid, but this synthetic procedure is less desirable because of the byproducts produced and the cost of the acid chlorides.
Examples of the "adduct acids" include adducts of acrylic acid, methacrylic acid, crotonic acid, etc. with linoleic acid, soybean oil fatty acid, tall oil fatty acid, etc. These adducts are normally prepared by thermal reaction at temperatures ≧200 preparation of these adduct acids are described, for example, in U.S. Pat. No. 3,753,968.
Aminoalkylpiperazines can be represented by the following formula: ##STR1## where R.sup.1 and R.sup.2 are each independently --H or --R.sup.3 --NH.sub.2, wherein R.sup.3 is a divalent aliphatic linkage, preferably a chain of --CH.sub.2 -- units with optional --CHR.sup.4 -- or CR.sup.4 R.sup.5 -- units, wherein R.sup.4 and R.sup.5 are independently alkyl groups, provided that at least one of R.sup.1 and R.sup.2 is --R.sup.3 --NH.sub.2 --. The divalent aliphatic linkages preferably have 2-6 carbon atoms.
Examples of the aminoalkylpiperazines include N-(2-aminoethyl)piperazine, N,N'-bis(2-aminoethyl)piperazine and N,N'-bis(3-aminopropyl)piperazine. N-(2-aminoethyl)piperazine and N,N'-bis(2-aminoethyl)piperazine are typical byproducts of the commercial production of ethylene amines from ammonia and ethylene oxide or ethylene dichloride. N,N'-bis(3-aminopropyl)piperazine is prepared by reacting piperazine with acrylonitrile to form N,N'-bis(2-cyanoethyl)piperazine, followed by hydrogenation of the nitrile groups to amine groups. Methods for the preparation of aminoalkylpiperazines are described, for example, in I. Ono, Kagaku Keizai, 26(6), pp.20-27 (1979), and Q. Sun and C. Zhu, Shanghai Diyi Yixueyuan Xuebao, 12(3), pp. 178-182 (1985).
The amine terminated polyamide curing agent can also be prepared by reacting an aminoalkylpiperazine with one or more long-chain dicarboxylic acids and optionally one or more other dicarboxylic acids. Such other dicarboxylic acid can be any dicarboxylic acid having carbon numbers from 4-20, which can be a long-chain or not a long-chain dicarboxylic such as azelaic acid, sebacic acid, and adipic acid. Preferably, the dicarboxylic acids are all long-chain dicarboxylic acids. A minor amount (up to about 25% of total carboxyl equivalents) of a monocarboxylic acid such as tall oil fatty acid may also be added as a chain terminator. To obtain the amine terminated polyamide curing agent useful for the invention, up to about 50% of the long-chain dicarboxylic acid, a dicarboxylic acid which is not a long-chain dicarboxylic acid can be used depending on the intended use of the product.
An accelerator can be included to increase the cure rate of the epoxy resin-curing agent system. Various amine-compatible accelerators can be used as long as they are soluble in the amine curing agents or water. Examples of accelerators include metal salts such as, for example, sulfonates, phosphonates, sulfates, tetrafluoroborates, carboxylates and nitrates of Groups IA, IIA and transition metal series of the Periodic Table (CAS version), preferably Mg, Ca, Zn and Sn salts, and complexes thereof; inorganic acids such as, for example, HBF.sub.4, H.sub.2 SO.sub.4, H.sub.2 NSO.sub.3 H and H.sub.3 PO.sub.4 ; carboxylic acids, preferably hydroxy-substituted carboxylic acids such as, for example, salicylic, lactic, glycolic and resorcylic; phenolic compounds such as, for example, phenol, t-butylphenol, nonylphenol and bisphenol A; imidazoles; cyanamide compounds such as dicyandiamide and cyanamide; sulfonamides such as, for example p-toluenesulfonamide, methanesulfonamide, N-methylbenzenesulfonamide and sulfamide; and imides such as, for example, phthalimide, succinimide, perylenetetracarboxylic diimide and saccharin.
The epoxy resin can be any epoxy resin which can be cured by the amine terminated polyamide curing agent. Generally, the epoxy resin can be any curable epoxy resin having a 1,2-epoxy equivalency greater than one and preferably, on the average, more than about 1.5 epoxide groups per molecule. The epoxy resin can be saturated or unsaturated, linear or branched, aliphatic, cycloaliphatic, aromatic or heterocyclic, and may bear substituents which do not materially interfere with the curing reaction. Such substituents can include bromine. The epoxy resin may be monomeric or polymeric, liquid or solid, but is preferably liquid at room temperature. Suitable epoxy resins include glycidyl ethers prepared by reacting epichlorohydrin with a compound containing at least one, preferably two or more, hydroxyl groups carried out under alkaline reaction conditions. Examples of epoxy resins suitable for use in the invention include polyglycidyl ethers of polyhydric phenols, epoxy novolacs or similar glycidated polyphenolic resins, polyglycidyl ethers of glycols or polyglycols, and polyglycidyl esters of polycarboxylic acids.
The preferred epoxy resin is a resin based on a polyglycidyl ether of a polyhydric phenol for waterborne coatings, including cathodic electrodeposition, applications (other than highly ultraviolet-resistant topcoats, for which an aliphatic epoxy resin is preferred). Polyglycidyl ethers of polyhydric phenols can be produced, for example, by reacting an epihalohydrin with a polyhydric phenol in the presence of an alkali. Examples of suitable polyhydric phenols include: 2,2-bis(4-hydroxyphenyl) propane (bisphenol-A); 2,2-bis(4-hydroxy-3-tert-butylphenyl) propane; 1,1-bis(4-hydroxyphenyl) ethane; 1,1-bis(4-hydroxyphenyl) isobutane; bis(2-hydroxy-1-naphthyl) methane; 1,5-dihydroxynaphthalene; 1,1-bis(4-hydroxy-3-alkylphenyl) ethane and the like. Suitable polyhydric phenols can also be obtained from the reaction of phenol with aldehydes such as formaldehyde (bisphenol-F). Fusion products of these polyglycidyl ethers of polyhydric phenols with phenolic compounds such as bisphenol-A are also suitable as epoxy resins, such as those described in U.S. Pat. Nos. 3,477,990 and 4,734,468. Commercial examples of preferred epoxy resins include, for example, EPON available from Shell Chemical Company.
In a typical waterborne application, the epoxy resin is preferably in an aqueous dispersion having a solids content from about 5% to about 75%. Generally, water and an epoxy resin having a functionality of greater than about 1.5 epoxide group per molecule are mixed under conditions effective to provide an oil-in-water emulsion in the presence of from about 1 to about 20 weight percent, based on the epoxy resin, of at least one non-ionic surfactant. Aqueous dispersions of some of these epoxy resins and surfactants used are described in U.S. Pat. Nos. 4,122,067 and 5,236,974 which are hereby incorporated by reference. Preferred commercial examples of these aqueous epoxy resin dispersions are EPI-REZ 3510-W-60, 3515-W-60, 3522-W-60, 3530-W-70, 3540-WY-510 (allaqueous dispersions of epoxy resins) available from Shell Chemical Company.
The epoxy resin composition of the invention may include other additives, such as flow control additives such as solvents or anti-sag agents, as well as other additives such as pigments, reinforcing agents, fillers, elastomers, stabilizers, extenders, plasticizers, anti-foaming agents, and flame retardants depending on the application. The epoxy resin composition is useful for coatings, as adhesives, and for sizing or impregnating substrates such as sheets, cords, yarns and prepregs for various applications.
For coating applications, the curable epoxy resin composition can also contain pigments of the conventional type such as iron oxides, lead oxides, strontium chromate, carbon black, titanium dioxide, talc, barium sulfate, phthalocyanine blue and green, cadmium red, chrome green, lead silicate, silica, silicates and the like. Such pigments can be added to the polyamide curing agent component or the epoxy resin component prior to mixing them together. However, iron blue pigment, calcium carbonate and pigments considered reactive because of their basic nature are not compatible in the epoxy resin coating system when used in appreciable quantities. These normally are added to the curing agent component only. Defoamers, tints, slip agents, thixotropes, etc., are common auxiliary components to most coatings and may be employed in the epoxy resin composition of the present invention.
Example 1 demonstrates the preparation of the liquid aminoalkylpiperazine-based amine terminated polyamine. Examples 2-7 demonstrate use of the aqueous dispersion of aminoalkylpiperazine-based amine terminated polyamide as curing agent. Dimer acid (�10% C.sub.18 monobasic acids, �80% C.sub.36 dibasic acids, �10% C.sub.54 tribasic acids) was obtained from Shell Chemical Co. N-(2-aminoethyl)piperazine was obtained from Dow Chemical Co. EPON Resin 828 (a diglycidyl ether of bisphenol A having epoxy equivalent weight of 185-192), EPON of bisphenol A having epoxy equivalent weight of 450-550), EPI-REZ Resin WD-510 (a water dispersible bisphenol A-based epoxy resin with an epoxide equivalent weight of 190-205), EPI-REZ aqueous dispersion, 60% solids, of a bisphenol A-based epoxy resin with an epoxide equivalent weight of approximately 185-215), EPI-REZ 3515-W-60 (an aqueous dispersion, 60% solids, of a bisphenol A-based epoxy resin with an epoxide equivalent weight of 225-275), EPI-REZ 3522-W-60, (an aqueous dispersion, 60% solids, of a bisphenol A-based epoxy resin with an epoxide equivalent weight of 625-745), EPI-REZ Resin 3530-W-70 (an aqueous dispersion, 70% solids, of an epoxy resin with an epoxide equivalent weight of approximately 250), EPI-REZ 3540-WY-55 (an aqueous dispersion, 55% solids, of a bisphenol A-based epoxy resin with an epoxide equivalent weight of 1600-2000) were obtained from Shell Chemical Company. HELOXY mixture of 1-dodecanol and 1-tridecanol having an epoxy equivalent weight of 275-295) and HELOXY of oligomers of propylene oxide with an epoxide equivalent weight of 305-335) were obtained from Shell Chemical Company. EPI-CURE Agent 3140 (a polyamide-amine curing agent based on dimer acid, fatty acid, and triethylenetetramine) and EPI-CURE polyamide-amine curing agent based on dimer acid, fatty acid, and a mixture of polyethylenepolyamines) were obtained from Shell Chemical Company.
EXAMPLE 1 Preparation of low amine hydrogen functionality liquid amine terminated polyamide by reaction of dimerized fatty acid with excess aminoalkylpiperazine
"Dimer acid" with a Gardner viscosity of Z4-1/4, (carboxyl equivalent weight of between approximately 280 and 290) from the Shell Chemical Company, was mixed in the ratios indicated in Table 1 below with N-(2-aminoethyl)piperazine (AEP), in 5-liter round-bottom flasks equipped with a heating mantle, a paddle stirrer, a thermocouple, a nitrogen purge, and a Vigreux column with a vacuum distillation takeoff. The system was purged with nitrogen and heating was started. Typically, when the pot temperature had reached 150-170 atmospheric pressure. Water distillation at atmospheric pressure continued until the pot temperature had been raised to 220-240 was held at this temperature until water distillation had stopped or had essentially stopped. Vacuum was then applied and vacuum distillation of excess amine was carried out until the pot temperature had risen back to 220-240 negligible. Vacuum stripping was then continued at this temperature for approximately another 15 minutes. The products were then allowed to cool to about 150 were then poured into jars. The products were characterized by amine nitrogen content (by titration) and viscosity. Results are shown in Table 1 below.
TABLE 1______________________________________Run #              1          2______________________________________Amine used         AEP        AEP  grams 1695 1725  moles 13.118 13.12.sup.e  Dimer acid,  grams 1837.5 1837.5  --COOH equivalents 6.358 6.42  Reactant ratio, moles amine/eq COOH 2.06 2.04  Reaction time, hours 6.5 3.7  Atmospheric pressure distillate, g 129.36 155.26  Vacuum distillate, grams 902.3 898.2  Final reaction temperature/ pressure.sup.a 238                         235  Nonvolatile product, grams 2460.9 2481.3  Amine nitrogen content, %, by titration 6.69 6.86  Amine nitrogen content, %, theoretical.sup.b 7.00 7.00  Amine nitrogen equiv. wt..sup.c 209.4 210.6  Amine hydrogen equiv. wt..sup.d 284.8 288.3  Ubbelohde kinematic viscosity, 40  mm.sup.2 /sec______________________________________ .sup.a Curing agents were prepared by mixing dimer acid with amine in a roundbottom flask equipped with a paddle stirrer, thermocouple and distilling head. The mixtures were heated (under nitrogen) to slow reflux for approximately 2 hours, followed by distillation at atmospheric pressure and finally stripping under pump vacuum at the temperature and pressure indicated above. .sup.b Calculated for product composed solely of condensation product of one molecule of dimer acid and two molecules of amine. .sup.c Calculated from amine nitrogen content determined by titration. .sup.d For polyamides made with AEP, the amine hydrogen equivalent weight was calculated by dividing the number average molecular weight (calculate from amine nitrogen content determined by titration) by 3 (with the assumption that the --NH.sub.2 and --NH groups have equal reactivity toward the dimer acid so that the average polyamide molecule contains 3 amine hydrogens). .sup.e From amine nitrogen content determined by titration (this lot of AEP apparently contained approximately 2% water)
EXAMPLE 2 This example covers the use of an AEP-dimer acid condensate in a waterborne dispersion
A 1-liter kettle was fitted with a paddle stirrer, a thermocouple and an addition funnel. To the kettle were added 100.0 grams of the product of Example 1, run #2. To the addition funnel were added 150.0 grams of deionized water for a total of 250.0 grams. The kettle was heated to 88 metered in from the addition funnel over a 30 minute period. After the water was added, the mixture was held at 88 an additional 30 minutes. The product was then poured into a glass bottle and stored for further characterization and used in Examples below. The product, at 40% solids, had a room temperature viscosity (Brookfield RVT, spindle #5) of 21 Pa�s (21000 cp).
TABLE 2______________________________________System #           1          2______________________________________Resin Composition  EPON.sup.a Resin 828  80  HELOXY.sup.a Modifier 9  20  20  EPI-REZ.sup.a Resin WD-510   80  Water  100  Curative Component, phr  (based on resin solids)  Product of Example 1, run #2 182  Water dispersion of curing agent -- 455 phr  prepared in text above  dispersion    (182 phr solids)  Handling Characteristics.sup.a  Resin Solids 100% 50%  Curative Solids 100% 40%  System Solids 100% 43%  Resin Viscosity, mPa   Curative Viscosity, mPa                           System Viscosity, mPa                          600.sup.f 11 200.sup.g  Combining Ratio by volume 1.82:1 2.27:1  Pot life, 100 gram mass.sup.b 45 minutes 55 minutes  Performance Properties.sup.c  Aluminum-Aluminum Peel Adhesion.sup.d 2.5 N/mm 2.1 N/mm   (14 pli) (12 pli)  Fiberglass Peel Adhesion.sup.e &amp;gt;13 N/mm &amp;gt;13 N/mm   (75 pli).sup.h (75 pli).sup.h______________________________________ .sup.a All systems tested at 25 .sup.b Time to gel as determined by manual probing with a tongue depressor. .sup.c Systems cured 1 hour @ 100 crosshead speed 50.8 cm/minute (20 inch/minute). .sup.d 0.127 mm (5 mil) aluminum, acid etched. .sup.e Tetraglas Plain tape, 1.59 mm (1/16")  fiberglass. .sup.f Viscosities measured by Brookfield RVT, spindle #29. .sup.g Viscosities measured by Brookfield RVT, spindle #5. .sup.h Failure occurred in the fiberglass tape substrate.
A mixed epoxy resin dispersion in water was prepared at room temperature as follows. A 3-liter reaction kettle was equipped with an anchor stirrer, thermocouple and condenser. To the kettle were added 113.4 grams of a 32% aqueous solution of a surfactant made by reacting EPON with 8000 molecular weight poly(ethylene oxide) glycol. To the surfactant, with stirring, were added 491 grams of EPON of 25 minutes. To this mixture, with stirring, were added 122.6 grams of HELOXY and stirring was continued for another 1.5 hours; the temperature at that point had reached 45 with the addition of 275 grams of deionized water. At the end of this period the temperature had dropped to 31 for an additional 45 minutes as the temperature was brought up to 54 another hour. At the end of this period, heating was removed and stirring was continued for another hour as the mixture cooled to room temperature. The final product had a Brookfield viscosity of 2.2 Pa�s and a number-average particle diameter of 690 nm. It is referred to as "Waterborne Resin Mixture A" in the experiments in the remainder of this example.
Three "polyamide" curing agent dispersions in water were prepared as follows. A 1-liter reaction kettle was equipped with an anchor stirrer, thermocouple and condenser. To the kettle were added 200 grams of amine-terminated "polyamide" curing agent (AEP-dimer acid "polyamide," EPI-CURE batch of AEP-dimer acid "polyamide" used in this example was prepared at the same reactant ratio of �2 moles AEP/carboxyl equivalent of dimer acid as the two batches in Example 1 and under similar conditions, but on a 30-kilogram scale.) The curing agent was heated to 100 curing agent were then added 300 grams of water over approximately 10 minutes with stirring maintained at a speed of 60 rpm. Heating maintained the reactor temperature at 97-100 addition was complete, heating was withdrawn and stirring was continued at 30-60 rpm as the mixture was allowed to cool. When the reactor temperature reached 83 cool to room temperature without stirring. The aqueous dispersion prepared from the AEP-dimer acid "polyamide" appeared smooth, milky and evenly opaque. The corresponding dispersions prepared from EPI-CURE Agents 3125 and 3140 appeared grossly heterogeneous, with some parts of the liquid appearing translucent and others appearing opaque. The dispersions prepared from EPI-CURE when diluted with water, appeared to contain some large particles visible to the naked eye. The dispersions prepared from EPI-CURE Agents 3125 and 3140 also were higher in viscosity than that prepared from the AEP-dimer acid polyamide (Table 3 below).
TABLE 3______________________________________Run #       1      2      3    4     5     6______________________________________Curing agent  dispersion preparation:  AEP-dimer    200  polyamide, parts  EPI-CURE Curing     200  Agent 3125, parts  EPI-CURE Curing      200  Agent 3140, parts  Water, parts    300 300 300  Brookfield viscosity     24  78 37.5  of dispersion, room  temperature, Pa   Dispersion appearance    Opaque, Trans- Trans- smooth lucent lucent  and and  opaque opaque  zones zones  Resin composition:  EPON Resin 100 100 100  828/HELOXY  Modifier  9 blend, parts  Waterborne Resin    154 154 154  Mixture A, parts  Curing agent  composition:  AEP-dimer polyamide, 171  parts  EPI-CURE Curing   48  Agent 3125, parts  EPI-CURE Curing    44  Agent 3140, parts  Waterborne curing    428 120 110  agent prepared  above in same column,  parts  Adhesion properties:.sup.a  Aluminum-aluminum, 2.12 0.35 0.14 1.24 0.25 0.28  T-peel, N/mm  PET-PET, &amp;gt;6.7.sup.b &amp;lt;0.05 &amp;lt;0.05 &amp;gt;0.70.sup.b 0.07 0.05  T-peel, N/mm______________________________________ .sup.a Tpeel adhesion measured per ASTM D1876 at 25.4 cm/minute. .sup.b Failure occurred in PET film substrate.
TABLE 4______________________________________Run #    1       2       3     4     5     6______________________________________Composition:  EPI-REZ Resin 167  3515-W-60.sup.a,  parts  EPI-REZ Resin  167  3522-W-60.sup.b,  parts  EPI-REZ Resin   143  3530-W-70.sup.c,  parts  EPI-REZ Resin    182  3540-WY-55.sup.d,  parts  EPI-REZ Resin      80  WD-510.sup.c, parts  HELOXY.sup.e      20  Modifier 9.sup.f,  parts  Water, parts     100  EPI-REZ Resin      135.67  3510-W-60.sup.a,  parts  HELOXY      14.33  Modifier 32.sup.h,  parts  Above curing 368 138 368  50 455 428  agent dis-  persion, parts  Films cured 1  hour at  100  Film Orange Orange Slight Smooth Heavy Orange  appearance peel peel orange  orange peelpeel  peel  Film clarity Clear Clear Slightly Clear Clear Clearcloudy  Pencil hardness 3H 3H 1H 3H 1H 3H  Films cured  at room  temperature:  Film Smooth Smooth Smooth Smooth Heavy Smooth  appearance     orange  peel  Film clarity Clear Cloudy Cloudy Cloudy Clear Clear  Tack after Slight None None None Tacky Tacky  2 hours  Pencil hardness 3B 3B &amp;lt;6B HB &amp;lt;6B 1H  after 24 hours______________________________________ .sup.a An aqueous dispersion (60% solids) of a bisphenol Abased epoxy resin with an epoxide equivalent weight of 225-275. .sup.b An aqueous dispersion (60% solids) of a bisphenol Abased epoxy resin with an epoxide equivalent weight of 625-745. .sup.c An aqueous dispersion (70% solids) of an epoxy resin with an epoxide equivalent weight of approximately 250. .sup.d An aqueous dispersion (55% solids) of a bisphenol Abased epoxy resin with an epoxide equivalent weight of 1600-2000. .sup.e A waterdispersible bisphenol Abased epoxy resin with an epoxide equivalent weight of 190-205. .sup.f A mixture of dodecyl and tridecyl glycidyl ethers with an epoxide equivalent weight of 275-295. .sup.g An aqueous dispersion (60% solids) of a bisphenol Abased epoxy resin with an epoxide equivalent weight of 185-215. .sup.h A mixture of diglycidyl ethers of oligomers of propylene oxide wit an epoxide equivalent weight of 305-335.
TABLE 5______________________________________        EPI-REZ Resin EPI-REZ Resin   3515-W-60 3515-W-60   water dispersion water dispersion   of product of of EPI-CURE  Paper saturant system Example 1, run #1 Curing Agent 3140______________________________________R.T. tensile properties  of resin-saturated  paper: (ASTM D-882)  Dry:  Strength, MPa 18.2  24.2  Modulus, MPa 1415 1740  Elongation, % 4.3  3.7  After water soak:  Strength, MPa 9.2 15.7  Modulus, MPa 222 59.5  Elongation, % 10.2   7.4  After MEK soak:  Strength, MPa 8.0 11.3  Modulus, MPa 266 355  Elongation, % 6.4  5.1______________________________________
One can see from Table 6 that the invention compositions showed much more rapid coating dry time at room temperature than the control system cured with EPI-CURE compositions likewise were much harder (pencil hardness F versus 5B) than the control composition and also had greater resistance to methyl ethyl ketone (MEK).
TABLE 6______________________________________Formulation          1       2       3______________________________________EPI-REZ                 25      25      25  Product of Example 1, run #1, parts 26.2 22.5  EPI-CURE   Water (pre-slurried with curing agent), parts 26.2 22.5 7.1  Viscosity (mPa   at indicated time:  Immediately after mixing 93500 91500 18000  30 minutes 23300 15900 18300  60 minutes  1300  4200 18000  90 minutes  1100  2700 19000  120 minutes  900  2500 18500  Dry times (hours),  room temperature:  Tack free &amp;lt;4 &amp;lt;4 &amp;gt;24  Cotton free  4  4 (&amp;gt;24)  Through dry 22 14.5 (&amp;gt;24)  Baked film properties  (30 min. @121  Pencil hardness (ASTM D3363) F F 5B  MEK resistance, double rubs &amp;gt;100 &amp;gt;100 50  Direct impact, J (ASTM D2794) &amp;gt;160 &amp;gt;160 &amp;gt;160  Reverse impact, J (ASTM D2794)  160  160 &amp;gt;160______________________________________
TABLE 7______________________________________Formulation       1        2        3______________________________________Waterborne Resin Mixture A, parts             47.5     47.5     47.5  Product of Example 1, run #1, parts 51.4  EPI-CURE   3055, parts  Blend of 85% (wt.) product of   39.9  Example 1, run #1, and  15% (wt.) N-(2-aminoethyl)  piperazine, parts  Additional water, parts 172 81.9 145.6  (used for forming curing  agent dispersion)  Baked film properties  (30 min. @121  Room temperature lap shear strength, 14.8 .+-. 1.2 9.6 .+-. 3.1 16.3                               .+-. 0.9  MPa (ASTM D-1002)______________________________________
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