Source: http://www.google.com/patents/US6013757?dq=7389243
Timestamp: 2015-06-02 13:43:10
Document Index: 700191478

Matched Legal Cases: ['arts    200', 'arts     200', 'arts      200', 'arts    300', 'arts    154', 'arts 171', 'arts  48', 'arts   44', 'arts 167', 'arts  167', 'arts   143', 'arts    182', 'arts     80', 'arts     20', 'arts     100', 'arts      135', 'arts      14', 'arts 368', 'arts               25', 'arts    26', 'arts             47', 'arts 51']

Patent US6013757 - Coating or impregnant of epoxy resin and aqueous polyamide-amine dispersion - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA substrate is coated or impregnated with a composition comprising an a) epoxy resin, b) a liquid amine-terminated polyamide curing agent prepared by condensing an aminoalkylpiperazine and a long-chain dicarboxylic acid, ester or chloride, and c) water....http://www.google.com/patents/US6013757?utm_source=gb-gplus-sharePatent US6013757 - Coating or impregnant of epoxy resin and aqueous polyamide-amine dispersionAdvanced Patent SearchPublication numberUS6013757 APublication typeGrantApplication numberUS 08/977,977Publication dateJan 11, 2000Filing dateNov 25, 1997Priority dateNov 16, 1995Fee statusPaidAlso published asUS5962629, US5998508Publication number08977977, 977977, US 6013757 A, US 6013757A, US-A-6013757, US6013757 A, US6013757AInventorsLarry Steven Corley, Derek Scott Kincaid, Glenda Carole YoungOriginal AssigneeShell Oil CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (31), Referenced by (10), Classifications (36), Legal Events (19) External Links: USPTO, USPTO Assignment, EspacenetCoating or impregnant of epoxy resin and aqueous polyamide-amine dispersion
US 6013757 AAbstract
A substrate is coated or impregnated with a composition comprising an a) epoxy resin, b) a liquid amine-terminated polyamide curing agent prepared by condensing an aminoalkylpiperazine and a long-chain dicarboxylic acid, ester or chloride, and c) water.
1. A cord substrate impregnated with 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 C18-50 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 cord substrate is selected from the group consisting of nylon, polyesters, fiberglass, graphite, and aramids.
3. The composition of claim 2, wherein the aminoalkylpiperazine is N-(2-aminoethyl)piperazine.
5. The composition of claim 1 wherein the substrate is selected from the group consisting of nylon, polyesters, fiberglass, graphite, and aramids.
6. A substrate coated with a curable epoxy resin composition comprising:(d) an epoxy resin having at least 1.5 epoxy groups per molecule; (e) a liquid amine terminated polyamide prepared by reacting at least one C18-50 dicarboxylic acid, dicarboxylic acid ester or dicarboxylic acid chloride and an amine compound consisting of an aminoalkylpiperazine; and (f) water; wherein said polyamide is mixed with water to provide an oil-in-water emulsion when preparing said composition. 7. A cured composition of claim 6.
This is a division, of application Ser. No. 08/558,357. filed Nov. 16, 1995, allowed.
This invention relates to aqueous dispersions of polyamide-amines. In one aspect, the invention relates to polyamide-amine curing agents for epoxy resin systems useful for waterborne applications.
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 itis 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.
According to the invention, an epoxy resin composition is provided comprising:
Accordingly, it is desirable to obtain aqueous polyamide-amine based curing agent useful for curing waterborne epoxy resins. These systems are particularly useful in waterborne epoxy resin impregnation systems and for waterborne epoxy resin coating systems. They tend to provide cured films with higher flexibility and impact resistance (e.g., good peel strength) than that typically given by currently used waterborne curing agents.
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� C., preferably at a final temperature within the range of from about 220� C. to about 260� C., for a time effective to produce a 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� C.). These liquid aminoalkylpiperazine-based amine terminated 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.
The term "dimer acids" refers to polymeric or oligomeric fatty acids typically made from addition polymerization, using heat and a catalyst, of unsaturated fatty acids, particularly tall oil fatty acids. These polymeric fatty acids typically have the composition of up to about 20% of C18 monobasic acids, about 45 to 95 % of C36 dibasic acids, and about 1 to 35 % of C54 tribasic and higher polymeric acids. The relative ratios of monomer, dimer, trimer and higher polymer in unfractionated dimer acid are dependent on the nature of the starting material and the conditions of polymerization and distillation. Methods for the polymerization of unsaturated fatty acids are described, for example, in U.S. Pat. No. 3,157,681.
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� C. Methods for the 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 R1 and R2 are each independently --H or --R3 --NH2, wherein R3 is a divalent aliphatic-linkage, preferably a chain of --CH2 -- units with optional --CHR4 -- or CR4 R5 -- units, wherein R4 and R5 are independently alkyl groups, provided that at least one of R1 and R2 is --R3 --NH2 --. 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, Kag Keizai, 26(6), pp.20-27 (1979), and Q. Sun and C. Zhu, Shanghai DiyiYixueyuan Xuebao, 12(3), pp. 178-182 (1985).
To obtain the aqueous dispersion of the curing agent, water is added until the desired percent solids is obtained which is generally from about 5% to about 75% solids content. Generally the amount of the liquid amine terminated polyamide component (b) is from about 30 to about 70 percent by weight, preferably from about 40 to about 60 percent by weight, based on the total dispersion. Generally, (c) water and (b) the liquid amine terminated polyamide are mixed under conditions effective to provide an oil-in-water emulsion. Although stable dispersions will generally form without the use of any surfactant, a surfactant may optionally be added to the mixture of amine terminated polyamide and water in order to modify the Theological behavior of the product dispersion. To obtain zero VOC dispersions, preferably no solvent is added to the emulsion or dispersion.
The curing agent is mixed with a sufficient amount of water to obtain an oil-in-water emulsion. Optimal conditions to prepare these emulsions involve first making a homogeneous mixture with stirring of the polyamide-amine and water at a temperature above about 70� C., preferably above about 80� C., still more preferably above about 90� C., and then cooling the mixture with stirring such that the mixture changes from a solution to an oil-in-water emulsion. Low stirring speeds or even no stirring during cooldown are desirable for a low viscosity product, whereas higher stirring speeds can be used during cooldown if a higher viscosity thixotropic product is desired.
It has been found that the curing agent of the invention readily forms a stable dispersion compared to other amine curing agents such as a polyamide-amine curing agent based on dimer acid, fatty acid, and triethylenetetramine (eg. EPI--CURE� Curing Agent 3115). Preferably the dispersion is produced containing at least from about 35% solids content to about 60% solids content for use in coatings applications. Preferably the dispersion is produced containing at least from about 5% solids content to about 50% solids content for use in cord and fiber impregnations.
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, HBF4,H2 SO4,H2 NSO3 H and H3 PO4 ; 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 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� Resins 862, 828, 826, 825 and 1001 available from Shell Chemical Company.
Aliphatic glycidyl ethers can be produced, for example, by reacting an epihalohydrin with an aliphatic diol (optionally containing ether linkages or sulfone linkages) in the presence of a Lewis acid catalyst followed by conversion of the halohydrin intermediate to the glycidyl ether by reaction with sodium hydroxide. Commercial examples of preferred epoxy resins include, for example, HELOXY� Modifiers 32 (a diglycidyl ether of a poly(propylene oxide)glycol), 68 (the diglycidyl ether of neopentyl glycol) and 107 (the diglycidyl ether of 1,4-cyclohexanedimethanol) available from Shell Chemical Company.
Examples of preferred aliphatic glycidyl ethers include those corresponding to the formulas: ##STR2## wherein: p is an integer from 2 to 12, preferably from 2 to 6; and
Examples of suitable aliphatic glycidyl ethers include, for example, diglycidyl ethers of 1,4-butanediol, neopentyl glycol, cyclohexanedimethanol, hexanediol, hydrogenated bisphenol A,and polypropylene glycol; and triglycidylethers of trimethylolethane and trimethylolpropane.
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� Resins 3510-W-60, 3515-W-60, 3522-W-60, 3530-W-70, 3540-WY-510 (all aqueous dispersions of epoxy resins) available from Shell Chemical Company.
The preferred epoxy resin systems of the invention contain one or more epoxy resins, a curing agent containing the amine terminated polyamide, water, and optionally an accelerator. The epoxy resin can be blended or mixed with the aqueous dispersion of the curing agent containing the amine terminated polyamide and optionally the accelerator simultaneously or in any order at a temperature below the cure temperature which is typically below about 100� C.
The curable epoxy resin composition can be cured at a temperature within the range of from about -40� C., preferably from about -10� C., to about 300� C., preferably to about 250� C., for a time effective to cure the epoxy resin. For standard coating applications the composition is preferably cured at a temperature from about -10� C. to about 75� C. For curing of impregnated cords, yarns or fibers, the composition is preferably cured at a temperature from about 45� C. to about 240� C.
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 impregnation, the curable epoxy resin composition or latex can optionally contain thixotropic agents and halogenated phenolic compounds (the latter especially for printed wiring board uses). The composition can be impregnated on a cord, fiber or yarn substrate (hereinafter "cord substrates") such as nylon, polyester, fiberglass, graphite and aramid, and then cured. These cord substrates are dipped in a curable epoxy resin composition and then cured. These cord substrates can be dipped once, twice or even three times in a dipping zone in a prepolymer or a resinous solution and then dried and/or cured. In the present embodiment at least one of these dipping or impregnation steps is carried out with the aqueous curable epoxy resin system of the invention. The aqueous curable epoxy resin composition can be used with any conventional cord treater. The curable epoxy resin system is preferably dried and cured at a temperature effective to cure the epoxy resin system which is generally at a temperature within the range of about 45� C. to about 240� C. These impregnated cords are useful as reinforcing cords or as fiber-rubber composites to be used with a thermoset elastomer matrix for belt cord, hose cord, tire cord and tow in various fields of applications, including automotive, industrial, agricultural and domestic.
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% C18 monobasic acids, ˜80% C36 dibasic acids, ˜10% C54 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� Resin 1001 (an oligomeric diglycidyl ether 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� Resin 3510-W-60 (an aqueous dispersion, 60% solids, of a bisphenol A-based epoxy resin with an epoxide equivalent weight of approximately 185-215), EPI-REZ� Resin 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� Resin 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� Modifier 9 (a glycidyl ether of a mixture of 1-dodecanol and 1-tridecanol having an epoxy equivalent weight of 275-295) and HELOXY� Modifier 32 (a diglycidyl ether of a mixture of oligomers of propylene oxide with an epoxide equivalent weight of 305-335) were obtained from Shell Chemical Company. EPI--CURE� Curing Agent 3140 (a polyamide-amine curing agent based on dimer acid, fatty acid, and triethylenetetramine) and EPI--CURE� Curing Agent 3125 (a polyamide-amine curing agent based on dimer acid, fatty acid, and a mixture of polyethylenepolyamines) were obtained from Shell Chemical Company.
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� C., water began to distill at atmospheric pressure. Water distillation at atmospheric pressure continued until the pot temperature had been raised to 220-240� C.; the pot 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� C. and the rate of amine offtake had become essentially negligible. Vacuum stripping was then continued at this temperature for approximately another 15 minutes. The products were then allowed to cool to about 150� C. under vacuum or under a stream of nitrogen and 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 13.12e  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 a 238� C./13 Pa                         235� C./17 Pa  Nonvolatile product, grams 2460.9 2481.3  Amine nitrogen content, %, by titration 6.69 6.86  Amine nitrogen content, %, theoretical b 7.00 7.00  Amine nitrogen equiv. wt.c 209.4 210.6  Amine hydrogen equiv. wt.d 284.8 288.3  Ubbelohde kinematic viscosity, 40� C., 22400 22300  mm2 /sec______________________________________ 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. b Calculated for product composed solely of condensation product of one molecule of dimer acid and two molecules of amine. c Calculated from amine nitrogen content determined by titration. 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 --NH2 and --NH groups have equal reactivity toward the dimer acid so that the average polyamide molecule contains 3 amine hydrogens). e From amine nitrogen content determined by titration (this lot of AEP apparently contained approximately 2% water)
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� C. and kept at this temperature with stirring. Water was then metered in from the addition funnel over a 30 minute period. After the water was added, the mixture was held at 88� C. with stirring for 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).
The product was then mixed, at the ratio indicated in system #2 of Table 2 below, with a dispersion (50% in water) of a mixture of 80% EPI-REZ� Resin WD-510 (a material analogous to EPON� Resin 828 but containing a surfactant system for water dispersibility) and 20% HELOXY� Modifier 9. A comparative non-waterborne system (system #1) contained a mixture of 80% EPON� Resin 828 and 20% HELOXY� Modifier 9, cured with the product of Example 1, run #2, at the same solids ratio as in the waterborne counterpart. The systems were applied to adhesive testing coupons made of aluminum or of fiberglass tape. The adhesive bonds were cured 1 hour at 100� C. Performance properties are shown in Table 2 below.
TABLE 2______________________________________System#        1            2______________________________________Resin Composition  EPON � Resin 828 80  HELOXY � Modifier 9 20 20  EPI-REZ � Resin WD-510  80  Water  100  Curative Component, phr  (based on resin solids)  Product of Example 1, run #2 182  Water dispersion of curing  455 phr dispersion  agent prepared in text above  (182 phr solids)  Handling Characteristicsa  Resin Solids 100% 50%  Curative Solids 100% 40%  System Solids 100% 43%  Resin Viscosity, mPa � s 600f 45g  Curative Viscosity, mPa � s 138000f 21000g  System Viscosity, mPa � s 19600f 11200g  Combining Ratio by volume 1.82:1 2.27:1  Pot life, 100 gram massb 45 minutes 55 minutes  Performance Propertiesc  Aluminum-Aluminum Peel 2.5 N/mm (14 pli) 2.1 N/mm (12 pli)  Adhesiond  Fiberglass Peel Adhesione &gt;13 N/mm (75 pli)h &gt;13 N/mm (75                       pli)h______________________________________ a All systems tested at 25� C. b Time to gel as determined by manual probing with a tongue depressor. c Systems cured 1 hour @ 100� C., tested at 25� C., crosshead speed 50.8 cm/minute (20 inch/minute). d 0.127 mm (5 mil) aluminum, acid etched. e Tetraglas Plain tape, 1.59 mm (1/16") � 50.8 mm (2") Egrade fiberglass. f Viscosities measured by Brookfield RVT, spindle #29. g Viscosities measured by Brookfield RVT, spindle #5. h Failure occurred in thc fiberglass tape substrate.
Use of waterborne AEP-based amine-terminated "polyamide" in comparison with other "polyamide" curing agents in adhesives for aluminum and poly(ethylene terephthalate) films
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� Resin 1001 with 8000 molecular weight poly(ethylene oxide) glycol. To the surfactant, with stirring, were added 491 grams of EPON� Resin 828 over a period of 25 minutes. To this mixture, with stirring, were added 122.6 grams of HELOXY� Modifier 9 over the next 25 minutes. Heating was then started and stirring was continued for another 1.5 hours; the temperature at that point had reached 45� C. Stirring was continued for another hour with the addition of 275 grams of deionized water. At the end of this period the temperature had dropped to 31� C. Stirring was continued for an additional 45 minutes as the temperature was brought up to 54� C. The mixture was kept at this temperature with stirring for 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� Curing Agent 3125 or EPI-CURE� Curing Agent 3140). (The 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� C. To the 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� C. during this time. After water 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� C., stirring was stopped and the mixture was allowed to 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� Curing 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� Curing Agents 3125 and 3140 also, when diluted with water, appeared to contain some large particles visible to the naked eye. The dispersions prepared from EPI-CURE� Curing Agents 3125 and 3140 also were higher in viscosity than that prepared from the AEP-dimer acid polyamide (Table 3 below).
The above aqueous dispersions of curing agents were mixed with Waterborne Resin Mixture A in the ratios indicated in Table 3 below (believed to be near-stoichiometric) and the mixed resin-curing agent dispersions were coated on adhesive test coupons of aluminum or polyethylene terephthalate (PET), using a steel drawdown blade to produce wet coatings 0.025 mm thick. The water was flashed off the wet films in a 60� C. oven for 5 minutes. After drying, the coated substrates were then placed together, laminated between sheets of release paper, and pressure rolled by hand. The adhesive bonds were cured 16 hours at room temperature followed by 1 hour at 100� C. Adhesion properties are shown in Table 3 below (runs #4, 5 and 6). For comparison, corresponding neat (non-waterborne) mixtures were made by combining a mixture of EPON� Resin 828 and HELOXY� Modifier 9 (same ratio as in Waterborne Resin Mixture A, but without water) with the AEP-dimer acid polyamide or EPI-CURE� Curing Agents 3125 or 3140 without water. Solids ratios of resin and curing agent were the same as for the corresponding waterborne systems. The non-waterborne comparative systems are runs #1, 2 and 3 in Table 3.
One can see from Table 3 that, for both the neat and waterborne systems, the adhesive peel strength is much greater for the resin cured with the AEP-dimer acid polyamide than for the same resin cured with the standard commercial polyamide curing agents EPI-CURE� 3125 and 3140. This was the case both for the aluminum and poly(ethylene terephthalate) substrates.
TABLE 3__________________________________________________________________________Run #            1   2   3   4   5     6__________________________________________________________________________Curing agent dispersion preparation:  AEP-dimer polyamide, parts    200  EPI-CURE Curing Agent 3125, parts     200  EPICURE Curing Agent 3140, parts      200  Water, parts    300 300 300  Brookfield viscosity of dispersion, room    24 78 37.5  temperature, Pa � s  Dispersion appearance    Opaque, Translucent Translucent smooth and opaque and opaque  zones zones  Resin composition:  EPON Resin 828/HELOXY Modifier 100 100 100  9 blend, parts  Waterborne Resin Mixture A, parts    154 154 154  Curing agent composition:  AEP-dimer polyamide, parts 171  EPI-CURE Curing Agent 3125, parts  48  EPI-CURE Curing Agent 3140, parts   44  Waterborne curing agent prepared    428 120 110  above in same column, parts  Adhesion properties:a  Aluminum-aluminum, T-peel, N/mm 2.12 0.35 0.14 1.24 0.25 0.28  PET-PET, T-peel, N/mm &gt;6.7b &lt;0.05 &lt;0.05 &gt;0.70b 0.07 0.05__________________________________________________________________________ a Tpeel adhesion measured per ASTM D1876 at 25.4 cm/minute. b Failure occurred in PET film substrate.
Use of product of Example 1, run #2, in formulating waterborne coatings based on aqueous dispersions of different epoxy resins
A dispersion ("Curing Agent Dispersion" in Table 4 below) of 40 parts of the product of Example 1, run #2, in 60 parts by weight of water was prepared by the same technique used in Example 2. This dispersion was mixed with different waterborne epoxy resins as indicated in Table 4 below and the mixed resin-curing agent aqueous dispersions were coated onto cold rolled steel using a doctor blade, producing wet films 5 mils (0.025 mm) thick. The films were allowed to dry at room temperature or alternatively were cured for 1 hour at 100� C. Film properties are shown in Table 4 below.
TABLE 4__________________________________________________________________________Run#            1   2   3   4   5   6__________________________________________________________________________Composition:  EPI-REZ Resin 3515-W-60a, parts 167  EPI-REZ Resin 3522-W-60b, parts  167  EPI-REZ Resin 3530-W-70c, parts   143  EPI-REZ Resin 3540-WY-55d, parts    182  EPI-REZ Resin WD-510e, parts     80  HELOXY � Modifier 9f, parts     20  Water, parts     100  EPI-REZ Resin 3510-W-60g, parts      135.67  HELOXY Modifier 32h, parts      14.33  Above curing agent dispersion, parts 368 138 368  50 455  428  Films cured 1 hour at 100� C.:  Film appearance Orange Orange Slight Smooth Heavy Orange   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 appearance Smooth Smooth Smooth Smooth Heavy Smooth  orange  peel  Film clarity Clear Cloudy Cloudy Cloudy Clear Clear  Tack after 2 hours Slight None None None Tacky Tacky  Pencil hardness after 24 hours 3B 3B &lt;6B HB &lt;6B 1H__________________________________________________________________________ a An aqueous dispersion (60% solids) of a bisphenol Abased epoxy resin with an epoxide equivalent weight of 225-275. b An aqueous dispersion (60% solids) of a bisphenol Abased epoxy resin with an epoxide equivalent weight of 625-745. c An aqueous dispersion (70% solids) of an epoxy resin with an epoxide equivalent weight of approximately 250. d An aqueous dispersion (55% solids) of a bisphenol Abased epoxy resin with an epoxide equivalent weight of 1600-2000. e A waterdispersible bisphenol Abased epoxy resin with an epoxide equivalent weight of 190-205. f A mixture of dodecyl and tridecyl glycidyl ethers with an epoxide equivalent weight of 275-295. g An aqueous dispersion (60% solids) of a bisphenol Abased epoxy resin with an epoxide equivalent weight of 185-215. h A mixture of diglycidyl ethers of oligomers of propylene oxide wit an epoxide equivalent weight of 305-335.
Use of an aqueous dispersion of the product of Example 1, run #1, to cure an aqueous epoxy resin dispersion in a paper saturant system
Five parts of the AEP-dimer acid polyamide prepared in Example 1, run #1, were dispersed in 95 parts of distilled water (using heat and a magnetic stirring bar) to make a cloudy but apparently stable dispersion. To 165.6 grams of this dispersion were added 10 grams of a 60% by weight aqueous dispersion of the diglycidyl ether of bisphenol A with a solids epoxide equivalent weight of approximately 250 (EPI-REZ� Resin 3515-W-60 from Shell Chemical Company). The resultant resin-curing agent dispersion contained 8.1% by weight total resin system solids.
A control slurry of 11.4 grams of a commercial polyamide curing agent, EPI-CURE� Curing Agent 3140 from Shell Chemical Company, and 11.4 grams of water was prepared. To this slurry was added 50 grams of EPI-REZ� Resin 3515-W-60 as above. The mixture was stirred until thoroughly mixed. Additional water (214.6 grams) was added to yield a final aqueous dispersion containing 15% by weight total resin system solids.
Whatman No. 4 chromatography paper was cut into 7"�7" (17.8 cm�17.8 cm) pieces. The pieces of paper were saturated with the two water dispersions above by pan dipping. The water was flashed from the papers by hanging them in a forced air oven at 66� C. for 15 minutes. The oven temperature was then increased to 149� C. for 10 minutes to cure the resin. The papers were weighed before and after resin dipping and heat treatment. The cured resin add-on was 22�2% by weight for the papers dipped in both resin-curing agent water dispersions. The cured paper-resin composites were then cut into 1"�4" (2.5 cm�10.2 cm) strips. The strips were tested for tensile properties (ASTM D-882) using an Instron tensile test machine. Some of the strips were then soaked for 10 minutes in water or methyl ethyl ketone (MEK), and the tensile properties of the soaked strips were determined by the same procedure. Results are shown in Table 5 below. The system containing the product of Example 1, run #1, shows higher tensile elongation than the control system under all three test conditions, although its tensile strength and modulus are lower as would be expected for an inherently less rigid system.
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______________________________________
Use of product of Example 1, run #1, in formulating waterborne coatings
The polyamide-amine curing agents shown in Table 6 below were each slurried with an equal weight of water to form a dispersion for easier mixing with a waterborne epoxy resin dispersion. To the curing agent slurries were then added amounts of EPI-REZ� Resin 3510-W-60 (a 60% by weight aqueous dispersion of the diglycidyl ether of bisphenol A with a solids epoxide equivalent weight of approximately 200) as shown in Table 6 below. Viscosities of the mixed resin-curing agent dispersions were determined periodically with a Brookfield viscometer. After being allowed to stand for an induction period of 30 minutes, the dispersions were coated onto cold rolled steel panels using a 2 mil (0.05 mm) drawdown blade. One panel of each set was allowed to remain at room temperature and the state of drying of the coating was periodically evaluated. Other panels were baked for 30 minutes at 121� C. and film properties were evaluated as shown in Table 6 below.
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� Curing Agent 3140. The heat-cured invention 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 � Resin 3510-W-60, parts               25       25       25  Product of Example 1, run #1, parts    26.2    22.5  EPI-CURE � Curing Agent 3140,       7.1  parts  Water (pre-slurried with curing    26.2    22.5     7.1  agent), parts  Viscosity (mPa � s, Brookfield)  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   &lt;4   &lt;4  &gt;24  Cotton free   4   4  (&gt;24)  Through dry   22    14.5  (&gt;24)  Baked film properties  (30 min. @ 121� C.):  Pencil hardness (ASTM D3363) F F 5B  MEK resistance, double rubs  &gt;100  &gt;100   50  Direct impact, J (ASTM D2794)  &gt;160  &gt;160  &gt;160  Reverse impact, J (ASTM D2794)  160  160  &gt;160______________________________________
Use of an aqueous dispersion of the product of Example 1, run #1, to cure an aqueous epoxy resin dispersion in an adhesive formulation
A mixed epoxy resin dispersion was prepared at room temperature as follows. A 1-liter reaction kettle was equipped with an anchor stirrer, thermocouple and condenser. To the kettle were added 89.4 grams of a 32% aqueous solution of a surfactant made by reacting EPON Resin 1001 with 8000 molecular weight poly(ethylene oxide) glycol and 30.8 grams of additional water. To this mixture, with stirring, were added 480.9 grams of EPON� Resin 828 over a period of 1.5 hours. At the end of this period, phase inversion had occurred to form an oil-in-water emulsion. Stirring was continued for an additional 30 minutes. During the following 30 minutes, 150 grams of HELOXYO Modifier 32 were added to the mixture, with continued stirring. At the end of this period, 292.8 grams of additional water were added to this mixture, likewise with stirring. The final product had a solids content of 62.1% and is referred to as "Waterborne Resin Mixture B" in the experiments in the remainder of this example.
Water slurries of different amine-functional curing agents were prepared by stirring the curing agent together with water in the relative amounts indicated in Table 7 below. To the water dispersions of curing agents were added, with stirring, portions of Waterborne Resin Mixture B in the amounts indicated in Table 7 below. The mixed resin-curing agent dispersions were then each coated with a #40 wire wound metering bar onto three sets of T-2024 aluminum adhesive testing coupons (76.2 cm�25.4 cm�1.5 mm) which had been previously etched for 20 minutes at 60� C. with a solution consisting of 30% sulfuric acid, 15% iron(III) sulfate, and 55% water by weight. The water contained in the resin-curing agent dispersions was flashed off each set of coupons at 66� C. for 15 minutes before the coupons were assembled together. The adhesive bond between the coupons was cured at 121� C. for 20 minutes. Lap shear strength of the specimens was then determined by a method based on ASTM D-1002. From Table 7 below, one can see the increased lap shear resistance of the invention systems (#1 and #3) based on the curing agent product of Example 1, run #1, in comparison with the control system #2 based on EPI-CURE� Curing Agent 3055 (an amidoamine curing agent based on the reaction product of a nondimerized fatty acid with a polyethylenepolyamine from Shell Chemical Co.).
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 � Curing Agent 3055,  12.6  parts  Blend of 85% (wt.) product of   39.9  Example 1, run #1, and 15% (wt.)  N-(2-aminoethyl)piperazine, parts  Additional water, parts (used for 172 81.9 145.6  forming curing agent dispersion)  Baked film properties (30 min. @ 14.8 � 1.2 9.6 � 3.1 16.3 �                               0.9  121� C.):  Room temperature lap shear strength,  MPa (ASTM D-1002)______________________________________
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS3655595 *Feb 20, 1969Apr 11, 1972Memorex CorpEpoxy binder for magnetic coating compositionUS4070225 *Nov 17, 1976Jan 24, 1978H. B. Fuller CompanyMethod of using structural adhesiveUS4082708 *Sep 20, 1976Apr 4, 1978H. B. Fuller CompanyAdhesive systems comprising a bisamino piperazine-containing polyamideUS4086197 *Jun 21, 1976Apr 25, 1978Societe Chimique Des CharbonnagesHardeners for epoxy resinsUS4115296 *Dec 16, 1976Sep 19, 1978Ciba-Geigy CorporationPolyhalocarboxylic acid salts as accelerators for curing epoxide resinsUS4188221 *May 8, 1978Feb 12, 1980Toyo Boseki Kabushiki KaishaPhotosensitive polyamide resin composition useful for making relief printing plateUS4206097 *Feb 27, 1979Jun 3, 1980Schering AktiengesellschaftSynthetic resin mixturesUS4268656 *Jan 16, 1980May 19, 1981National Starch And Chemical CorporationCo-curing agents for epoxy resinsUS4332711 *Dec 3, 1979Jun 1, 1982Shell Oil CompanyThermosetting resinous binder compositions, their preparation and use as coating materialsUS4362847 *Apr 20, 1981Dec 7, 1982Shell Oil CompanyHeat-curable thermosetting resin binder compositions comprising a non-acidic resinous compound, a non-acidic polyester cross-linking agent, and a transesterification catalystUS4569971 *Aug 15, 1983Feb 11, 1986Rutgerswerke AktiengesellschaftHardeners for epoxy resinsUS4698396 *Apr 28, 1986Oct 6, 1987Schering AktiengesellschaftHardenable synthetic resin mixturesUS4717746 *Jul 26, 1985Jan 5, 1988Chem-PlastAdhesion promoters of plastisols, capable of maintaining plastisol color stable towards the effect of the application thermal treatmentUS5017675 *Jan 16, 1990May 21, 1991Hoechst AgUse of polyamidoamines as curing agents for epoxy resins and curable mixtures containing these substances wherein the acid component has oxyalkylene(repeating)unitsUS5296556 *Aug 9, 1991Mar 22, 1994Union Camp CorporationThree-component curable resin compositionsUS5296557 *Jul 2, 1992Mar 22, 1994Union Camp CorporationTwo-component curable hot melt compositionsUS5301940 *Aug 27, 1993Apr 12, 1994Mizuno CorporationBaseball bat and production thereofUS5319004 *Feb 26, 1993Jun 7, 1994Hoechst AktiengesellschaftHardener for epoxy resins comprising reaction products of polyamidoamines, secondary polyamines and epoxy-polyol adductsUS5385986 *May 5, 1994Jan 31, 1995Union Camp CorporationAdhesive of amine-terminated polyamide and epoxy resinUS5424371 *Feb 17, 1994Jun 13, 1995Union Camp CorporationAdhesive of amine-terminated, piperazine-containing polyamide and epoxy resinUS5428083 *Aug 20, 1993Jun 27, 1995Union Camp CorporationOne-component, curable epoxy/polyamide resin dispersions with enhanced stability containing one or more amino acidsUS5447785 *Jul 9, 1993Sep 5, 1995Toray Industries, Inc.Cloth prepreg, process for producing the same and reinforcing fabricUS5576416 *Dec 13, 1994Nov 19, 1996Air Products And Chemicals, Inc.Amide-containing self-emulsifying epoxy curing agentUS5605944 *Apr 27, 1995Feb 25, 1997Union Camp CorporationHeat-resistant adhesive for use especially in making sterilizable packagingUS5612448 *Apr 21, 1995Mar 18, 1997Union Camp CorporationCurable adhesive compositions containing polyamide resinsEP0423577A1 *Oct 6, 1990Apr 24, 1991Bayer AgPolyamidelastomers, their preparation and useJP7648081A * Title not availableJPH06162564A * Title not availableJPH06173734A * Title not availableJPH06329979A * Title not availableJPS60219281A * Title not available* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS6395845Dec 15, 1998May 28, 2002Resolution Performance Products LlcWaterproofing membrane from epoxy resin and amine-terminated polyamideUS6500912Sep 12, 2000Dec 31, 2002Resolution Performance Products LlcEpoxy resin systemUS6773754Dec 10, 2002Aug 10, 2004Hexcel Composites, Ltd.Accelerated curing of epoxy gelcoatsUS6864349Dec 13, 2002Mar 8, 2005Arizona Chemical CompanyAqueous suspensions containing polymerized fatty acid-based polyamidesUS7475786 *Aug 3, 2005Jan 13, 2009Ppg Industries Ohio, Inc.Can coatings, methods for coating can and cans coated therebyUS7528183Dec 2, 2004May 5, 2009Air Products And Chemicals, Inc.Method of preparation of a water based epoxy curing agentUS7615584Mar 17, 2009Nov 10, 2009Air Products And Chemicals, Inc.Method of preparation of a water based epoxy curing agentUS8840963Apr 27, 2011Sep 23, 2014Taesan Engineering Co., LtdEnvironmentally friendly water-based epoxy resin composition and a use thereforEP1544230A1Dec 19, 2003Jun 22, 2005Air Products And Chemicals, Inc.Method of preparation of a water based epoxy curing agentWO2011136568A2 *Apr 27, 2011Nov 3, 2011Taesan Engineering Co., Ltd.Environmentally friendly water-based epoxy resin composition and a use therefor* Cited by examinerClassifications U.S. Classification528/289, 428/413, 442/150, 524/608, 442/168, 442/164, 428/418, 524/607, 442/169International ClassificationC08G69/26, C08G59/54, C08J3/24, C08G69/34, C08L77/00, C08G59/50, C08L63/00, C09D163/00Cooperative ClassificationC09D163/00, Y10T442/2861, Y10T442/2902, Y10T442/2746, C08G69/265, C08J3/24, Y10T428/31511, Y10T442/2893, C08G69/26, C08J2363/00, Y10T428/31529, C08G59/54, C08G69/34European ClassificationC08J3/24, C09D163/00, C08G69/26, C08G69/26K, C08G69/34, C08G59/54Legal EventsDateCodeEventDescriptionFeb 3, 2015ASAssignmentOwner name: HEXION INC., OHIOFree format text: CHANGE OF NAME;ASSIGNOR:MOMENTIVE SPECIALTY CHEMICALS INC.;REEL/FRAME:034882/0816Effective date: 20150115Apr 3, 2013ASAssignmentOwner name: JPMORGAN CHASE BANK, N.A., DELAWAREFree format text: PATENT SECURITY AGREEMENT;ASSIGNOR:MOMENTIVE SPECIALTY CHEMICALS INC.;REEL/FRAME:030146/0970Effective date: 20130328Owner name: WILMINGTON TRUST, NATIONAL ASSOCIATION, MINNESOTAFree format text: PATENT SECURITY AGREEMENT;ASSIGNOR:MOMENTIVE SPECIALTY CHEMICALS INC.;REEL/FRAME:030146/0946Effective date: 20130328Mar 28, 2013ASAssignmentOwner name: MOMENTIVE SPECIALTY CHEMICALS INC. (F/K/A HEXION SFree format text: TERMINATION AND RELEASE OF SECURITY INTEREST IN PATENT RIGHTS;ASSIGNOR:JPMORGAN CHASE BANK, N.A.;REEL/FRAME:030111/0021Effective date: 20130328Apr 19, 2012ASAssignmentOwner name: HEXION SPECIALTY CHEMICALS, INC., OHIOFree format text: CORRECTIVE ASSIGNMENT TO CORRECT THE RECEIVING PARTY NAME PREVIOUSLY RECORDED ON REEL 027805, FRAME0642;ASSIGNOR:RESOLUTION PERFORMANCE PRODUCTS CORP;REEL/FRAME:028078/0190Effective date: 20050531Mar 5, 2012ASAssignmentOwner name: MOMENTIVE SPECIALTY CHEMICALS INC., OHIOFree format text: CHANGE OF NAME;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:027805/0802Effective date: 20101001Owner name: RESOLUTION PERFORMANCE PRODUCTS CORP, OHIOFree format text: CERTIFICATE OF CONVERSION;ASSIGNOR:RESOLUTION PERFORMANCE PRODUCTS LLC;REEL/FRAME:027805/0621Effective date: 20050531Owner name: N SPECIALTY CHEMICALS, INC., OHIOFree format text: MERGER;ASSIGNOR:RESOLUTION PERFORMANCE PRODUCTS CORP;REEL/FRAME:027805/0642Effective date: 20050531Jul 11, 2011FPAYFee paymentYear of fee payment: 12Feb 5, 2010ASAssignmentFree format text: SECURITY AGREEMENT;ASSIGNORS:HEXION LLC;HEXION SPECIALTY CHEMICALS, INC.;BORDEN CHEMICAL FOUNDRY, LLC;AND OTHERS;REEL/FRAME:023905/0451Owner name: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENTFree format text: SECURITY AGREEMENT;ASSIGNORS:HEXION LLC;HEXION SPECIALTY CHEMICALS, INC.;BORDEN CHEMICAL FOUNDRY, LLC;AND OTHERS;REEL/FRAME:023905/0451Effective date: 20100129Owner name: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENTFree format text: SECURITY AGREEMENT;ASSIGNORS:HEXION LLC;HEXION SPECIALTY CHEMICALS, INC.;BORDEN CHEMICAL FOUNDRY, LLC AND OTHERS;REEL/FRAME:23905/451Effective date: 20100129Jan 29, 2010ASAssignmentFree format text: SECURITY INTEREST;ASSIGNORS:HEXION SPECIALTY CHEMICALS, INC.;BORDEN CHEMICAL FOUNDRY, LLC;BORDEN CHEMICAL INVESTMENTS, INC.;AND OTHERS;REEL/FRAME:023963/0038Owner name: WILMINGTON TRUST FSB, AS COLLATERAL AGENT, MINNESOOwner name: WILMINGTON TRUST FSB, AS COLLATERAL AGENT,MINNESOTFree format text: SECURITY INTEREST;ASSIGNORS:HEXION SPECIALTY CHEMICALS, INC.;BORDEN CHEMICAL FOUNDRY, LLC;BORDEN CHEMICAL INVESTMENTS, INC. AND OTHERS;REEL/FRAME:23963/38Effective date: 20100129Owner name: WILMINGTON TRUST FSB, AS COLLATERAL AGENT,MINNESOTFree format text: SECURITY INTEREST;ASSIGNORS:HEXION SPECIALTY CHEMICALS, INC.;BORDEN CHEMICAL FOUNDRY, LLC;BORDEN CHEMICAL INVESTMENTS, INC.;AND OTHERS;REEL/FRAME:023963/0038Effective date: 20100129Owner name: WILMINGTON TRUST FSB, AS COLLATERAL AGENT, MINNESOFree format text: SECURITY INTEREST;ASSIGNORS:HEXION SPECIALTY CHEMICALS, INC.;BORDEN CHEMICAL FOUNDRY, LLC;BORDEN CHEMICAL INVESTMENTS, INC.;AND OTHERS;REEL/FRAME:023963/0038Effective date: 20100129Jan 28, 2010ASAssignmentOwner name: RESOLUTION PERFORMANCE PRODUCTS LLC, OHIOFree format text: RELEASE OF SECURITY INTEREST;ASSIGNOR:GENERAL ELECTRIC CAPITAL CORPORATION;REEL/FRAME:023861/0751Effective date: 20100128Jul 11, 2007FPAYFee paymentYear of fee payment: 8Nov 21, 2006ASAssignmentOwner name: WILMINGTON TRUST COMPANY, AS COLLATERAL AGENT,DELAFree format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:18535/701Free format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:18535/556Owner name: JPMORGAN CHASE BANK, N.A. AS ADMINISTRATIVE AGENT,Free format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:018535/0556Effective date: 20061103Owner name: WILMINGTON TRUST COMPANY, AS COLLATERAL AGENT,DELAFree format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:18535/701Effective date: 20061103Owner name: WILMINGTON TRUST COMPANY, AS COLLATERAL AGENT,DELAFree format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:018535/0701Effective date: 20061103Owner name: WILMINGTON TRUST COMPANY, AS COLLATERAL AGENT, DELFree format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:018535/0701Effective date: 20061103Owner name: JPMORGAN CHASE BANK, N.A. AS ADMINISTRATIVE AGENT,Free format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:018535/0556Effective date: 20061103Owner name: WILMINGTON TRUST COMPANY, AS COLLATERAL AGENT, DELFree format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:018535/0701Effective date: 20061103Owner name: JPMORGAN CHASE BANK, N.A. AS ADMINISTRATIVE AGENT,Free format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:18535/556Effective date: 20061103Jul 14, 2006ASAssignmentOwner name: JPMORGAN CHASE BANK, N.A. AS COLLATERAL AGENT,NEWOwner name: JPMORGAN CHASE BANK, N.A. AS COLLATERAL AGENT, NEWFree format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:017946/0151Effective date: 20060505Owner name: JPMORGAN CHASE BANK, N.A. AS COLLATERAL AGENT, NEWFree format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:017946/0151Effective date: 20060505Owner name: JPMORGAN CHASE BANK, N.A. AS COLLATERAL AGENT,NEWFree format text: SECURITY AGREEMENT;ASSIGNOR:HEXION SPECIALTY CHEMICALS, INC.;REEL/FRAME:017946/0151Effective date: 20060505Aug 31, 2005ASAssignmentOwner name: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENTFree format text: SECURITY AGREEMENT;ASSIGNORS:RESOLUTION PERFORMANCE PRODUCTS LLC;RESOLUTION SPECIALTY MATERIALS LLC;BORDEN CHEMICAL, INC.;REEL/FRAME:016480/0648Effective date: 20050831Owner name: WILMINGTON TRUST COMPANY, AS COLLATERAL AGENT, DELFree format text: SECURITY AGREEMENT;ASSIGNORS:RESOLUTION PERFORMANCE PRODUCTS LLC;RESOLUTION SPECIALTY MATERIALS LLC;BORDEN CHEMICAL, INC.;REEL/FRAME:016522/0428Effective date: 20050831Jan 25, 2005ASAssignmentOwner name: GENERAL ELECTRIC CAPITAL CORPORATION, AS COLLATERAFree format text: SECURITY AGREEMENT;ASSIGNOR:RESOLUTION PERFORMANCE PRODUCTS LLC;REEL/FRAME:015596/0703Effective date: 20050124Owner name: RESOLUTION PERFORMANCE PRODUCTS LLC, TEXASFree format text: RELEASE OF PATENT SECURITY AGREEMENT;ASSIGNOR:MORGAN STANLEY & CO., INCORPORATED;REEL/FRAME:015603/0117Effective date: 20050120Owner name: RESOLUTION PERFORMANCE PRODUCTS LLC 1600 SMITH STRFree format text: RELEASE OF PATENT SECURITY AGREEMENT;ASSIGNOR:MORGAN STANLEY & CO., INCORPORATED /AR;REEL/FRAME:015603/0117Free format text: SECURITY AGREEMENT;ASSIGNOR:RESOLUTION PERFORMANCE PRODUCTS LLC /AR;REEL/FRAME:015596/0703Owner name: RESOLUTION PERFORMANCE PRODUCTS LLC 1600 SMITH STRFree format text: RELEASE OF PATENT SECURITY AGREEMENT;ASSIGNOR:MORGAN STANLEY & CO., INCORPORATED /AR;REEL/FRAME:015603/0117Effective date: 20050120Owner name: GENERAL ELECTRIC CAPITAL CORPORATION, AS COLLATERAFree format text: SECURITY AGREEMENT;ASSIGNOR:RESOLUTION PERFORMANCE PRODUCTS LLC /AR;REEL/FRAME:015596/0703Effective date: 20050124Jan 5, 2004FPAYFee paymentYear of fee payment: 4Jan 5, 2004SULPSurcharge for late paymentJul 30, 2003REMIMaintenance fee reminder mailedJan 22, 2002ASAssignmentOwner name: RESOLUTION PERFORMANCE PRODUCTS LLC, TEXASFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SHELL OIL COMPANY;REEL/FRAME:012506/0484Effective date: 20001129Owner name: RESOLUTION PERFORMANCE PRODUCTS LLC 1600 SMITH STROwner name: RESOLUTION PERFORMANCE PRODUCTS LLC 1600 SMITH STRFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SHELL OIL COMPANY /AR;REEL/FRAME:012506/0484Owner name: RESOLUTION PERFORMANCE PRODUCTS LLC 1600 SMITH STRFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SHELL OIL COMPANY /AR;REEL/FRAME:012506/0484Effective date: 20001129Owner name: RESOLUTION PERFORMANCE PRODUCTS LLC 1600 SMITH STRFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SHELL OIL COMPANY;REEL/FRAME:012506/0484Effective date: 20001129Apr 23, 2001ASAssignmentOwner name: MORGAN STANLEY & CO. INCORPORATED, NEW YORKFree format text: SECURITY AGREEMENT;ASSIGNOR:RESOLUTION PERFORMANCE PRODUCTS LLC;REEL/FRAME:011700/0546Effective date: 20001114Owner name: MORGAN STANLEY & CO. INCORPORATED 35TH FLOOR 1221Owner name: MORGAN STANLEY & CO. INCORPORATED 35TH FLOOR 1221Free format text: SECURITY AGREEMENT;ASSIGNOR:RESOLUTION PERFORMANCE PRODUCTS LLC /AR;REEL/FRAME:011700/0546Owner name: MORGAN STANLEY & CO. INCORPORATED 35TH FLOOR 1221Free format text: SECURITY AGREEMENT;ASSIGNOR:RESOLUTION PERFORMANCE PRODUCTS LLC;REEL/FRAME:011700/0546Effective date: 20001114Owner name: MORGAN STANLEY & CO. INCORPORATED 35TH FLOOR 1221Free format text: SECURITY AGREEMENT;ASSIGNOR:RESOLUTION PERFORMANCE PRODUCTS LLC /AR;REEL/FRAME:011700/0546Effective date: 20001114RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services