MICROENCAPSULATED EPOXY ADHESIVE SYSTEM

Abstract: A microencapsulated epoxy adhesive system is dis­ closed comprising in admixture epoxy resin capsules and encapsulated Anacamine TL (Pacific Anchor Chemical Co.) as the curing agent. When applied, for example to a zinc plated bolt and the bolt is tightened, the capsules break and the resin cures and provides good breakaway torques.

Description: MICROENCAPSULATED EPOXY ADHESIVE SYSTEM The present invention relates to an encapsulated epoxy adhesive system and, more particularly, to a water based adhesive system employing a hydrophobic curing agent. Most common epoxy adhesives are prepared from a two-part system comprising an epoxy resin and a curing agent. Prior to application, the two parts are mixed and the resin and curing agent mixture are applied to the bonding site where the resin is. cured into a hard adherent mass. The common two-part adhesive system is inconvenient to work with because the two parts must be mixed and the adhesive cannot be applied directly to the bond site. One of the techniques that has been used to make the two part system more convenient has been to microencapsulate the epoxy resin and the curing agent. Encapsulated resin and curing agent do not react. Therefore, a mixture of the capsules can be formed and applied directly to a bonding site. There when the capsules are broken the resin and curing agent react and the epoxy resin bonds. Encapsulated adhesive systems such as this have been employed with threaded fasteners. The encapsulated resin and curing agent are applied to the fastener. As the fastener is tightened, the capsules break and the adhesive bond is formed. Some of the problems which hae been associated with prior epoxy adhesive systems have been that the curing agents used are relatively hygroscopic and have a short shelf life, and the systems have employed a polymeric vehicle. Capsules of curing agent produced by prior encapsulation techniques have been to some extent moisture permeable and the shelf life of the system has not been appreciably enhanced. In accordance with the present invention these drawbacks have been overcome by an encapsulted adhesive system employing a hydrophobic and therefore less hygroscopic curing agent. In accordance with a preferred embodiment of the invention, the polymeric vehicle is replaced by water without sacrificing the adhesive qualities of a polymer based system. The system of the present invention has the following advantages: 1. Much higher breakAway torques on 3/8" bolts. 2. Much greater consistency and reproducibility. 3. Much less moisture sensitivity which means coated bolts may not have to be protected from the environment. 4. Much longer pot-life. This enables a l-part ready-to-apply aqueous based epoxy adhesive. In accordance with the present invention an encapsulated epoxy adhesive system is provided comprising epoxy resin capsules and an encapsulated hydrophobic curing agent. The curing agent is preferably Anacamine TL by Pacific Anchor Chemical Corp. Anacamine TL is a 45% solution of methylene dianaline in a non-volatile plasticizer. The epoxy system of the present invention is prepared by forming epoxy resin capsules. These capsules can be formed using techniques which are well known in the art. One convenient method is to form a polyvinyl alcohol capsule wall via coacervation and graft onto it a urea-resorcinol-formaldehyde resin. Epon 828 by Shell Oil Co. is a suitable epoxy resin but those skilled in the art will recognize that other epoxy resins can be used. These capsules may range in size from about 10 to about 1000 micron and preferably 50 to 150 micron. Normally the epoxy content of the capsules is on the order of 86%. The capsules may be used as a free flowing powder although it is not necessary to isolate them. The epoxy capsules are, in one embodiment of the invention, mixed with a coacervate emulsion of the curing agent. Using Anacamine TL as an example, this is accomplished by 1.) dispersing a 75% solution of Ancamine TL in xylene into a Gelvitol 20-90 PVA solution as 50-100 micron droplets, 2) at about 450C coacervating the PVA and promoting encapsulation of the Ancamine TL by the sequential addition of solutions of gum arabic, resorcinol and sodium sulfate, 3) allowing the swollen walled capsules to settle overnight, and 4) decanting off the supernatant phase and gently agitating the coacervate phase with a spatula to produce a 1-20 micron "coacervate emulsion" of the Ancamine TL. Thereafter the epoxy capsules are added to the emulsion together with sufficient binder solution to prepare a slurry with a viscosity suitable for hand application. One such formulation is shown below: Epoxy Capsules 4.0 parts Cocervate emulsion 4.0 parts Binder Solution As required A suitable binder for the above formulation is a solution of 2.5% Elvanol PVA 71-30 and 0.5% Kelzans xanthum gum. Another method of preparing the Ancamine TL coacervate emulsion is by preparing the PVA-resorcinol coacervate without the curing agent and decanting off the supernatant after settling overnight. Then the Ancamine TL curing agent is emulsified into the coacervate using the Waring Blendor and with or without the addition of some of the supernatant to adjust viscosity. The emulsion prepared by this method will be referred to as a "precoacervate emulsion". In accordance with a preferred embodiment of the present invention, water is substituted for the xanthum gum/PVA binder solution in the coating formulation discussed above. It has been found that in some applications no viscosity builder or added binder is necessary. The PVA coacervate serves as the binder. In addition, by eliminating the xanthum gum which promotes bacterial growth, the problem caused by the limited shelf life of this component is eliminated. Initial testing indicates that the test results obtained through use of water as the diluent in the coating formulation are comparable to those obtained through use of the xanthum gum/PVA binder. Preparing this formulation, it is been found desirable to use less water in preparing the Ancamine TL coacervate emulsion. The result is a coacervate emulsion from which a supernatant phase need not be decanted, and which requires no additional water as a binder for the preparation of the coating formulation. The entire process can be carried out in much less time than that required by the original procedure, for example, a total manufacturing time of 2.5 hours. Initial test results are very encouraging. Settling of the coacervate Ancamine TL complex does occur during storage, but is not expected to present any formulation or coating difficulties. In comparison to a system containing a binder, it has been found that a simple water dilution provides good breakaway torques, but addition of a binder may provide better prevailing-off torques in some cases. This may be due to the binder system filling the bolt threads to a greater extent. The water - no binder system is more cost effective and production-oriented. The adhesive system of the present invention is cured by breaking the microcapsules such that the resin and curing agent contact and react. Prior to curing and after application, the coating should be allowed to dry. If it does not, the breakaway torque is diminished and the results are not as reproducible. A typical drying condition is 15 minutes at 1000C. Excessive heating may volatize components necessary for an optimum cure that yield good breakaway torques, but a certain amount of drying is essential to eliminate excess moisture from the coating. A coating which is more thoroughly dried in a relatively rapid manner may provide more abrasive interference and, therefore, higher prevailing off torques. The effect of the drying conditions on one adhesive system is shown below. Prevailing Breakaway Drying Off Torque Torque (inch-pounds) Conditions 67 182 5 min. at 1000C 76 s 151 10 min. at 1000C 97 158 15 min. at 1000C 12 103 5 min. at 750C 26 142 10 min. at 750C 32 173 15 min. at 750C 79 180 20 min. at 750C 19 178 5 hours at ambient The effect of the epoxy capsule size on the torque is shown in the following table for a water diluent system. Capsule Prevailing Breakaway Size U (Majority Off Torque Torque (inch-pounds) of Capsules 74 158 50-150 61 149 50-150 61 130 100 47 206 125 86 168 53 59 170 50-150 51 154 150 The table below shows the effect of cure time on the torques for a water diluent-no binder system. Prevailing Breakaway Cure Off Torque Torque (inch-pounds) Time 18 55 8 hrs. 55 180 16 hrs. 68 214 24 hrs. 65 192 48 hrs. 106 190 72 hrs. Having described fe invention in detail and by reference to preferred embodiments thereby it will be apparent to those skilled in the art that numerous variations and modifications thereof are possible without departing from the invention as claimed.

Claims: CIhIMS 1. An encapsulated epoxy adhesive comprising epoxy resin microcapsules and a coacervate emulsion of a hydrophobic curing agent dispersed in a binder solution. 2. An encapsulated epoxy adhesive comprising epoxy resin microcapsules and a coacervate emulsion of a hydrophobic curing agent dispersed in an aqueous based system without additional binder. 3. An encapsulated epoxy adhesive of claim 1 or 2, wherein said hydrophobic curing agent is methylene dianaline. 4. An encapsulated epoxy adhesive of claim 1, or claim 1 in combination with claim 3, wherein said binder solution comprises polyvinyl alcohol and Xanthum gum. 5. An encapsulated epoxy adhesive of any preceding claim, wherein said epoxy capsules are about 50 to 150 microns. 6. The encapsulated epoxy adhesive of any preceding claim, wherein said epoxy resin microencapsules are formed by interfacial polymerization of urea resorcinol formaldehyde resin. 7. A process for bonding a threaded fastener which comprises applying the encapsulated epoxy adhesive of any preceding claim, to the fastener and engaging the threads and thereby breaking the capsules and causing the epoxy resin to cure.

Inventors: DAVIS, COLIN E., HART, RONALD L., WORK, DALE E.
Applicants: CAPSULATED SYSTEMS, INC.
Application year: 1982
Main classification: C09J3
IPC codes: F16B39, C09J7, C08J3, C09J163, F16B33