CA1229696A - Rapid cure epoxy adhesive sealant - Google Patents
Rapid cure epoxy adhesive sealantInfo
- Publication number
- CA1229696A CA1229696A CA000398831A CA398831A CA1229696A CA 1229696 A CA1229696 A CA 1229696A CA 000398831 A CA000398831 A CA 000398831A CA 398831 A CA398831 A CA 398831A CA 1229696 A CA1229696 A CA 1229696A
- Authority
- CA
- Canada
- Prior art keywords
- curing agent
- epoxy resin
- curing
- adhesive sealant
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/241—Preventing premature crosslinking by physical separation of components, e.g. encapsulation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Material Composition (AREA)
- Epoxy Resins (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A putty-like epoxy adhesive sealant composition comprised of a first band of an uncured epoxy resin composition and a second band comprising a composition capable of rapidly curing the uncured epoxy resin composition within about ten minutes from the time when said first band and said second band are combined to form a substantially uniform mixture. The second band comprises an inner core of a fast curing agent enveloped by an outer surrounding wrap of a curing agent composition capable of protecting said fast curing agent from premature reaction with said uncured epoxy resin, and from reaction with the atmosphere where the curing agent becomes oxidized and prematurely hard. Substantially equal amounts of said first band and said second band are combined to form a substantially uniform mixture which cures to form a cured epoxy adhesive sealant within about ten minutes.
A putty-like epoxy adhesive sealant composition comprised of a first band of an uncured epoxy resin composition and a second band comprising a composition capable of rapidly curing the uncured epoxy resin composition within about ten minutes from the time when said first band and said second band are combined to form a substantially uniform mixture. The second band comprises an inner core of a fast curing agent enveloped by an outer surrounding wrap of a curing agent composition capable of protecting said fast curing agent from premature reaction with said uncured epoxy resin, and from reaction with the atmosphere where the curing agent becomes oxidized and prematurely hard. Substantially equal amounts of said first band and said second band are combined to form a substantially uniform mixture which cures to form a cured epoxy adhesive sealant within about ten minutes.
Description
it Buckley on US. Letters Patent No. 3,708,379 and 3,837,981 describe elastomeric tape and epoxy tape, respectively. The epoxy tape described particularly in the latter patent is marketed commercially 5 as an adhesive sealant for a wide variety of applications.
A commercial form of epoxy tape made in accord wit Patent No.
3,837,981 has a band of uncured epoxy ribbon which is brilliant blue in close side-by-side relation with a band of a curing composition which is yellow. When substantially equal portions of the two bands 10 of material are mixed to form a uniform mixture, an adhesive sealant is formed which may be applied or used for any desired purpose. the adhesive-sealant formed on uniform mixing of substantially equal portions of the epoxy resin and curing agent compositions has a putty-like consistency, and when used to adhere or seal has inherent ability 15 to stay where it is applied even without support or clumping means to hold the objects being adhered together during the time required for the curing of the epoxy resin.
Epoxy tape products made in accord with Patent No. 3,837,981 may be lo D fated so as to fully cure to a solid epoxy adhesive in 20 approximately four to twenty-four hours. For general applications the time required for curing of the adhesive sealant is practical and not objectionable.
As will be appreciated, there are instances when it is desircible to have an extremely fast curing epoxy adhesive sealant, that is, one 25 which may be applied and cure in a matter of a few minutes rather than hours. Fast curing epoxy adhesive sealants are known, however, such products have not heretofore been known to exist in a form similar to that illustrated in Patent No. 3,837,981. Typically, fast curing epoxy adhesive sealants exist in liquid form where one combines a 30 portion of a liquid epoxy resin with a portion of a liquid curing agent. The disadvantages of such products are obvious, and include the problem of cross contamination of the epoxy resin and curing agent which could result in loss of the supply of each component and the necessity for packaging each component separately with the expense 35 inherent in this procedure.
err exists, therefore, a need in the art for a fast cure epoxy adhesive sealant of the type illustrated in Patent No. 3,837,981. In I
other words, there exists a need for a East cure epoxy adhesive sealant having a putty-like consistency described in the aforesaid patent, a product which does not need special storage conditions or packaging and one which is available for use immediately through the 5 simple expediency of hand mixing. It is not necessary that the product of this invention be in any particular configuration illustrated in Patent No. 3,837,981 although the product may exist in the side-by-side configuration depicted in that patent, or in any form in which the respective bands are in reasonably continuous form even lo though there is no actual touching of the bands in side-by-side relationship. mix need has not been satisfied heretofore because of the nature of the agents necessary to accomplish relatively fast cure of epoxy resins. Typically, such fast cure agents are extremely air sensitive, being rendered unsuitable for use by oxygen, humidity or 15 other components of the atmosphere. must it has not been possible to make use of fast curing agents unless they have been packaged in containers which are impervious to the atmosphere.
The present invention has satisfied the need in the art for a fast cure epoxy adhesive sealant which is in putty form, protected 20 from adverse effects of the atmosphere and useful by simple mixing and molding techniques.
:~.2;2~6~
Description of the Invention According to this invention, a putty like room temperature, fast cure adhesive sealant comprising a first band of an uncured reactive polymer or resin adhesive sealant composition and a second band, said 5 second band comprising a composition capable of curing or polymerizing said uncured reactive polymer or resin composition when said first and second bands are combined to form a substantially uniform mixture, is improved wherein said second band comprises an agent capable of curing or polymerizing said uncured reactive resin or polymer to a hard lo adhesive sealant within about ten minutes from the time when said uncured resin or polymer composition and said curing cc~position are combined to form a substantially uniform mixture.
no preferred embodiments of this invention encompass a formulation of an uncured epoxy resin and curing aunt capable of 15 forming a useful adhesive sealant within about five minutes after mixing to a Shore A hardness of 30.
In the appended drawings, Fig. l is a plan view illustrating an embodiment of the rapid cure adhesive sealant of this invention, Figs
A commercial form of epoxy tape made in accord wit Patent No.
3,837,981 has a band of uncured epoxy ribbon which is brilliant blue in close side-by-side relation with a band of a curing composition which is yellow. When substantially equal portions of the two bands 10 of material are mixed to form a uniform mixture, an adhesive sealant is formed which may be applied or used for any desired purpose. the adhesive-sealant formed on uniform mixing of substantially equal portions of the epoxy resin and curing agent compositions has a putty-like consistency, and when used to adhere or seal has inherent ability 15 to stay where it is applied even without support or clumping means to hold the objects being adhered together during the time required for the curing of the epoxy resin.
Epoxy tape products made in accord with Patent No. 3,837,981 may be lo D fated so as to fully cure to a solid epoxy adhesive in 20 approximately four to twenty-four hours. For general applications the time required for curing of the adhesive sealant is practical and not objectionable.
As will be appreciated, there are instances when it is desircible to have an extremely fast curing epoxy adhesive sealant, that is, one 25 which may be applied and cure in a matter of a few minutes rather than hours. Fast curing epoxy adhesive sealants are known, however, such products have not heretofore been known to exist in a form similar to that illustrated in Patent No. 3,837,981. Typically, fast curing epoxy adhesive sealants exist in liquid form where one combines a 30 portion of a liquid epoxy resin with a portion of a liquid curing agent. The disadvantages of such products are obvious, and include the problem of cross contamination of the epoxy resin and curing agent which could result in loss of the supply of each component and the necessity for packaging each component separately with the expense 35 inherent in this procedure.
err exists, therefore, a need in the art for a fast cure epoxy adhesive sealant of the type illustrated in Patent No. 3,837,981. In I
other words, there exists a need for a East cure epoxy adhesive sealant having a putty-like consistency described in the aforesaid patent, a product which does not need special storage conditions or packaging and one which is available for use immediately through the 5 simple expediency of hand mixing. It is not necessary that the product of this invention be in any particular configuration illustrated in Patent No. 3,837,981 although the product may exist in the side-by-side configuration depicted in that patent, or in any form in which the respective bands are in reasonably continuous form even lo though there is no actual touching of the bands in side-by-side relationship. mix need has not been satisfied heretofore because of the nature of the agents necessary to accomplish relatively fast cure of epoxy resins. Typically, such fast cure agents are extremely air sensitive, being rendered unsuitable for use by oxygen, humidity or 15 other components of the atmosphere. must it has not been possible to make use of fast curing agents unless they have been packaged in containers which are impervious to the atmosphere.
The present invention has satisfied the need in the art for a fast cure epoxy adhesive sealant which is in putty form, protected 20 from adverse effects of the atmosphere and useful by simple mixing and molding techniques.
:~.2;2~6~
Description of the Invention According to this invention, a putty like room temperature, fast cure adhesive sealant comprising a first band of an uncured reactive polymer or resin adhesive sealant composition and a second band, said 5 second band comprising a composition capable of curing or polymerizing said uncured reactive polymer or resin composition when said first and second bands are combined to form a substantially uniform mixture, is improved wherein said second band comprises an agent capable of curing or polymerizing said uncured reactive resin or polymer to a hard lo adhesive sealant within about ten minutes from the time when said uncured resin or polymer composition and said curing cc~position are combined to form a substantially uniform mixture.
no preferred embodiments of this invention encompass a formulation of an uncured epoxy resin and curing aunt capable of 15 forming a useful adhesive sealant within about five minutes after mixing to a Shore A hardness of 30.
In the appended drawings, Fig. l is a plan view illustrating an embodiment of the rapid cure adhesive sealant of this invention, Figs
2, 4 and 5 are cross-sectional views of embodiments of the invention, 20 while Fig. 3 is a cross-sectional view taken along 3-3 of Fig. l.
The room temperature, fast cure adhesive sealant of this invention has to principal components. First, it includes an uncured reactive polymer or resin, and second, a curing system for the reactive polymer or resin. In preferred embodiments, epoxy resins 25 which are complex polymeric reaction products of polyhedra phenols with polyfunctional halohydrins, are used. Useful epoxy resins are described more cc~pletely in Patent No. 3,837,98l. Useful reactive polymers include styrenes resins which are cure by free radical polymerization with organ peroxide curing agents. Also silicone 30 adhesive sealants where the silicone polymer would be cured by moisture sensitive organ tin cross linking agents are encased by this invention.
While this invention encompasses room temperature, fast cure adhesive sealants encompassing polyester and silicone resins, it will 35 be described in detail with respect to epoxy resin adhesive sealant compositions. Ire curing system for the uncured epoxy resin compositions useful in this invention comprises two components, each Sue being a curing agent for epoxy resins. Polyamide compositions are typically used as curing agents for polyamide resins.
As is known, specific epoxy resins react differently with specific curing agents. One can vary the time required for complete 5 curing of an epoxy resin by versing the specific polyamide curing agents and/or varying the amount of polyamide curing agent. Curing agents which can be expected to provide a rapid or fast cure of an epoxy resin, i.e., a cure which is complete within about -ten minutes from the time when the epoxy resin composition and curing composition 10 are combined to form a substantially uniform mixture, are generally recognized as being relatively air sensitive. Air sensitive epoxy resin curing systems generally comprise liquid polymercaptan polymers and accelerators such-as an amino phenol, which undergo such degradation as to lose their ability to cause curing of an epoxy resin 15 as the result of interaction with the atmosphere. It has been found that a room temperature fast cure epoxy resin adhesive sealant may be formulated using only a polymercaptan curing agent, and curing will be effected within about 5 to about 10 minutes. It has also been found that adhesive sealants in which curing occurs in 5 minutes or less may 20 be formulated if the curing agent includes accelerators as jell as the polymercaptan polymer.
m e fast cure curing agent, i.e. a curing agent effective to cause curing of the epoxy resin used in the epoxy tape of this invention within about ten minutes, may comprise a liquid 25 polymercaptan polymer and/or an amino phenol. Epoxy resins have been cured with polymercaptan-aminophenol curing agent systems in the past.
The air sensitive nature of such curing systems, and their liquid form, has heretofore made it impossible to use such curing systems in epoxy tape products of the type described in Patent No. 3,837,981.
Liquid polymercaptan polymers useful in the fast cure curing agent of this invention include those having a mercaptan value (milliequivalents per gram), of 1 to 20, preferably 3 to 4. Such polymers are available commercially under the trademark Capture from Diamond Shamrock, Inc.
In en*xxlL~ents where extremely rapid cure (less than five minutes) is desired the liquid polymercaptan polymer is combined with an amino phenol. Useful amuses are available commercially under the trade names DYE 30 and Do 10 from Room & Hays Company. The ~.~2~;96 polymercaptan polymer and amino phenol may be combined in a ratio of from about 20:1 to bout 5:1, preferably about 6:1 to form the fast cure curing agent of this invention. It is possible -that either the polymercaptan or the amino phenol components could be used alone to 5 effect cure of the epoxy resin present in the compositions of this invention. However, a significant attribute of the invention lies in the fact that the adhesive sealant may be mixed and applied by hand.
It is kin that the amino phenol curing agents may cause skin irritation, thus it is desired -to minimize contact of these agents 10 with the skin. Accordingly, the amino phenol curing agents are used only in those levels sufficient to effect Requiem temperature rapid cure within the desired 10 minute period. This may be accomplished so long as the curing agent comprises I by weight or less of the amino phenol cc~nponent.
me polymercaptan polymer and amino phenol fast cure curing agents are rather low viscosity liquids, and they are air sensitive compounds as stated Ahab. These components are made useful in an epoxy type product of the type described in Patent No. 37837,981 by cabining them with components to provide compositions having physical 20 properties required for forming a potluck product. Thus, the fast cure curing agent may be ec~nbined with various fillers, plasticizers colorants and other special purpose ingredients. In preferred embcd:hr~nts, the low viscosity liquid fast cure curing agent is eambined with a high viscosity polyamide resin or blend of polyamide 25 resins in a ratio of about 1:1 to about 2-1, and an inert carrier such as tale to form a putty-like composition which nay be extruded in tape form.
While the blend of room temperature fast cure curing agent and polyamide rosin described above may have a putty-like consistency so 30 as to be amenable to extrusion in tape form, it is air sensitive, and thus is not amenable to use as curing agent for an epoxy resin in the embodiments depicted and described in Patent No. 3,833,g81. Such a product is unlike that depicted in Fig. 4 of Patent No. 3,837,981 ea~prising epoxy resin base and curing agent. The amount of polyamide 35 curing agent required for this purpose is not critical so long as the room tRImperature fast cure curing agent is protected from exposure to the atmosphere. This is generally accomplished by enveloping the putty-like room temperature, fast cure curing agent with a layer of 9Ç;9-'~
polyc~mQde curing agent from about 0.5 to 2 mm in thickness Any inert putty like material which is compatible with the epoxy resin may be useful in forming the protective envelope. The envelope can be applied by mutual extrusion of the room temperature fast cure curing 5 agent and polyc~lide or the curing agent could be placed in a molten polyamide resin bath from which a coating of the polyamide would adhere to the curing agent.
Fig. 2 illustrates an epoxy tape in which Band B contains the epoxy resin composition, band A contains the fast cure curing agent 10 and band C contains the polyamide resin curing composition which serves to protect the fast cure curing agent from atmospheric degradation. Alternative embodiments of the invention are depicted in Figs. 3, 4 and 5. Fig 4 depicts an alternative embodiment in which one strip (B) comprises the epoxy resin, while the other comprises the 15 room temperature fast cure curing agent (A) and the polyamide resin curing composition (C) which serves to protect the room temperature, fast cure curing agent from atmospheric degradation. In such form, the separate strips are carried on release paper or other carrier and packaged as a single unit.
Fig. 5 illustrates an embodiment in which curing agent A and epoxy resin s are each wrapped or enveloped by the polyamide curing composition C. This may be accomplished by extrusion of the materials, or, alternatively, bands A and B could be placed in a bath of molten polyamide curing composition from which the curing 25 composition C will adhere to bands A and s in the form depicted in Fig. 5. In this embodiment as well as those illustrated in the other figures, it will be appreciated that the curing composition C
functions in a manner analogous to a container, and is unique in this role, since it becomes part of and is consumed with use of the 30 adhesive sealant, and yet does not have to be removed or segregated from the adhesive-sealant prior to use.
Figs. 1 and 3 illustrate a method of sealing ends of the epoxy tape before and after removal of portions of the tape for use as an epoxy adhesive sealant so as to maintain the protective shield about 35 the air sensitive room temperature fast cure curing agent.
The room temperature curing agent, whether in the form of polyamide, polymercaptan and/or amino phenol, should be present in an amount sufficient to cross link from about 80 to about 120%, preferably I
about 100%, of the available cross-linking sites of the epoxy resin in the tape.
As mentioned, the epoxy resin and the curing agent therefore are admixed with various fillers, plasticizers, and colorants to form the 5 putty like compositions which are extruded into separate shapes or into an epoxy tape of the type described in Patent No. 3,837,981~
IJseful fillers for this purpose include talc, powdered alumina and asbestos fiber. Fillers such as these provide the epoxy resin and the curing agent compositions with physical properties and the putty-like 10 consistency necessary for extrusion into tape form. The fillers are incorporated into the epoxy resin and the curing agent compositions in amounts sufficient to produce a putty-like mass which can be easily extruded into the desired epoxy tape. Pc~7dered talc such as Mist Ron Vapor available cc~rnercially from United Sierra Division of Cypress 15 Mines Corporation, is an especially preferred filler, since it yields a handle able putty-like mass with both epoxy resins and the curing agent compositions Putty-like products prepared with this filler skew less tendency to stick to the hands than do compositions prepared with other fillers. Useful plasticizers include resinous polyols and 20 other agents which serve to yield a more flexible cured product.
A variety of coloring agents may be included in the epoxy or the curing agent compositions as desired. Useful coloring agents include pigments like titanium dioxide which provides a white color; carbon black or black color end various organic and inorganic pigments for 25 o'er colors It it desirable that the respective hands of epoxy resin and curing agent composition be of contrasting color to serve as an indicator of complete and thorough mixing.
rho use the room temperature, fast cure products of this invention, a portion of the tape comprising substantially equal 30 lengths of the epoxy resin band and the curing agent band is selected and the compositions are mixed together. The mixing may be acc~nplished by hand or with the aid of mechanical assistance. Mixing permits the components, i.e. the epoxy resin and the room temperature fast cure curing agent, to react and effect curing, in situ. Zen the 35 epoxy resin and the room temperature fast cure curing agent bands of the tape are of contrasting color, it is easy to determine when a uniform mixture has been obtained simply by continuing mixing until 9Çi the mixture has a uniform color. I-t will be appreciated that pigment may be included in one or both buds of the composition.
me overall extrusion process for preparing the products of this invention is analogous to that described in Patent No. 3,837,981. In 5 this process, the respective putty-like compositions may be extruded from three extrudes which lay down the respective bands illustrated in Figs. 2 and 4. After extrusion, any desired length of the tape may be simply rolled up and packaged in any desired manner. mere is no need for special packaging requirements to give a useful shelf life to 10 the tape. when the epoxy tape of this invention is used as an adhesive sealant, any desired quantity of the epoxy tape made of approximately equal lengths of each band in the tape are selected and kneaded together under ambient conditions forming a uniform mixture.
The resulting putty-like or dough-like epoxy adhesive sealant has a 15 relatively short pot life and must be applied rather promptly as substantial curing is effected at ambient temperatures within about ten minutes from the time when the epoxy resin composition and the room temperature fast cure curing composition are combined to form a substantially uniform mixture. mere must be some time after mixing 20 by hand in which the product remains workable for each application.
Accordingly, the product is formulated so that substantial curing to the point of unw~rkability by hand occurs within about 5 minutes from the time of mixing. mix point is characterized by a Dormitory hardness shore A) of 30. The product reaches a Shore A of 60 within 25 10 minutes from time of mixing, and thus is an extremely rapid, room temperature curing adhesive sealant.
The epoxy formed from the epoxy tape of this invention substantially cures within ten minutes or less from the time of initial mixing to a useful, tough, solid, epoxy adhesive. me epoxy 30 resin formed from the epoxy tape with this invention has excellent adhesive-sealant properties, and may be utilized to adhere ceramic, wood and metal and like materials to aluminum, concrete, steel, ceramic and like substances. The epoxy composition will cure under water making it useful in many marine environments. me invention may 35 be illustrated in the following example:
Lowe 471 parts of an epoxy resin Eon 828) having an epoxy equivalent weight of 185 to 192 are mixed with 525 pounds of powdered talc, Mist Ron Vapor by United Sierra Division of Cypress Mines Corporation, forming a highly viscous, smooth material.
A curing agent composition is prepared by mixing 17 parts of a semisolid polyamide resin having an amine value of 90 and a viscosity of 10 poises at 150C. (Versamid~ 100 of General Mills) with 30 parts of a liquid polyamide resin having an amine value of 200 to 300 (Assumed 215 of A Chemicals, Inc.), with 60 parts of powdered talc 10 list Ron Vapor ) in a sigma blade mixer maintained at a temperature not exceeding 120F. until a uniform mixture is formed. A third mixture is prepared by mixing 30 parts of a semisolid polyamide resin having an amine value of 90 and a viscosity of 10 poises at 150C.
(Versamid~ 100), with 48 parts of liquid polymercaptan polymer having 15 a mercaptan value of 3.6 milliequivalents per gram tcapcure~ of Diamond Shamrock), 8 parts of amino phenol DUMP 10 of Room & Hays) and 100 parts of powdered talc (Mist Ron Vapor ) in a able arm putty mixer maintained at a temperature not exceeding 120F. until a uniform mixture is formed. Substantially equal portions, by weight, of each 20 of the three mixtures are formed into slugs and fed separately into extrudes which simultaneously lay dawn bands of each mixture in the form depicted in the drawings. A room temperature fast curing epoxy adhesive is formed which will substantially cure to Shore A hardness of 30 within about 5 minutes after initial mixing.
The room temperature, fast cure adhesive sealant of this invention has to principal components. First, it includes an uncured reactive polymer or resin, and second, a curing system for the reactive polymer or resin. In preferred embodiments, epoxy resins 25 which are complex polymeric reaction products of polyhedra phenols with polyfunctional halohydrins, are used. Useful epoxy resins are described more cc~pletely in Patent No. 3,837,98l. Useful reactive polymers include styrenes resins which are cure by free radical polymerization with organ peroxide curing agents. Also silicone 30 adhesive sealants where the silicone polymer would be cured by moisture sensitive organ tin cross linking agents are encased by this invention.
While this invention encompasses room temperature, fast cure adhesive sealants encompassing polyester and silicone resins, it will 35 be described in detail with respect to epoxy resin adhesive sealant compositions. Ire curing system for the uncured epoxy resin compositions useful in this invention comprises two components, each Sue being a curing agent for epoxy resins. Polyamide compositions are typically used as curing agents for polyamide resins.
As is known, specific epoxy resins react differently with specific curing agents. One can vary the time required for complete 5 curing of an epoxy resin by versing the specific polyamide curing agents and/or varying the amount of polyamide curing agent. Curing agents which can be expected to provide a rapid or fast cure of an epoxy resin, i.e., a cure which is complete within about -ten minutes from the time when the epoxy resin composition and curing composition 10 are combined to form a substantially uniform mixture, are generally recognized as being relatively air sensitive. Air sensitive epoxy resin curing systems generally comprise liquid polymercaptan polymers and accelerators such-as an amino phenol, which undergo such degradation as to lose their ability to cause curing of an epoxy resin 15 as the result of interaction with the atmosphere. It has been found that a room temperature fast cure epoxy resin adhesive sealant may be formulated using only a polymercaptan curing agent, and curing will be effected within about 5 to about 10 minutes. It has also been found that adhesive sealants in which curing occurs in 5 minutes or less may 20 be formulated if the curing agent includes accelerators as jell as the polymercaptan polymer.
m e fast cure curing agent, i.e. a curing agent effective to cause curing of the epoxy resin used in the epoxy tape of this invention within about ten minutes, may comprise a liquid 25 polymercaptan polymer and/or an amino phenol. Epoxy resins have been cured with polymercaptan-aminophenol curing agent systems in the past.
The air sensitive nature of such curing systems, and their liquid form, has heretofore made it impossible to use such curing systems in epoxy tape products of the type described in Patent No. 3,837,981.
Liquid polymercaptan polymers useful in the fast cure curing agent of this invention include those having a mercaptan value (milliequivalents per gram), of 1 to 20, preferably 3 to 4. Such polymers are available commercially under the trademark Capture from Diamond Shamrock, Inc.
In en*xxlL~ents where extremely rapid cure (less than five minutes) is desired the liquid polymercaptan polymer is combined with an amino phenol. Useful amuses are available commercially under the trade names DYE 30 and Do 10 from Room & Hays Company. The ~.~2~;96 polymercaptan polymer and amino phenol may be combined in a ratio of from about 20:1 to bout 5:1, preferably about 6:1 to form the fast cure curing agent of this invention. It is possible -that either the polymercaptan or the amino phenol components could be used alone to 5 effect cure of the epoxy resin present in the compositions of this invention. However, a significant attribute of the invention lies in the fact that the adhesive sealant may be mixed and applied by hand.
It is kin that the amino phenol curing agents may cause skin irritation, thus it is desired -to minimize contact of these agents 10 with the skin. Accordingly, the amino phenol curing agents are used only in those levels sufficient to effect Requiem temperature rapid cure within the desired 10 minute period. This may be accomplished so long as the curing agent comprises I by weight or less of the amino phenol cc~nponent.
me polymercaptan polymer and amino phenol fast cure curing agents are rather low viscosity liquids, and they are air sensitive compounds as stated Ahab. These components are made useful in an epoxy type product of the type described in Patent No. 37837,981 by cabining them with components to provide compositions having physical 20 properties required for forming a potluck product. Thus, the fast cure curing agent may be ec~nbined with various fillers, plasticizers colorants and other special purpose ingredients. In preferred embcd:hr~nts, the low viscosity liquid fast cure curing agent is eambined with a high viscosity polyamide resin or blend of polyamide 25 resins in a ratio of about 1:1 to about 2-1, and an inert carrier such as tale to form a putty-like composition which nay be extruded in tape form.
While the blend of room temperature fast cure curing agent and polyamide rosin described above may have a putty-like consistency so 30 as to be amenable to extrusion in tape form, it is air sensitive, and thus is not amenable to use as curing agent for an epoxy resin in the embodiments depicted and described in Patent No. 3,833,g81. Such a product is unlike that depicted in Fig. 4 of Patent No. 3,837,981 ea~prising epoxy resin base and curing agent. The amount of polyamide 35 curing agent required for this purpose is not critical so long as the room tRImperature fast cure curing agent is protected from exposure to the atmosphere. This is generally accomplished by enveloping the putty-like room temperature, fast cure curing agent with a layer of 9Ç;9-'~
polyc~mQde curing agent from about 0.5 to 2 mm in thickness Any inert putty like material which is compatible with the epoxy resin may be useful in forming the protective envelope. The envelope can be applied by mutual extrusion of the room temperature fast cure curing 5 agent and polyc~lide or the curing agent could be placed in a molten polyamide resin bath from which a coating of the polyamide would adhere to the curing agent.
Fig. 2 illustrates an epoxy tape in which Band B contains the epoxy resin composition, band A contains the fast cure curing agent 10 and band C contains the polyamide resin curing composition which serves to protect the fast cure curing agent from atmospheric degradation. Alternative embodiments of the invention are depicted in Figs. 3, 4 and 5. Fig 4 depicts an alternative embodiment in which one strip (B) comprises the epoxy resin, while the other comprises the 15 room temperature fast cure curing agent (A) and the polyamide resin curing composition (C) which serves to protect the room temperature, fast cure curing agent from atmospheric degradation. In such form, the separate strips are carried on release paper or other carrier and packaged as a single unit.
Fig. 5 illustrates an embodiment in which curing agent A and epoxy resin s are each wrapped or enveloped by the polyamide curing composition C. This may be accomplished by extrusion of the materials, or, alternatively, bands A and B could be placed in a bath of molten polyamide curing composition from which the curing 25 composition C will adhere to bands A and s in the form depicted in Fig. 5. In this embodiment as well as those illustrated in the other figures, it will be appreciated that the curing composition C
functions in a manner analogous to a container, and is unique in this role, since it becomes part of and is consumed with use of the 30 adhesive sealant, and yet does not have to be removed or segregated from the adhesive-sealant prior to use.
Figs. 1 and 3 illustrate a method of sealing ends of the epoxy tape before and after removal of portions of the tape for use as an epoxy adhesive sealant so as to maintain the protective shield about 35 the air sensitive room temperature fast cure curing agent.
The room temperature curing agent, whether in the form of polyamide, polymercaptan and/or amino phenol, should be present in an amount sufficient to cross link from about 80 to about 120%, preferably I
about 100%, of the available cross-linking sites of the epoxy resin in the tape.
As mentioned, the epoxy resin and the curing agent therefore are admixed with various fillers, plasticizers, and colorants to form the 5 putty like compositions which are extruded into separate shapes or into an epoxy tape of the type described in Patent No. 3,837,981~
IJseful fillers for this purpose include talc, powdered alumina and asbestos fiber. Fillers such as these provide the epoxy resin and the curing agent compositions with physical properties and the putty-like 10 consistency necessary for extrusion into tape form. The fillers are incorporated into the epoxy resin and the curing agent compositions in amounts sufficient to produce a putty-like mass which can be easily extruded into the desired epoxy tape. Pc~7dered talc such as Mist Ron Vapor available cc~rnercially from United Sierra Division of Cypress 15 Mines Corporation, is an especially preferred filler, since it yields a handle able putty-like mass with both epoxy resins and the curing agent compositions Putty-like products prepared with this filler skew less tendency to stick to the hands than do compositions prepared with other fillers. Useful plasticizers include resinous polyols and 20 other agents which serve to yield a more flexible cured product.
A variety of coloring agents may be included in the epoxy or the curing agent compositions as desired. Useful coloring agents include pigments like titanium dioxide which provides a white color; carbon black or black color end various organic and inorganic pigments for 25 o'er colors It it desirable that the respective hands of epoxy resin and curing agent composition be of contrasting color to serve as an indicator of complete and thorough mixing.
rho use the room temperature, fast cure products of this invention, a portion of the tape comprising substantially equal 30 lengths of the epoxy resin band and the curing agent band is selected and the compositions are mixed together. The mixing may be acc~nplished by hand or with the aid of mechanical assistance. Mixing permits the components, i.e. the epoxy resin and the room temperature fast cure curing agent, to react and effect curing, in situ. Zen the 35 epoxy resin and the room temperature fast cure curing agent bands of the tape are of contrasting color, it is easy to determine when a uniform mixture has been obtained simply by continuing mixing until 9Çi the mixture has a uniform color. I-t will be appreciated that pigment may be included in one or both buds of the composition.
me overall extrusion process for preparing the products of this invention is analogous to that described in Patent No. 3,837,981. In 5 this process, the respective putty-like compositions may be extruded from three extrudes which lay down the respective bands illustrated in Figs. 2 and 4. After extrusion, any desired length of the tape may be simply rolled up and packaged in any desired manner. mere is no need for special packaging requirements to give a useful shelf life to 10 the tape. when the epoxy tape of this invention is used as an adhesive sealant, any desired quantity of the epoxy tape made of approximately equal lengths of each band in the tape are selected and kneaded together under ambient conditions forming a uniform mixture.
The resulting putty-like or dough-like epoxy adhesive sealant has a 15 relatively short pot life and must be applied rather promptly as substantial curing is effected at ambient temperatures within about ten minutes from the time when the epoxy resin composition and the room temperature fast cure curing composition are combined to form a substantially uniform mixture. mere must be some time after mixing 20 by hand in which the product remains workable for each application.
Accordingly, the product is formulated so that substantial curing to the point of unw~rkability by hand occurs within about 5 minutes from the time of mixing. mix point is characterized by a Dormitory hardness shore A) of 30. The product reaches a Shore A of 60 within 25 10 minutes from time of mixing, and thus is an extremely rapid, room temperature curing adhesive sealant.
The epoxy formed from the epoxy tape of this invention substantially cures within ten minutes or less from the time of initial mixing to a useful, tough, solid, epoxy adhesive. me epoxy 30 resin formed from the epoxy tape with this invention has excellent adhesive-sealant properties, and may be utilized to adhere ceramic, wood and metal and like materials to aluminum, concrete, steel, ceramic and like substances. The epoxy composition will cure under water making it useful in many marine environments. me invention may 35 be illustrated in the following example:
Lowe 471 parts of an epoxy resin Eon 828) having an epoxy equivalent weight of 185 to 192 are mixed with 525 pounds of powdered talc, Mist Ron Vapor by United Sierra Division of Cypress Mines Corporation, forming a highly viscous, smooth material.
A curing agent composition is prepared by mixing 17 parts of a semisolid polyamide resin having an amine value of 90 and a viscosity of 10 poises at 150C. (Versamid~ 100 of General Mills) with 30 parts of a liquid polyamide resin having an amine value of 200 to 300 (Assumed 215 of A Chemicals, Inc.), with 60 parts of powdered talc 10 list Ron Vapor ) in a sigma blade mixer maintained at a temperature not exceeding 120F. until a uniform mixture is formed. A third mixture is prepared by mixing 30 parts of a semisolid polyamide resin having an amine value of 90 and a viscosity of 10 poises at 150C.
(Versamid~ 100), with 48 parts of liquid polymercaptan polymer having 15 a mercaptan value of 3.6 milliequivalents per gram tcapcure~ of Diamond Shamrock), 8 parts of amino phenol DUMP 10 of Room & Hays) and 100 parts of powdered talc (Mist Ron Vapor ) in a able arm putty mixer maintained at a temperature not exceeding 120F. until a uniform mixture is formed. Substantially equal portions, by weight, of each 20 of the three mixtures are formed into slugs and fed separately into extrudes which simultaneously lay dawn bands of each mixture in the form depicted in the drawings. A room temperature fast curing epoxy adhesive is formed which will substantially cure to Shore A hardness of 30 within about 5 minutes after initial mixing.
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a putty-like epoxy adhesive sealant comprising a first band of an uncured reactive epoxy resin composition and a second band, said second band comprising a composition capable of curing said epoxy resin when said first and second bands are combined to form a substantially uniform mixture the improvement wherein said second band comprises an inner core of a fast cure curing agent capable of curing said uncured epoxy resin to a hard, adhesive sealant within about ten minutes from the time when said epoxy resin composition and said curing composition are combined to form a substantially uniform mixture, enveloped by an inert putty-like outer surrounding wrap of a composition capable of protecting said fast cure curing agent from premature reaction with the atmosphere and with said uncured epoxy resin.
2. The epoxy adhesive sealant of claim 1 wherein said curing agent is capable of curing said uncured epoxy resin to an adhesive sealant having a Shore A hardness of about 30 in about five minutes.
3. The epoxy adhesive sealant of claim 1 wherein said curing agent is capable of curing said uncured epoxy resin to an adhesive sealant having a Shore A hardness of about 60 in about ten minutes.
4. The epoxy adhesive sealant of claim 1 wherein said composition comprising the outer surrounding wrap enveloping said fast curing agent is capable of curing said epoxy resin when said fast cure curing agent and said curing agent are combined with said epoxy resin to form a substantially uniform mixture.
1?
1?
5. The epoxy adhesive sealant of claim 1 wherein said curing agent band is capable of curing said uncured epoxy resin to a hard, adhesive sealant within from about 5 to about 10 minutes from the time when said epoxy resin composition and said curing composition are combined to form a substantially uniform mixture.
6. the epoxy adhesive sealant of claim 1 wherein said fast cure curing and said epoxy resin are enveloped by an outer surrounding wrap of a composition capable of protecting said fast cure curing agent and epoxy resin from premature reaction with the atmosphere and one another.
7. The epoxy adhesive sealant of claim 1 wherein the fast-cure curing agent comprises a polymercaptan having a mercaptan value of 1 to 20.
8. The epoxy adhesive sealant of claim 7 wherein the fast-cure curing agent includes an amino-phenol in a weight ratio to the polymercaptan of from 1:5 to 1:20.
9. The epoxy adhesive sealant of claim 1 wherein the fast-cure curing agent is used in conjunction with one or more polyamide resins in a weight ratio of from 1:1 to 2:1.
10. The epoxy adhesive sealant of claim 1 wherein the outer surrounding wrap comprises a polyamide curing agent for the epoxy resin and has a thickness of from 0.5 to 2 mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US24700181A | 1981-03-24 | 1981-03-24 | |
| US247,001 | 1981-03-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229696A true CA1229696A (en) | 1987-11-24 |
Family
ID=22933114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000398831A Expired CA1229696A (en) | 1981-03-24 | 1982-03-19 | Rapid cure epoxy adhesive sealant |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS57202367A (en) |
| CA (1) | CA1229696A (en) |
| DE (1) | DE3210608A1 (en) |
| GB (1) | GB2097401B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10633153B2 (en) | 2014-02-25 | 2020-04-28 | Henkel Ag & Co. Kgaa | Administration unit for composition |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8305313D0 (en) * | 1983-02-25 | 1983-03-30 | Raychem Ltd | Curable fabric |
| GB8305309D0 (en) * | 1983-02-25 | 1983-03-30 | Raychem Ltd | Fabric member |
| GB8305312D0 (en) * | 1983-02-25 | 1983-03-30 | Raychem Ltd | Curable sheet |
| JPH07108970B2 (en) * | 1990-03-07 | 1995-11-22 | 和義 植松 | Sealant for oil leakage prevention of transformers and oil leakage prevention method |
| DE69206999T2 (en) * | 1991-09-11 | 1996-05-23 | Minnesota Mining & Mfg | Adhesive film |
| DE4438577A1 (en) | 1994-10-28 | 1996-05-02 | Basf Ag | Self-supporting dowel compound for chemical fastening technology |
| JP4627834B2 (en) * | 2000-02-23 | 2011-02-09 | 株式会社アルテコ | Reactive putty covering |
| DE10026649A1 (en) * | 2000-05-29 | 2001-12-13 | Siemens Ag | Repairing metal linings of containers, e.g. storage tanks for fuel elements in nuclear power stations, involves covering the damaged area and-or weld-seam with an adhesive |
| KR101952462B1 (en) * | 2010-12-29 | 2019-02-26 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Structural hybrid adhesives |
| GB201717562D0 (en) * | 2017-10-25 | 2017-12-06 | Whitfield Corp | Sealant composition |
| US20230054693A1 (en) * | 2021-08-19 | 2023-02-23 | TE Connectivity Services Gmbh | Thermoset Sealant Film |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5226536A (en) * | 1975-08-25 | 1977-02-28 | Taoka Chem Co Ltd | Adhesive composition |
| JPS52111958A (en) * | 1976-03-16 | 1977-09-20 | Kubota Ltd | Putty-like epoxy adhesives |
| JPS5910689B2 (en) * | 1978-11-09 | 1984-03-10 | 日東電工株式会社 | Epoxy resin putty |
-
1982
- 1982-03-19 CA CA000398831A patent/CA1229696A/en not_active Expired
- 1982-03-23 GB GB8208441A patent/GB2097401B/en not_active Expired
- 1982-03-23 DE DE19823210608 patent/DE3210608A1/en not_active Withdrawn
- 1982-03-24 JP JP57045769A patent/JPS57202367A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10633153B2 (en) | 2014-02-25 | 2020-04-28 | Henkel Ag & Co. Kgaa | Administration unit for composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0257592B2 (en) | 1990-12-05 |
| DE3210608A1 (en) | 1982-11-04 |
| GB2097401A (en) | 1982-11-03 |
| JPS57202367A (en) | 1982-12-11 |
| GB2097401B (en) | 1985-01-23 |
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