WO2005030894A2 - Adhesive compositions - Google Patents
Adhesive compositions Download PDFInfo
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- WO2005030894A2 WO2005030894A2 PCT/US2004/031133 US2004031133W WO2005030894A2 WO 2005030894 A2 WO2005030894 A2 WO 2005030894A2 US 2004031133 W US2004031133 W US 2004031133W WO 2005030894 A2 WO2005030894 A2 WO 2005030894A2
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- Prior art keywords
- adhesive composition
- composition
- epoxy
- acrylate
- reactive
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Classifications
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/105—Esters of polyhydric alcohols or polyhydric phenols of pentaalcohols
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/04—Epoxynovolacs
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
Definitions
- the present invention relates to curable adhesive compositions. More specifically, the invention relates to curable adhesive compositions that are particularly well adapted for anchoring materials in or to concrete or masonry.
- certain aspects of the invention relate to epoxy-based systems and methods for anchoring materials in or to concrete or masonry, while others relate to curable epoxy adhesive compositions, while still others relate to the bonded structures produced using such compositions and/or methods.
- anchor bolts are employed in various fields of engineering and construction as strengthening or reinforcing members in rock formations, or concrete or masonry structural bodies.
- the bolts which are typically metallic, are inserted into holes, gaps or openings in the rock formations, or concrete or masonry structural bodies, and are fixed or anchored therein by means of an anchor composition.
- Objects that have been attached to concrete or masonry using anchor bolts include, but are not limited to, electrical conduits, panels, piping and wall sections.
- Adhesive anchors are preferred over mechanical anchors for anchoring in soft concrete or masonry because, among other reasons, adhesive anchors place less stress on the concrete or masonry.
- the term "masonry” shall include, but is not limited to, stone, brick, ceramic tile, cement tile, hollow concrete block and solid concrete block.
- the anchor composition cures or hardens (polymerizes) to form a strong bond between the rock formation, or the concrete or masonry structural body, and the bolt. It has been known to use curable synthetic resins as the primary adhesive for the safe fastening of anchoring rods, bolts and similar devices in solid rock, masonry, concrete and the like. Typically, but not exclusively, certain of the starting components of the adhesive composition are kept separate from one another and then combined at or near the point of fastening.
- a useful anchor composition should provide a strong bond between the concrete or masonry and the material to be anchored to the concrete or masonry, be easy to dispense at the location of use, and is preferably not noxious or offensive to the user. It is also preferred in certain embodiments that the adhesive is capable of achieving a substantial portion of its ultimate strength in a relatively short period of time.
- curable adhesive compositions currently used in the industry, and in particular the field of anchoring in or to concrete, rock, and like materials, are based on compounds that are polymerized or cured by condensation and/or ring-chain conversion polymerization of monomers, oligomers, prepolymers and like compounds that have at least one functional group, typically at least one functional group along the polymer backbone, such as hydroxyl groups, and at least one terminal functional group, such as oxide groups.
- epoxy- based adhesive compositions are typically cured by one or more of these mechanisms.
- the epoxy resin and a curing or hardening agent are typically mixed immediately prior to use, and cure within a certain amount of time.
- the incorporation of reactive multi-functional acrylate into adhesive compositions according to the present invention is capable of enhancing the bonding strength of the adhesive, particularly at relatively high temperatures, such as at about 80°C.
- the present invention provides an adhesive that is relatively odorless, is readily injectable at relatively low temperatures, such as at about 5°C, and has a relatively fast cure time.
- the epoxy of the present composition preferably comprises an epoxy containing at least one cyclic group, such as a novalac epoxy.
- the composition further comprises at least one amine curing agent.
- compositions comprise an novalac epoxy and at least one amine curing agent, with the amine preferably also containing a cyclic group, even more preferably an amine containing a C4 - C8 cyclic group.
- the reactive multi-functional acrylate accelerator of the present invention may be used to best advantage in adhesives based on condensation and/or ring-chain conversion polymerization, it is believed that use of the reactive multi-functional acrylate may also provide substantial benefit to adhesives generally, including those adhesives which undergo free radical vinyl addition polymerization, acid catalyzed vinyl addition polymerization, base catalyzed vinyl addition polymerization, and combinations of two or more of any of these forms of polymerization.
- the present invention provides epoxy-based adhesive compositions, systems and methods that utilize at least one reactive multi-functional acrylate accelerator.
- reactive multifunctional acrylate refers to compounds that have at least two acrylate functionalities that are reactive, under the conditions used to cure the adhesive, with at least one of the compounds involved in the curing reaction or formed by the curing reaction.
- R may be any group which does not substantially interfere with or prevent reaction of the multifunctional acrylate compound with the polymerizable resin.
- R is independently H or a substituted or unsubstituted alkyl, aryl, oxyalkyl, arylalkyl, or oxyalkylaryl.
- each R is H.
- the preferred epoxy-based adhesive compositions of the present invention have a cure time of about three (3) hours or less and achieve a 24 hour no-torque pull-out strength of at least about 85 KN at about 72 °F.
- curable time refers to the time it takes from the initiation of curing reaction for the curable adhesive composition to achieve about 80% of its ultimate load capacity or strength under substantially dry conditions, with ambient temperature at about 72°F.
- no torque pull-out strength refers to the pullout strength of the adhesive measured at a time and under conditions in which there has been no substantial preceding torque applied to the bolt being tested.
- the preferred compositions of the present invention also achieve a 24 hour torqued pullout strength of at least about 50 KN at about 72 °F.
- room temperature is used herein to refer to a temperature of 72 °F.
- the term "torqued pull-out strength" refers to the pullout strength of the adhesive measured at a time, which is subsequent to the application of sufficient torque to begin turning of the bolt within the hole.
- the preferred compositions of the present invention also achieve a 1-hour torque resistance of at least about 15 N-m at about 72°F. The techniques used for measuring pullout force and torque resistance are described in the Experimental Protocol section hereof.
- the present compositions and systems also preferably are substantially free of offensive odors, as would be produced by the presence of substantial amounts of mercaptans in the formulation.
- the present invention provides a composition, preferably for use in systems and methods for anchoring materials in or to concrete or masonry, that comprises a first composition and a second composition that are brought together at or about the time of use.
- the first composition comprises a resin component, preferably at least one epoxy resin, and at least one reactive multi-functional acrylate accelerator
- the second composition includes a hardening or curing agent, said hardening or curing agent preferably comprising at least one amine-curing agent.
- the first and second compositions are brought into intimate contact to form a curable adhesive composition.
- Applicants have found that exceptional results can be achieved in accordance with the present invention by use of the present reactive multifunctional acrylate with polymerizable resins comprising, and preferably consisting essentially of, polymerizable epoxy compounds, optionally but preferably in combination with a select reactive diluent for the polymerizable epoxy compound.
- the reactive diluent comprises one or more compounds which have at least one oxide ring reactive with the polymerizable epoxy and which are compatible with the reactive multifunctional acrylate.
- the reactive diluent comprises a diglycidal ether.
- the reactive diluent of the present invention may or may not constitute an epoxy compound in accordance with the present invention. It is sometimes common practice to refer to such a combination of polymerizable polymer and reactive diluent as a "resin,” and such terminology will sometimes be used herein to refer to such combinations. It is contemplated that the relative amounts of the components in the present compositions can vary widely depending on the particulars of the contemplated use, and all such variety is within the scope hereof.
- multi-functional acrylate compound(s) are present in the adhesive compositions in amounts of from about 5 wt% to about 25 wt%, more preferably from about 8 wt% to about 20 wt%, and even more preferably from about 10 wt% to about 15 wt%.
- multi-functional acrylate compound(s) are present in the adhesive compositions in amounts of from about 14 wt% to about 18 wt%. Applicants have found that at least in certain cases it may be beneficial to consider the amount of the multifunctional acrylate used relative to the active components in the formulation.
- the multi-functional acrylate compound(s) are present in the adhesive composition in amounts of from about 5 pbwa to about 25 pbwa, more preferably about 10 pbwa to about 20 pbwa and even more preferably from about 15 pbwa to about 20 pbwa.
- pbwa as used herein means "part by weight based on active components.”
- active components refers to those components of the composition which participate in the curing of the composition, either directly as a reactant or indirectly as a catalyst, curing agent, accelerator, inhibitor and the like.
- the weight percentages and pbwa of the components in the present adhesive compositions as specified herein refer to the composition after it has been formulated for use in bonding.
- the percentages and pbwa values refer to the adhesive composition based on the combination of parts A and B of such compositions, unless otherwise specifically noted.
- the multi-functional acrylate compound(s) are present in the adhesive composition in amounts of from about 15 pbwa to about 25 pbwa.
- the resin component, and particularly the polymerizable epoxy compound(s) plus any reactive diluent is preferably present in the adhesive compositions of the present invention in amounts of from about 15 wt% to about 50 wt%, more preferably from about 25 wt% to about 45 wt%, and even more preferably from about 25 wt% to about 40 wt%, particularly when such resin includes a reactive diluent, preferably a diglycidyl ether.
- trie resin component, and particularly the polymerizable epoxy compound(s) plus any reactive diluent is present in the adhesive compositions of the present invention in amounts of from about 25 wt% to about 35 wt%.
- the present composites have an epoxy: reactive diluent weight ratio of from about 5:1 to about 30:1 , more preferably from about 5:1 to about 20:1 , and even more preferably from about 10:1 to about 15:1.
- an epoxy: acrylate weight ratio of from about 1.2:1 to about 5:1 , more preferably from about 1.3:1 to about 4.3:1 , and even more preferably from about 2:1 to about 3:1.
- the curable composition may be dispensed using various methods known to those skilled in the art.
- the composition may be dispensed using a dual cartridge device similar to a caulk gun, or the composition may be dispensed using a glass or film capsule.
- the composition may also be dispensed in bulk from bulk containers using meter-mix equipment, which is known to those skilled in the art. See, for example, U.S. Pat. Nos. 4,651 ,875, 4,706,806 and 4,729,696, the disclosures of which are hereby incorporated by reference. It is recognized that the amounts of the various components of the composition may vary depending on the type of dispensing system used.
- the curable composition is foi med by the mixing of a first composition and a second composition. Typically, the mixing occurs immediately before the curable composition is to be used.
- the first composition and the second composition which are contained in separate cartridges of the dispensing gun, may be mixed as they are ejected from the cartridges and applied to the surfaces to be bonded, such as to either the concrete or masonry and/or the anchoring device in the case of anchor compositions.
- the capsule is typically comprised of two chambers that contain the first composition and the second composition respectively. When the glass capsule is crushed, the two chambers are crushed and the contents are allowed to mix, forming the anchor composition.
- the epoxy-based adhesives of the present invention comprise epoxy and amine-based curing or hardening agent for the epoxy.
- curing agent refers to one or more components which are capable of catalyzing and/or accelerating the polymerization and/or crosslinking reaction of the resin component, which in preferred embodiments comprises one or more epoxy compounds. It is contemplated that the relative proportion of epoxy to amine in the curable composition may vary widely within the scope hereof in order to accommodate the needs and requirements of any particular application.
- the reactive compositions of the present invention have a epoxy:am'ne weight ratio of from about 0.3:1 to about 4:1 , more preferably from about 0.5: i to about 2:1 and even more preferably from about 1 :1 to about 2:1. In certain preferred embodiments, the reactive compositions of the present invention have an epoxy:amine weight ratio of from about 1 :1 to about 1.5:1
- epoxy compound refers to a compound or combination of two or more compounds that contain a reactive epoxy group or oxirane ring.
- materials broadly called epoxides, include monomeric epoxy compounds and epoxides of the polymeric type and can be aliphatic, cycloaliphatic, aromatic or heterocyclic. These materials preferably have, on the average, at least 1.5 polymerizable epoxy groups per molecule, and even more preferably two or more epoxy groups per molecule.
- the polymeric epoxides include linear polymers having terminal epoxy groups (e.g., a diglycidyl ether of a polyoxyalkylene glycol), polymers having skeletal oxirane units (e.g., polybutadiene polyepoxide), and polymers having pendent epoxy groups (e.g., a glycidyl methacrylate polymer or copolymer).
- the epoxides may be pure compounds but are generally mixtures containing one, two, or more epoxy groups per molecule. The "average" number of epoxy groups per molecule is determined by dividing the total number of epoxy groups in the epoxy-containing material by the total number of epoxy molecules present.
- the epoxy-containing materials may vary from low molecular weight monomeric materials to high molecular weight polymers and may vary greatly in the nature of their backbone and substituent groups.
- the backbone may be of any type and substituent groups thereon can be any group free of an v active hydrogen atom, which is reactive with an oxirane ring at room temperature.
- Illustrative of permissible substituent groups include halogens, ester groups, ethers, sulfonate groups, siloxane groups, nitro groups, phosphate groups, etc.
- the molecular weight of the epoxy-containing materials may vary widely, including in preferred embodiments from about 50 to 100,000 or more. Mixtures of various epoxy-containing materials can also be used in the compositions of this invention.
- the epoxy compounds of the present invention may be cycloaliphatic epoxides.
- cycloaiiphatic epoxides include diepoxides of cycloaliphatic esters of dicarboxylic acids such as bis(3,4-epoxycyclohexylmethyl)oxalate, bis8(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6- methylcyclohexylmethyl)adipate, bis(3,4-epoxycyclohexylmethyl)pimelate, and the like.
- Other suitable diepoxides of cycloaliphatic esters of dicarboxylic acids are described in, for example, U.S. Pat. No.
- cycloaliphatic epoxides include 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexane carboxylates such as 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexane carboxylate; 3,4-epoxy-1 -methylcyclohexylmethyl-3,4-epoxy-1 - methylcyclohexane carboxylate; 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4- epoxycyclohexane carboxylate; 3,4-epoxy-2-88methylcyclohexylmethyl-3,4-epoxy- 2-methylcyclohexane carboxylate; 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy- 3-methylcyclohexane carboxylate; 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy
- epoxy compounds which are readily available include epoxy novalacs, diglyidyl ethers of bisphenol F, octadecylene oxide, glycidylmethacrylate, diglycidyl ether of bisphenol A (e.g., those available under the trade designations EPON 828, EPON 1004 and EPON 1010 from Shell Chemical Co., DER-331 , DER-332, and DER-334, from Dow Chemical Co.), vinylcyclohexene dioxide (e.g., ERL-4206 from Union Carbide Corp.), 3,4- epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (e.g., ERL-4221 from Union Carbide Corp.), 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6 ⁇ methylcyclohexene carboxylate (e.g., ERL-4201 from Unio2n Carbide Corp.), bis(3,4-ep
- ERL-4289 from Union Carbide Corp.
- bis(2,3-epoxycyclopentyl) ether e.g., ERL-0400 from Union Carbide Corp.
- aliphatic epoxy modified with polypropylene glycol e.g., ERL-4050 and ERL-4052 from Union Carbide Corp.
- dipentene dioxide e.g., ERL-4269 from Union Carbide Corp.
- epoxidized polybutadiene e.g., OXIRON 2001 from FMC Corp.
- silicone resin containing epoxy functionality flame retardant epoxy resins (e.g., DER-580, a brominated bisphenol type epoxy resin available from Dow Chemical Co.), 1 ,4-butanediol diglycidyl ether of phenolformaldehyde novolak (e.g., DEN-431 and DEN-438 from Dow Chemical Co.), and resorcinol diglycidyl ether (e.g., KOPO
- epoxy which comprises a combination of diglyidyl ethers of bisphenol F and diglyidyl ethers of bisphenol A (e.g., those available under the trade designation DER-352, from Dow Chemical Co.).
- epoxy novalac resins it is contemplated that a wide variety of such resins may be used in the adhesives of the present invention. In general, however, it is generally preferred that the epoxy novalac resins of the present invention have an average functionality of from about 2 to about 3, and even more preferably of about 2.5.
- Such resins also preferably have a weight per epoxide (WPE) as measured by ASTM D 1652 of from about 160 to about 190, more preferably of from about 165 to about 185, and even more preferably of from about 168 to about 178.
- WPE weight per epoxide
- Such resins also preferably have a viscosity at 25° C of from about 300 to about 550 poise, more preferably of from about 320 to about 500, and even more preferably of from about 345 to about 485.
- a preferred epoxy novalac resin is sold by Resolution Performance Products under the trade designation EPON 160.
- the use of epoxy resin, which comprises epoxy novalac is generally preferred when it is desirable for the adhesive composition to perform well, especially in terms of pull out force, at relatively high temperatures.
- the composition produce a pullout force of at least 50KN at about 80°C.
- the epoxy resin comprise from about 20 % by weight to about 60% by weight of epoxy novalac, more preferably from about 30 % to about 50% by weight of epoxy novalac, and even more preferably from about 35 % to about 45 % epoxy novalac.
- epoxy resins having a wide range of molecular weights and other characteristics are adaptable for use in accordance with the present invention. It is generally preferred, however, that the epoxy resins of the present invention possess an epoxy equivalent weight (EEW) of from about 180 to about 192.
- the epoxy resins have a viscosity of from about 6,000 to about 14,000 cps at about 25°C.
- the epoxy resins suitable for use in the present invention may thus comprise one or more compounds, such as epoxy prepolymers, having more than one epoxide group per molecule available for reaction with the curing agent of the present invention.
- Such epoxy prepolymers include but are not limited to polyglycidyl ethers of polyvalent phenols, for example pyrocatechol, resorcinol, hydroquinone; 4,4'-dihydroxydiphenyl methane; 4,4'-dihydroxy-3-3'- dimethyldiphenyl methane; 4,4'-dihydroxydiphenyl dimethyl methane; 4,4'dihydroxydiphenyl methyl methane; 4,4'-dihydroxydiphenyl cyclohexane; 4,4'- dihydroxy-3,3'-dimethyldiphenyl propane; 4,4'-dihydroxydiphenyl sulfone; or tris-(4- hydroxyphenyl)methane; polyglycidyl ethers of novalacs (i.e., reaction products of monohydric or polyhydric phenols with aldehydes, formaldehyde in particular, in the presence of acid catalysts); polyglycidyl ether
- epoxy-containing materials which are particularly useful in the practice of this invention, particularly as reactive diluent for the epoxy portion of the resin, include glycidyl ether monomers as disclosed in U.S. Patent No. 5,385,990, which is incorporated herein by reference. It is contemplated that one or more epoxy compounds as described above are readily adaptable for use within the scope of the present invention.
- the epoxy compound comprises in major proportion, and even more preferably is comprised of at least about 80% by weight of difunctional bisphenol A/epichlorohydrin derived liquid epoxy resin having a epoxide equivalent weight of from about 180 to about 200, and even more preferably from about 185 to about 195.
- the epoxy compound comprises in major proportion, and even more preferably is comprised of at least about 80% by weight, and even more preferably consists essentially of a liquid epoxy formed by the reaction product of epichlorohydrin with bisphenol-A and bisphenol-F having a epoxide equivalent weight of from about 160 to about 200, and even more preferably from about 170 to about 185.
- epoxide equivalent weight means the grams of epoxy compound or resin containing one gram equivalent of epoxide, as determined by the Shell Analytical Method HC-427D-89 (perchloric acid method).
- Certain preferred epoxies also preferably have a viscosity at 25°C of from about 100 to about 175 poise, and even more preferably from about 110 to about 150 poise, as measured by Shell
- Analytical Method HC-397A-87 Such a preferred epoxy resin, which satisfies these requirements is available from Shell Resins under the trade designation EPON Resin 828. Certain other preferred epoxies preferably have a viscosity at 25°C of from about 5000 to about 6000 mPa.s, and even more preferably from about 5400 to about 5900 mPa.s, as measured by ASTM D-445. Such a preferred epoxy resin, which satisfies these requirements is available from Dow Plastics under the trade designation D.E.R. 352. In preferred embodiments, reactive diluents are incorporated into the epoxy resin to, inter alia, control the flow characteristics of the adhesive composition.
- Suitable reactive diluents preferably have at least one reactive terminal end portion (including an epoxy group), and even more preferably also have a saturated or unsaturated cyclic backbone.
- Preferred reactive terminal ether portions include glycidyl ether and vinyl ether.
- Suitable reactive diluents include: 1 ,4-butanediol diglycidyl ether; 1 ,4- cyclohexane-dimethanol; the diglycidyl ether of resorcinol; diglycidyl ether of cyclohexane dimethanol; diglycidyl ether of neopentyl glycol; triglycidyl ether of trimethylolpropane dipentene; and the divinyl ether of cyclohexanedimethanol.
- reactive diluents include "WC-68" from Rhone Poulenc, Epodil 741 , 749 and 757 from Air Products and Chemicals Incorporated (Allentown, PA), Rapicure, a divinyl ether of cyclohexanedimethanol available from Allied-Signal Corp. of Morristown, N. J, and glycidyl neodeconate sold under the tradename CADURA E-10 by Shell Oil.
- Highly preferred for use in the epoxy resin as a reactive diluent is the 1 ,4-butanediol diglycidyl ether sold by Air Products under the trade designation Epodil 750.
- the epoxy comprises, and preferably consists essentially of, epoxy resin and reactive diluent.
- the epoxy resin: reactive diluent weight ratio is from about 11 :1 to about 13:1 , and even more preferably about 12:1.
- the epoxy resin comprises from about 90% by weight to about 98% by weight of epoxy and from about 2% by weight to about 10% by weigh of reactive diluent.
- the epoxy resin comprised about 93% by weight of epoxy (preferably EPON 828) and about 3% by weight of reactive diluent (preferably Epodil 750).
- the reactive multifunctional acrylate comprises, and preferably consists essentially of, multifunctional methacrylate compounds.
- the reactive multifunctional acrylate comprises at least one compound that is at least tri-functional, and in certain embodiments at least one compound that is at least tetra-functional, and ever more preferable a combination of at least one of each.
- the reactive multifunctional acrylate of the present invention may comprise a combination of two or more multi-functional acrylate compounds, with each independently having the same or different levels of functionality.
- the multifunctional acrylate consists essentially of compounds that are tri- and tetra- functional.
- a preferred tri-functional acrylate is trimethylolpropane triacrylate, which is sold under the trade designation SR-351 by Sartomer Company of Exton, PA, USA.
- a preferred penta-functional acrylate is dipentaerythritol pentaacrylate, which is sold under the trade designation SR-399 by Sartomer Company of Exton, PA, USA.
- Each of these preferred multi-functional acrylates includes inhibitor, particularly methyl hydroquinone, in a concentration of less than about 100 ppm based on the total weight of the acrylate and inhibitor.
- the reactive multifunctional acrylates of the present invention act to provide numerous and effective cross-linking sites for the adhesive composition as it cures, thus improving the density and other physical properties of the cured adhesive, such as pull out strength and fire resistance.
- the relative amount of the different types and functionalities of reactive multifunctional acrylate included in the present compositions may vary widely depending on numerous factors, such as for example the desired cure rate and strength, as well as the type and nature of the other components of the composition.
- the preferred embodiments of the present adhesive compositions comprise tri- and penta-functional acrylates in a tri:penta weight ratio of from 0.05:1 to about 1 :1 , more preferably from about 0.08:1 to about 0.5:1 , and even more preferably from about 0.1 :1 to about 0.4:1.
- the present invention can include any one of known and available curing agents, it is generally preferred that the curing agent compromise an amine-curing agent.
- the amine curing agent of the present invention may be any substance known as an amine-type curing agent for epoxy resins; it is generally preferred, however, that the curing agent comprise, and preferably consist essentially of, a mixture of aliphatic amines.
- the amine(s) include, on average, greater than two hydrogen atoms active towards the epoxide resin.
- the amines can contain one or more primary, secondary or tertiary nitrogen atoms.
- Suitable amines are aliphatic, cycloaliphatic, aromatic and heterocyclic amines, such as bis-(4-aminophenyl)-methane, aniline/formaldehyde resins, benzylamine, octylamine, propane-1 ,3-diamine, 2,2-dimethyl-1 ,3- propanediamine (neopentanediamine), hexamethylenediamine, diethylenetriamine, bis(3-aminopropyl)-amine, N,N-bis(3-aminopropyl)-methylamine, triethylenetetraamine, tetraethylenepentaamine, pentaethylenehexaamine, 2,2,4- trimethylhexane-1 ,6-diamine, m-xylylenediamine, 1 ,2-and 1 ,4-diaminocyclohexane, bis-(4-aminocyclohexyl)-methane, bis-(4
- Mannich base is the aliphatic Mannich base made by Air Products under the trade designation Ancamine 1856.
- Another type of preferred amines are the adduct modified aliphatic amines, with three such amines being available from Air Products under the trade designations Ancamine 1768, Ancamine 1638 and Ancamine 2089M.
- Suitable amines also include the polyoxyalkyleneamines, known as Jeffamines, made by Hunstman Chemical, for example the Jeffamines EDR 148, D 230, D 400, or T 403, xylene diamine and bis(aminocyclohexyl) methane.
- cycloaliphatic amines methylene- di(cyclohexyl) amine (also known as PACM), 3-aminomethyl-3,5,5 - trimethyl- cyclohexylamine (alternatively 5-amino-1 ,3,3 - trimethyl-cyclohexanemethylamine) (also known as isophoronediamine or IPDA) are preferred.
- Other curing agents include, for example, polyamines and polyamide curing agents.
- the curing agent comprises at lease one Mannich amine and at least one adduct modified amine.
- the Mannich:adduct modified amine are present in a weight ratio of from about 0.5:1 to about 3:1 , more preferably from about 0.5:1 to about 2:1 , and even more preferably from about 1 :1 to about 2:1.
- the aliphatic amine compound(s) have a glass transition temperature, when cured with an epoxy, of from about 125°F to about 140°F, and even more preferably from about 125°F to about 135°F, and an amine value of at least about 350 mg KOH/g, more preferably of from about 350 mg KOH/g to about 1500 mg KOH/g.
- a combination of at least two amine compounds wherein a first of said compounds has an amine value of from about 800 to about 1500 mg KOH/g and at least a second amine compound has an amine value of from about 350 to about 800 mg KOH/g, and even more preferably from about 380 mg KOH/g to about 550 mg KOH/g.
- the "glass transition temperature” refers to the property as measured by ASTM D3418-82. It is contemplated that the amine-curing agent may be present in a wide variety of concentration ranges within the broad scope of the present invention.
- the present compositions comprise from about 10 wt% to about 55 wt% of amine curing agent, more preferably from about 10 wt% to about 40 wt% and even more preferably from about 10 wt% to about 30 wt%.
- the amine curing agent is present in the adhesive compositions in amounts of from about 20 pbwa to about 70 pbwa, and even more preferably from about 25 pbwa to about 40 pbwa.
- the use of curing agent, which comprises one or more cycloaliphatic amines is generally preferred when it is desirable for the adhesive composition to perform well, especially in terms of pull out force, at relatively high temperatures.
- the composition produce a pull out force of at least 50KN at about 80°C.
- the curing agent comprise from about 25 % by weight to about 50% by weight of cycloaliphatic amines, more preferably from about 30 % to about 40% by weight of cycloaliphatic amines, and even more preferably about 35 % cycloaliphatic amines.
- a preferred free-radical inhibitor is hydroquinone.
- suitable free- radical inhibitors include, but are not limited to, trimethylhydroquinone, hydroquinone monomethyl ether, t-butyl catechol and naphthaquinone. It is also contemplated that more than one free radical inhibitor may be employed in the anchor composition.
- the polymerization inhibitor preferably comprises, more preferably comprises in major proportion, and even more preferably consists essentially of hydroquinone.
- inhibitors may be used alone or in combination with hyrdoquinone, such as for example, parabenzoquinone, methylhydroquinone, catechol and the like which are conventionally employed as polymerization inhibitors. While it is contemplated that the amount of inhibitor in the composition may vary widely depending on numerous factors particular to each application and contemplated use, it is generally preferred that the inhibitor is present in amounts of from about 0.005 wt% to about 0.5 wt%, and even more preferably from about 0.01 t% to about 0.1 wt%.
- the resin composition of this invention can be more easily cured by adding a curing catalyst, an initiator, or both.
- Representative initiators include aldehyde-amine condensation product, organic sulfonyl chlorides and tertiary amines, with tertiary amines being generally preferred.
- the initiator comprises an amino substituted phenol, more preferably a tertiary amino substituted phenol, and even more preferably a phenol having at least two and preferably three tertiary amine substituents.
- One preferred tertiary amine is 2,4,6-tris(dimethylaminomethy!) phenol available from Air Products under the trade designation ANCAMINE K54.
- activating agents can be used in combination in accordance with the present invention.
- suitable activators are tertiary amines such as N,N- dimethyl aniline, N,N-dimethyl toluidine, N,N-diethylaniline, N,N-diethyl toluidine, N,N-di -(2-hydroxy-ethy)- p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N- bis(hydroxypropyl)-p-toluidine and the like.
- the curing catalysts may in certain embodiments also include organic peroxides such as methylethylketone peroxides, t-butyl peroxybenzoates, benzoyl peroxides, dicumyl peroxides and the like.
- organic peroxides such as methylethylketone peroxides, t-butyl peroxybenzoates, benzoyl peroxides, dicumyl peroxides and the like.
- THIXOTROPTIC AGENTS The present anchor composition may also comprise a thixotropic agent.
- the preferred thixotropic agent of the present invention causes the composition to become more fluid, i.e. less viscous, when agitated, stirred or mixed or otherwise subjected to such shear forces. It is useful to include a thixotropic agent in the anchor composition to insure that the composition has the desired viscosity during application and after the composition is applied.
- thixotropic agent may be added to inhibit or prevent slump or sag of the composition when the application may require injecting the composition into a horizontal hole or a hole in the ceiling.
- a thixotropic agent may be added to an anchor composition to prevent the settling of other solid components of the composition and to increase the viscosity of the composition.
- the thixotropic agent also facilitates dispensing of the composition because when a shear force is applied, e.g. expulsion of the composition from a dispensing gun, the thixotropic agent makes the resulting composition less viscous, and therefore, more easy to expel from the cartridges of the dispensing gun.
- the thixotropic agent may be found in I the anchor composition in an amount in the range of from about 0.5 wt% to about 10 wt%, and more preferably from about 1 wt% to about 5 wt%.
- the use of thixotropic agent is not needed when the anchor composition is dispensed using a glass capsule.
- An example of a suitable preferred thixotropic agent is fumed silica.
- the various silicas made by the various methods known in the art, including pyrolysis of silicon tetrachloride and precipitation.
- Other suitable thixotropic agents include the various organoclays and various fibers.
- the thixotropic agent may also be considered a filler.
- a suitable silica thixotropic agent is Aerosil.RTM R202, which may be obtained from the Degussa Corporation of Ridgefield Park, N.J. It is also contemplated that more than one thixotropic agent may be used in the anchor composition FILLERS
- the anchor composition of the present invention also preferably comprises one or more fillers. Fillers are typically added to compositions for various reasons, including to reduce shrinkage of the composition that may occur during polymerization and to reduce the cost of the composition, as fillers replace a portion of the more expensive components of the anchor composition. The filler may also provide for improved bond strength of the anchor composition when polymerized and help to prevent the settling out of other particulate materials in the composition.
- the filler is an inert, inorganic, solid, particulate compound.
- inert it is meant that the filler does not detrimentally interact with any other component of the composition.
- suitable fillers include, but are not limited to, crushed glass, glass beads, quartz, silica, limestone, alumina, various clays, diatomaceous earth and other materials such as mica, flint powder, kryolite, alumina trihydrate, talc, sand, pyrophyllite, blanc fixe, granulated polymers such as polyethylene, hollow glass and polymer beads, zinc oxide, novaculite, calcium sulfate and mixtures thereof.
- Preferred fillers are quartz, glass and silica. Fillers may be treated with coupling agents to improve bonding to the polymer matrix. Examples of coupling agents, which may be used to treat the fillers are silanes, titanates and zirconates. Preferably, the present compositions contain fillers an amount of from about
- filler 10% to about 80% by weight of the composition, more preferably from about 20 wt% to about 70 wt%, and even more preferably from about 20 wt% to about 50 wt%.
- the exact particle size of the filler will depend on the desired consistency of the composition and the method for dispensing the anchor composition. For example, fillers having a large average particle size (300 microns and larger) may clog static mixers that are used in dispensing systems such as dispensing guns. On the other hand, fillers having a large particle size can be used in glass capsules. Preferred particle sizes are about 50 microns or larger.
- a particle size smaller than 50 microns may be desired. It is also recognized that filler having a particle size less than 50 microns may be used in combination with other fillers, some having particle sizes greater than 50 microns.
- the anchor composition may also contain a fragrance.
- a fragrance is used in an anchoring composition to mask any odor of the composition that is thought undesirable or unpleasant.
- a preferred fragrance is Atlanta Fragrance 16332.
- a pigment may be employed to color the anchoring composition. Suitable pigments are known to those skilled in the art.
- the anchor composition is formed by mixing a first composition and a second composition.
- the first ' composition contains the epoxy compound and preferably also at least a substantial amount, and preferably substantially all of the reactive diluent if present.
- the first composition also preferably contains the multifunctional acrylate, which itself preferably contains an inhibitor to inhibit curing of the adhesive until desired, the second composition preferably contains an amine catalyst.
- the first composition comprises epoxy resin, multifunctional acrylate accelerator and filler.
- the first composition may also comprise a thixotropic agent, a chain transfer agent, a free-radical inhibitor, a fragrance, an activator, a promoter and/or a pigment.
- the second composition may also include a filler, a thixotropic agent, a fragrance, and/or a pigment. It is also contemplated that both the first composition and the second composition may contain some of the same components.
- the weight ratio of the first composition to the second composition may be in the range of 0.5 to 1 to about 2 to 1. Preferably, the weight ratio of the first composition (Part A) to the second composition (Part B) is about 1.5 to 1.
- Preparation of Two Part Anchor Compositions The appropriate amounts of polymerizable epoxy resin are prepared. To the resin is add the appropriate amount of multifunctional acrylate, reactive diluent and other ingredients. The composition is mixed, preferably using a dispenser. Next, the thixotropic agent is added with shear mixing followed by addition of the filler. If more than one filler is to be included in the anchor composition, it is preferable to add the first filler, then mixed, then added to the second filler and so on until the desired number of fillers have been added to the composition until Part A of the composition is complete. The same general procedure as described above is used to make Part B consisting of curing agent, thixotropic agent, activator filler, pigment and other ingredients.
- a medium weight concrete block approximately 4"X.8"X16" substantially free of surface moisture is used.
- five replicate pull out and torque resistance tests are run for each adhesive composition tested.
- First, three equally spaced 110 mm deep holes approximately 14 mm wide are drilled in the 8"x16" side of the concrete block. Then, the holes are cleaned with a brush, with compressed air and a vacuum.
- An adhesive composition is injected into the drilled holes, and a 1/4"-20 threads per inch.
- X 12mm stainless steel rod type 304 is inserted into the adhesive-containing hole with a twisting motion. The time before pull out and torque testing is in the range of about 0.5 hours to about 72 hours, as reported.
- the stainless steel rod is torqued, and the amount of torque required to begin rotation of the rod is recorded.
- torqued pull- out tests the stainless steel rod after the torque resistance is measured is then connected at the indicated time to a universal tester, such as an Instron universal tester, Model TTC, Instron Corporation, Canton, Mass. or its equivalent, and the rods are pulled at 0.27minute until failure. The maximum load and failure type was then recorded. Pullout tests which are not torqued are measured in the same manner, except the torquing operation is omitted.
- One measure of real word performance of anchor adhesives is the torqued pull out force of the adhesive.
- the preferred anchor compositions of the present invention provide a torque resistance at about 1 hour after application at about room temperature of at least about 15 N-m, and at torqued pullout performance about 24 hours at about room temperature of at least about 65 KN.
- the material that has been anchored to the concrete or masonry, or the concrete or masonry itself fails before the adhesive composition.
- the compositions of the present invention are capable of achieving a torque resistance at one hour at room temperature of at least about 15 N-m, and a pull out performance (without torquing) at about 24 hours at about room temperature of at least about 90 KN and at about 24 hours at about 80°C of at least about 45 KN.
- Adhesive RE-500 Torque Resistance 1 Hr. (N-m) 0 Pullout, 5 Hr. (no torque) (KN) 47 Pullout, 6 Hr. (no torque) (KN) 84 Pullout, 24 Hr.(no torque) (KN) 90
- EXAMPLE 1 A two part adhesive composition having a Part A: Part B weight ratio of 1.5:1 and the following formulations for Part A and Part B is prepared and used according to the above protocols:
- Epoxy resin (Epon 828) 59.21 27.33 48.96
- ANCK54 4.67 1.44 2.57
- the present composition is capable of producing its maximum strength of about 100 KN approximately four hours after application, while a full five hours after application the prior art product is well below its maximum strength and substantially below the strength of the present composition. Moreover, the present composition is capable of generating significant torque resistance only 1 hour after application, while the prior art product produces no substantial torque resistance even after six hours.
- a two part adhesive composition having a Part Apart B weight ratio of 1.5:1 and the following formulations for Part A and Part B is prepared and used according to the above protocols:
- Epoxy resin (Epon 160) 25.68 12.02 9.55
- Pigment 0.0 0.0 0 includes 270 ppm me HQ ** includes 125 HQ and 175 me HQ
- the present composition is capable of producing a pull out force of 54 KN at about 80°C.
Abstract
Description
Claims
Priority Applications (6)
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EP04784824A EP1673411A4 (en) | 2003-09-26 | 2004-09-22 | Adhesive compositions |
CN2004800315839A CN1871299B (en) | 2003-09-26 | 2004-09-22 | Adhesive compositions |
JP2006528145A JP4805830B2 (en) | 2003-09-26 | 2004-09-22 | Adhesive composition |
CA2539937A CA2539937C (en) | 2003-09-26 | 2004-09-22 | Adhesive compositions |
NZ546208A NZ546208A (en) | 2003-09-26 | 2004-09-22 | Adhesive composition |
AU2004276280A AU2004276280B2 (en) | 2003-09-26 | 2004-09-22 | Adhesive compositions |
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US10/946,191 US7244793B2 (en) | 2003-09-26 | 2004-09-21 | Adhesive compositions |
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WO2005030894A2 true WO2005030894A2 (en) | 2005-04-07 |
WO2005030894A3 WO2005030894A3 (en) | 2005-09-09 |
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EP (2) | EP1673411A4 (en) |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101747882A (en) * | 2010-01-11 | 2010-06-23 | 中国石油大学(华东) | Tectorial membrane sand solidifying system suitable for low-temperature reservoir sand prevention |
US8058345B2 (en) | 2002-11-08 | 2011-11-15 | Illinois Tool Works Inc. | Curable adhesive compositions containing reactive multi-functional acrylate |
CN109536103A (en) * | 2018-11-21 | 2019-03-29 | 洛阳科博思新材料科技有限公司 | A kind of preparation method of the high-strength anchoring adhesive of chemical anchor bolts |
Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10357355A1 (en) * | 2003-12-09 | 2005-07-14 | Henkel Kgaa | 2 K adhesives for vehicle construction |
US8313604B2 (en) * | 2005-07-04 | 2012-11-20 | Denki Kagaku Kogyo Kabushiki Kaisha | Curable composition and temporary fixation method of member using it |
KR100830257B1 (en) | 2007-02-07 | 2008-05-16 | 주식회사 케이씨씨 | Epoxy resin composition for use of the storage tank of liquefied natural gas line |
TWI398482B (en) * | 2007-08-14 | 2013-06-11 | Swancor Ind Co Ltd | Epoxy Resin Formulations for Large Composites |
US20090048422A1 (en) * | 2007-08-14 | 2009-02-19 | Swancor Industrial Co., Ltd. | Resin composition for composite material parts |
CN101412896B (en) * | 2007-10-17 | 2012-07-25 | 比亚迪股份有限公司 | Bicomponent epoxy adhesive and preparation thereof |
CN101368078B (en) * | 2008-09-19 | 2011-12-07 | 航天材料及工艺研究所 | Adhesive for bonding and mending cork wood and formulation method thereof |
US8517641B2 (en) * | 2009-07-21 | 2013-08-27 | Illinois Tool Works Inc. | Anchoring adhesive combination and integrated method of applying it |
US9534076B2 (en) * | 2009-07-30 | 2017-01-03 | Illinois Tool Works Inc. | Flooring underlayments |
KR20130106281A (en) * | 2010-06-08 | 2013-09-27 | 헨켈 코포레이션 | Dual cure adhesives |
US9416300B2 (en) | 2011-01-16 | 2016-08-16 | Simpson Strong-Tie Company, Inc. | Low temperature curable adhesive compositions |
US8334346B2 (en) | 2011-01-16 | 2012-12-18 | Quentin Lewis Hibben | Low temperature curable adhesive compositions |
JP2013091774A (en) * | 2011-10-05 | 2013-05-16 | Canon Inc | Epoxy resin composition |
JP2013094992A (en) * | 2011-10-28 | 2013-05-20 | Canon Inc | Sealant for inkjet head |
CN102516922B (en) * | 2011-11-28 | 2014-01-08 | 中国铁道科学研究院金属及化学研究所 | Embedded sleeve anchoring adhesive, and preparation method and application thereof |
US20140302733A1 (en) * | 2013-04-09 | 2014-10-09 | The Boeing Company | Chemically Curable Bonding Film Adhesive with Uniform Thickness |
CN103254379B (en) * | 2013-05-17 | 2015-07-01 | 江苏文昌电子化工有限公司 | Phosphorus-containing/nitrogen-containing phenolic resin and preparation method thereof |
WO2015072800A1 (en) * | 2013-11-18 | 2015-05-21 | 삼성에스디아이 주식회사 | Adhesive composition for polarizing plate |
JP6265697B2 (en) | 2013-11-18 | 2018-01-24 | サムスン エスディアイ カンパニー,リミテッドSamsung Sdi Co.,Ltd. | Adhesive composition for polarizing plate |
CN104531029A (en) * | 2014-12-18 | 2015-04-22 | 烟台泰盛精化科技有限公司 | Chip four-corner binding glue and preparation method thereof |
KR101922043B1 (en) * | 2014-12-24 | 2019-02-14 | 주식회사 엘지화학 | Adhesive composition for double-sided adhesive tape, double-sided adhesive tape for touch screen panel and method of producing the same |
FR3084889B1 (en) * | 2018-08-08 | 2021-02-19 | Illinois Tool Works | TWO-COMPONENT ADHESIVE COMPOSITION BASED ON EPOXIDE RESIN |
KR20210127599A (en) * | 2019-02-14 | 2021-10-22 | 헌츠만 어드밴스드 머티리얼스 아메리카스 엘엘씨 | Low Density Epoxy Syntactic Structural Adhesives for Automotive Applications |
WO2021019741A1 (en) * | 2019-07-31 | 2021-02-04 | 昭和電工マテリアルズ株式会社 | Adhesive set |
CN112391138A (en) * | 2020-11-06 | 2021-02-23 | 福建省高镖建材有限公司 | Epoxy dry-hanging adhesive and preparation method thereof |
EP4119589A1 (en) | 2021-07-16 | 2023-01-18 | Hilti Aktiengesellschaft | Epoxy resin mixtures comprising epoxide-acrylate hybrid molecules and multicomponent reactive resin compositions therefrom |
EP4119594A1 (en) | 2021-07-16 | 2023-01-18 | Hilti Aktiengesellschaft | Acrylate-containing binders for fixing purposes |
EP4119590A1 (en) | 2021-07-16 | 2023-01-18 | Hilti Aktiengesellschaft | Epoxide-acrylate hybrid molecules and their use for chemical anchoring |
CN114231186B (en) * | 2021-12-15 | 2023-04-18 | 武汉市科达云石护理材料有限公司 | Fast-curing modified dry-hanging adhesive and preparation method and application thereof |
Family Cites Families (56)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2750395A (en) | 1954-01-05 | 1956-06-12 | Union Carbide & Carbon Corp | Diepoxides |
US2890194A (en) | 1956-05-24 | 1959-06-09 | Union Carbide Corp | Compositions of epoxides and polycarboxylic acid compounds |
US3066112A (en) * | 1959-01-30 | 1962-11-27 | Rafael L Bowen | Dental filling material comprising vinyl silane treated fused silica and a binder consisting of the reaction product of bis phenol and glycidyl acrylate |
US3317465A (en) * | 1963-06-26 | 1967-05-02 | Robertson Co H H | Combination catalyst-inhibitor for betahydroxy carboxylic esters |
US3377406A (en) * | 1963-12-16 | 1968-04-09 | Shell Oil Co | Process of esterification of polyepoxides with ethylenically unsaturated monocarboxylic acids in the presence of onium salts of inorganic acids |
US3345401A (en) * | 1964-10-19 | 1967-10-03 | Shell Oil Co | Process for preparing polyesters and resulting products |
US3373221A (en) * | 1964-11-04 | 1968-03-12 | Shell Oil Co | Reaction products of unsaturated esters of polyepoxides and unsaturated carboxylic acids, and polyisocyanates |
US3256226A (en) * | 1965-03-01 | 1966-06-14 | Robertson Co H H | Hydroxy polyether polyesters having terminal ethylenically unsaturated groups |
US3564074A (en) * | 1966-11-28 | 1971-02-16 | Dow Chemical Co | Thermosetting vinyl resins reacted with dicarboxylic acid anhydrides |
US3548030A (en) * | 1968-03-27 | 1970-12-15 | Dow Chemical Co | Vinyl ester resins containing esterified secondary hydroxy groups |
US3634542A (en) * | 1969-08-04 | 1972-01-11 | Shell Oil Co | Unsaturated polyesters esterified with polycarboxylic acid anhydride and containing polyepoxide |
US3637618A (en) * | 1970-03-11 | 1972-01-25 | Shell Oil Co | Unsaturated polyesters from epoxides and ethylenically unsaturated monocarboxylic acid mixed with solid epoxide resin |
US4051195A (en) * | 1975-12-15 | 1977-09-27 | Celanese Polymer Specialties Company | Polyepoxide-polyacrylate ester compositions |
LU82111A1 (en) * | 1980-01-25 | 1981-09-10 | Labofina Sa | SOLVENT-FREE COATING COMPOSITIONS |
JPS57100126A (en) * | 1980-12-15 | 1982-06-22 | Mitsubishi Petrochem Co Ltd | Curable resin composition |
US4536524A (en) | 1981-04-21 | 1985-08-20 | Capsulated Systems, Inc. | Microencapsulated epoxy adhesive system |
EP0066447A1 (en) * | 1981-05-25 | 1982-12-08 | Mitsubishi Gas Chemical Company, Inc. | Reaction of a phenol, aldehyde and amine to produce hardening agent for epoxy resins |
US4383090A (en) * | 1981-09-28 | 1983-05-10 | Diamond Shamrock Corporation | Polyepoxide curing by polymercaptans and a reaction product of amino acids or lactams with amines |
JPS6028478A (en) | 1983-07-27 | 1985-02-13 | Asahi Chem Ind Co Ltd | Bolt-setting fixing agent with high corrosion resistance |
DE3416094A1 (en) | 1984-04-30 | 1985-10-31 | Hilti Ag, Schaan | DESTROYABLE CARTRIDGE FOR MULTI-COMPONENT DIMENSIONS |
GB8419036D0 (en) * | 1984-07-26 | 1984-08-30 | Thiokol Chemicals Ltd | Liquid copolymers |
DE3442383A1 (en) | 1984-11-20 | 1986-06-19 | Hilti Ag, Schaan | DESTRUCTIBLE MOUNTING CARTRIDGE |
DE3617702C2 (en) | 1985-04-18 | 1997-04-10 | Hilti Ag | Use of curable acrylate derivatives as fixing mortar |
DE3514031A1 (en) | 1985-04-18 | 1986-10-23 | Hilti Ag, Schaan | ACRYLATE RESIN ADHESIVES AND THEIR USE FOR ANCHORINGS |
US4935454A (en) * | 1986-09-26 | 1990-06-19 | Amp Incorporated | Broad spectrum light and heat curable sealant composition and method of using same |
JPS6257430A (en) * | 1985-09-05 | 1987-03-13 | Asahi Chem Ind Co Ltd | Bonding of polyoxymethylene |
US4910269A (en) * | 1987-06-29 | 1990-03-20 | Texaco Chemical Co. | Polyether polyamine-piperazine cured cycloaliphatic epoxy resin compositions |
US4803232A (en) * | 1987-07-30 | 1989-02-07 | Lord Corporation | Rubber-modified epoxy adhesive compositions |
US4766186A (en) * | 1987-09-03 | 1988-08-23 | Texaco Inc. | Epoxy adhesive |
DE3812814A1 (en) * | 1988-04-16 | 1989-11-02 | Hilti Ag | USE OF TWO-COMPONENT REACTION RESIN FOR FASTENING PURPOSES |
US5547599A (en) | 1989-03-17 | 1996-08-20 | Raytheon Company | Ferrite/epoxy film |
JPH02269782A (en) * | 1989-04-11 | 1990-11-05 | Mitsubishi Gas Chem Co Inc | Epoxy resin coating composition |
DE4131457A1 (en) | 1991-09-21 | 1993-03-25 | Basf Ag | CARTRIDGE OR CARTRIDGE FOR CHEMICAL FASTENING TECHNOLOGY |
DE4231161A1 (en) | 1992-09-17 | 1994-03-24 | Hilti Ag | Mortar and device for fixing anchoring means in boreholes |
US5385990A (en) | 1992-11-02 | 1995-01-31 | Lord Corporation | Structural adhesive composition having high temperature resistance |
US5643994A (en) | 1994-09-21 | 1997-07-01 | Illinois Tool Works Inc. | Anchoring systems and methods utilizing acrylate compositions |
US5965635A (en) * | 1995-06-07 | 1999-10-12 | Illinois Tool Works Inc. | Alkylacrylate ester composition for anchoring materials in or to concrete or masonry |
DE4437497A1 (en) | 1994-10-20 | 1996-04-25 | Basf Ag | Dowel compound for chemical fastening technology |
JP3815694B2 (en) * | 1995-02-27 | 2006-08-30 | 旭化成ケミカルズ株式会社 | Adhesive for building structures |
JPH08325358A (en) * | 1995-06-02 | 1996-12-10 | Toyo Ink Mfg Co Ltd | Curable resin composition for building material of civil engineering work |
US6015845A (en) * | 1995-11-16 | 2000-01-18 | Asahi Kasei Kogyo Kabushiki Kaisha | Binder for building structure |
GB9609439D0 (en) * | 1996-05-04 | 1996-07-10 | Zeneca Ltd | Polymerisable composition |
JP3598649B2 (en) * | 1996-05-07 | 2004-12-08 | 東洋インキ製造株式会社 | Curable resin composition |
ATE191090T1 (en) * | 1996-07-29 | 2000-04-15 | Ciba Sc Holding Ag | LIQUID, RADIATION-CURED COMPOSITION, PARTICULARLY FOR STEREOLITHOGRAPHY |
JPH10182938A (en) * | 1996-12-24 | 1998-07-07 | Toyo Ink Mfg Co Ltd | Curable resin composition and resin composition |
US5891942A (en) | 1997-05-01 | 1999-04-06 | Fibre Glass-Evercoat Company, Inc. | Coating composition with improved water and mar resistance |
KR100591468B1 (en) * | 1998-08-03 | 2006-06-20 | 코그니스 코포레이션 | Epoxy curing agent of phenol-aldehyde reacted with polyamine |
US20020035111A1 (en) | 1998-10-09 | 2002-03-21 | Rifat Pamukcu | Method of inhibiting neoplastic cells with tetracyclic pyrido[3,4-B] indole derivatives |
DE19852720A1 (en) * | 1998-11-16 | 2000-05-18 | Fischer Artur Werke Gmbh | Two-component compound for chemical fasteners |
JP4678456B2 (en) * | 2000-06-28 | 2011-04-27 | Dic株式会社 | Epoxy resin composition |
US6291555B1 (en) * | 2000-07-26 | 2001-09-18 | Illinois Tool Works Inc | Highly viscous chemical anchoring adhesive |
JP2002053668A (en) * | 2000-08-04 | 2002-02-19 | Yokohama Rubber Co Ltd:The | Low temperature curable resin composition |
US6939610B1 (en) * | 2002-07-31 | 2005-09-06 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Thermal insulating coating for spacecrafts |
AU2003259674A1 (en) * | 2002-11-08 | 2004-05-27 | Illinois Tool Works Inc. | Curable adhesive compositions containing reactive multi-functional acrylate |
US7544739B2 (en) * | 2002-11-08 | 2009-06-09 | Illinois Tool Works Inc. | Curable adhesive compositions containing reactive multi-functional acrylate |
US20040176550A1 (en) * | 2003-03-05 | 2004-09-09 | Adlamco, Inc. | Epoxy-acrylate/amine adhesive composition |
-
2004
- 2004-09-21 US US10/946,191 patent/US7244793B2/en not_active Expired - Fee Related
- 2004-09-22 CN CN2004800315839A patent/CN1871299B/en not_active Expired - Fee Related
- 2004-09-22 CA CA2539937A patent/CA2539937C/en not_active Expired - Fee Related
- 2004-09-22 EP EP04784824A patent/EP1673411A4/en not_active Withdrawn
- 2004-09-22 AU AU2004276280A patent/AU2004276280B2/en not_active Ceased
- 2004-09-22 EP EP11004197.7A patent/EP2366738B1/en not_active Not-in-force
- 2004-09-22 NZ NZ546208A patent/NZ546208A/en not_active IP Right Cessation
- 2004-09-22 WO PCT/US2004/031133 patent/WO2005030894A2/en active Application Filing
- 2004-09-22 NZ NZ585267A patent/NZ585267A/en not_active IP Right Cessation
- 2004-09-22 JP JP2006528145A patent/JP4805830B2/en not_active Expired - Fee Related
-
2007
- 2007-07-16 US US11/778,481 patent/US8026321B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of EP1673411A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8058345B2 (en) | 2002-11-08 | 2011-11-15 | Illinois Tool Works Inc. | Curable adhesive compositions containing reactive multi-functional acrylate |
CN101747882A (en) * | 2010-01-11 | 2010-06-23 | 中国石油大学(华东) | Tectorial membrane sand solidifying system suitable for low-temperature reservoir sand prevention |
CN109536103A (en) * | 2018-11-21 | 2019-03-29 | 洛阳科博思新材料科技有限公司 | A kind of preparation method of the high-strength anchoring adhesive of chemical anchor bolts |
Also Published As
Publication number | Publication date |
---|---|
EP2366738A1 (en) | 2011-09-21 |
EP2366738B1 (en) | 2016-01-27 |
AU2004276280B2 (en) | 2008-08-14 |
NZ585267A (en) | 2011-06-30 |
CN1871299B (en) | 2010-05-12 |
CA2539937A1 (en) | 2005-04-07 |
JP4805830B2 (en) | 2011-11-02 |
AU2004276280A1 (en) | 2005-04-07 |
WO2005030894A3 (en) | 2005-09-09 |
EP1673411A2 (en) | 2006-06-28 |
US8026321B2 (en) | 2011-09-27 |
NZ546208A (en) | 2010-06-25 |
JP2007518840A (en) | 2007-07-12 |
EP1673411A4 (en) | 2009-02-25 |
US20050090626A1 (en) | 2005-04-28 |
CA2539937C (en) | 2011-01-11 |
US20090131608A1 (en) | 2009-05-21 |
US7244793B2 (en) | 2007-07-17 |
CN1871299A (en) | 2006-11-29 |
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