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    • 专利摘要:
    A polymerizable large-composition adhesive or filling composition comprising from 5 to 75% by weight of a mixture of one or more elastomers with one or more partially thermoplastic polymers selected from the group consisting of core / shell impact modifiers, polychloroprene elastomers and elastomeric polymers, of 0.5 to 35% by weight of an unsaturated polyester resin or vinyl ester resin, and from 20 to 80% by weight of an alkyl acrylate or methacrylate monomer, and wherein the partially thermoplastic polymers are crosslinked to render them insoluble or only partially soluble in the monomer, and wherein the elastomers in the monomers are completely soluble.
    公开号:AT13638U2
    申请号:TGM50141/2013U
    申请日:2004-10-05
    公开日:2014-05-15
    发明作者:
    申请人:Ips Corp；
    IPC主号:
    专利说明:

    Description BACKGROUND OF THE INVENTION FIELD OF THE INVENTION: This invention relates to polymerizable vinyl adhesive or filler compositions useful in a variety of adhesive, coating, filling, repair and related applications. More particularly, this invention relates to two part room temperature curing polymerizable vinyl adhesive compositions comprising blends of free radical polymerizable monomers and additives that generate heat and undergo expansion and contraction during the polymerization process. The improved compositions include blends of elastomers, thermoplastic resins, acrylate, methacrylate and styrene monomers and polyester or vinyl ester resins that can be used in large masses or thick cross-sections without gas evolution and cavitation from the exothermic curing reaction. It also relates to improvements in the ability of adhesives based on the compositions to bond thermoplastic and thermoset materials, and to bind such materials with a reduced tendency to cause "read-through" in the bonded regions The ability of the compositions to cure with a tack-free surface and low residue odor, especially when formulated to have long open-time applications involving large parts or assemblies, and further relates to improvements in physical properties and adhesive bonding capabilities of the modified compositions. BACKGROUND: Polymerizable vinyl adhesive compositions useful for a variety of adhesive, coating, filling, repair, and related applications are well known in the art include formulations based on acrylate and methacrylate monomers, styrenic monomer and styrene derivatives, as well as polyester and vinyl ester resins. The compositions are generally liquids or pastes which polymerize and cure when two separately packaged components, one containing a polymerization initiator, generally a peroxide, and the other containing a promoter, generally an amine, are mixed immediately prior to use become.
    A particularly useful group of polymerizable vinyl compositions comprises mixtures of dissolved or dispersed polymers in acrylate or methacrylate monomers. Such compositions can provide a number of performance benefits for Kloffoffbindung and related applications, including high bond strength, adhesion to a variety of materials with minimal surface preparation, and rapid cure. Methyl methacrylate is a preferred monomer for these adhesives because of its relatively low cost and high strength properties in formulated compositions. This group of polymerizable compositions is recognized by those skilled in the art to be superior in many respects to those based on polyester resins and vinyl ester resins, particularly with regard to their ductility and adhesion to a variety of material surfaces.
    Polyester resins generally contain styrene, which causes less cost than methyl methacrylate. They are widely used in automotive body fillers, polyester marine putty, and other fill, bind, and repair materials. Polyester / styrene compositions are preferred for applications that emphasize the ability to economically fill voids and voids with adequate functional performance rather than those that emphasize physical properties and related performance attributes at cost. Thus, a surprising aspect of this invention is the achievement of improvements in the performance of the compositions of the invention through the incorporation of polyester resins.
    Many of the benefits provided by the compositions of the invention are useful for the above non-adhesive applications. However, adhesive applications are among the most sophisticated of those anticipated for such compositions. For this reason, the discussion and examples that follow, and the improvements of the invention will emphasize adhesive applications, with the understanding that they can be easily extended to the other applications mentioned.
    The growing acceptance of methacrylate adhesives has broadened their use to ever larger assemblies and applications, resulting in more demanding application requirements. For example, large manufactured assemblies require longer open time adhesives. For adhesive applications, open time, working time, and open time are interchangeable terms that define the time that elapses between mixing the separated adhesive components and achieving a degree of polymerization or cure that prevents effective bond formation. At the end of open working time, the adhesive either reaches a very high viscosity, forms a skin on the surface, or both, preventing effective wetting for good bond formation. For other applications, this interval is often referred to as gel time or pot life of the composition, which is the time after mixing that makes it too thick or viscous to proceed with its application. Conventional prior art techniques and techniques for increasing the open working time of adhesives by delaying the onset of curing or curing rate of the composition with chemical inhibitors or retarders often introduce undesirable negative factors or trade-offs in the use or performance characteristics of the compositions.
    Another factor in using adhesives to bond large assemblies is the size of the gap between the bonded components. As the size of the parts to be bonded increases, so does the size of the gap between the fitting parts. In particular, this may be a problem with open-formed fiber structures that outweigh boats, large vehicle assemblies, architectural structures, bridge decks, and other large structures. When traditional polymerizable methacrylate adhesives are employed in such thick voids, the exothermic conversion of the cure and the volatility of the monomer generally causes gas evolution and the formation of voids in the adhesive bond, resulting in inadequate bond integrity and part-performance. The above-described additive techniques for increasing the open-time can also be used to reduce the exothermic and gas evolution problem, but generally the same negative application and performance characteristics result. Another technique, also discussed below, is the use of inert fillers to reduce this exothermic effect. However, such fillers often have a negative impact on the strength and durability of the compositions in adhesive applications.
    Yet another factor addressed by the compositions of the invention, particularly in the assembly of boats and vehicles, is a phenomenon called "read-through" or "print-through". This is a problem of appearance that can result when an adhesive is used to bond an internal reinforcement, stiffener, backing or other component to an outer panel or "skin" that has a smooth or glossy finish such surfaces are generally referred to as "cash register A" surfaces. At the end of the curing process or during post-curing processes, certain adhesives, particularly those that undergo exothermic polymerization and that change in size due to expansion and contraction during the exotherm and cooling associated with the curing process, may form exterior surface irregularities The irregularity is generally a subsidence, silhouette, distortion or other
    Disruption of the surface, which is visible to the eye and which is aesthetically objectionable. The incidence and severity of the problem generally increases with the thickness of the bond and the total weight of adhesive included. The causes of such appearance problems can be complex, including contributions from the specific nature of the bound substrates. These include thickness of the part, state of cure of thermoset parts when bonded, the thermal conductivity and expansion coefficients of the bonded materials, the properties of coatings applied to the parts, and other factors. Regardless of what other factors may be involved in the development of read-through or print-through, it is generally observed that adhesives less prone to exotherm and experience of changes in extents during cure have less propensity to contribute to the phenomenon ,
    A number of techniques have been used in efforts to overcome this problem. These often involve the addition of materials that effectively reduce the level of reactive monomer to reduce its contribution to dimensional changes, shrinkage and exotherm. These materials include inert liquid plasticizers which act as diluents and fillers which act as diluents and absorb some of the heat of the polymerization. A related art involves the use of hollow, expanding microspheres that increase the volume of the curing mass and help balance the shrinkage. Yet another technique is the use of thermoplastic polymers which phase-separate during the polymerization process and produce internal voids in the material which counterbalance shrinkage. However, as in the case of the gas evolution problem noted above, the exclusive addition of these inert ingredients in amounts sufficient to effectively reduce read-through is generally detrimental to the performance of the adhesive. However, they may be used to advantage in combination with the improvements of the composition of the invention.
    As noted above, the common method of addressing the open-time problem and the exothermic gas evolution problem, both related to the rate of cure conversion, is the reactivity of the composition by using smaller proportions of polymerization initiators, choosing less reactive initiating species Adding retarding additives or chain transfer agents, or reducing a combination of these techniques. However, as highlighted in U.S. Patent 5,859,160, referred to below, these techniques may allow other undesirable competing side reactions, such as oxygen inhibition, or interfere with effective polymerization and bond formation. The disadvantages of such air inhibition, as noted in U.S. Patent 5,932,638, also referred to below, include weaknesses in adhesive bonding, increased odor resulting from escaping, unreacted monomer, and tackiness problems of the surface of the adhesive. The problem is particularly acute when low levels of catalytic species and added retarding agents are used to extend the open-time of methacrylate-based adhesive compositions to periods of about 45 minutes to one hour or more. The problem is further aggravated by low ambient application temperatures which can further reduce the cure rate and prevent completion of the free radical curing process.
    Another well-known technique for retarding the cure rate and thereby increasing the time available for application of polymerizable vinyl compositions including methacrylate adhesives is the addition of certain substituted styrenic monomers such as α-methylstyrene. When the composition is based on methyl methacrylate, styrene as well as substituted styrenes are effective as disclosed in U.S. Patent 5,653,345.
    U.S. Patent 5,859,160 discloses the styrenic monomer technique in more detail, but does not provide specific references or examples of adhesive applications or properties or effects of the added styrenic monomers on them. It is claimed that the cure rate delay takes place without adversely affecting the completion of the cure and the properties of the curable composition after it has cured. The use of the invention in formulating adhesive composition is suggested. It is well known to those skilled in the art that the addition of styrenic monomers to certain methacrylate compositions, especially when combined with low levels of catalytic species to extend open time and reduce exothermic gas evolution, can have a negative effect on the curing behavior of adhesives.
    U.S. Patent No. 6,291,593 discloses methacrylate adhesive compositions containing a retarding additive to increase open time and / or reduce the exothermic peak cure temperature. Zinc compounds such as zinc chloride are preferred.
    U.S. Patent 5,932,638 discloses the use of certain para-halogenated aniline derivatives to overcome the problems associated with poor surface hardening of adhesive compositions resulting from air inhibition. Compositions containing up to about 10% by weight of unsaturated polyester resin are disclosed. The cited improvement in surface hardening is a reduction in the thickness of the uncured surface layer exposed to the air, from about 0.025 inches (0.635 mm) to about 0.002 (0.0508 mm) to about 0. 003 inches (0.7062 mm) ). However, actual commercial experience has shown that even the lesser amounts of non-cured adhesive referred to can be sufficient to cause serious residual odor problems. Such problems can occur when, for example, the incompletely cured surface of a squeezed bead or "fillet weld" of adhesive is in a restricted area such as stringers of a boat The problem can be exacerbated if the fillet weld or other uncured adhesive bond area with a spatula or any other device which lubricates a thin film of the adhesive against an exposed surface such as the hull The resulting thin film of adhesive is particularly susceptible to the effects of air-trapping Captured vapors may eventually migrate to the enclosed cabin area of the boat and ingress produce objectionable or unacceptable degree of odor despite the very low levels that are present This is because the detectable odor threshold level for methyl methacrylate monomer is about 0.5 parts per million or less.
    There is clearly a need for improved adhesive compositions that provide extended open-time, the ability to cure in large, thick masses without gas evolution, provide fully cured, tack-free surfaces with little or no residual odor consisting of unpolymerized Monomer, and cure with reduced read-through effects on the finished outer surfaces of boats, vehicles and other appearance-sensitive assemblies, while maintaining or improving the performance of the cured adhesive.
    It has now been discovered that the combination of polyester or vinyl ester resins and certain acrylate or methacrylate adhesive compositions provides these needed improvements. In contrast to the technique of adding specific retarding additives, which involves a risk of adverse effects on adhesive properties, as outlined above, the addition of polyester resins can provide many benefits which will become apparent in the following discussion.
    U.S. Patent 5,932,638 discloses the optional inclusion of from 0% to about 10% by weight of a polyester resin in methacrylate compositions.
    U.S. Patent 5,859,160 also discloses the optional inclusion of from 0% to about 10% by weight of an unsaturated polyester resin in methacrylate adhesive compositions.
    The '638 and' 160 patents cite U.S. Patents 3321351, 4223115, 4293665 and 4467071, which disclose the inclusion of unsaturated polyester resins in methacrylate
    Disclose adhesive compositions. As in the above references, '115,' 665 and '071 patents disclose the optional inclusion of from 0 to about 10 weight percent of unsaturated polyester resin. Example IV in each of the '115 and' 665 patents which claims improvements in metal adhesive bond resistance by the addition of phosphate ester materials includes 3% by weight of an unsaturated polyester resin.
    In all of the references cited above, the methacrylate composition contains at least about 10 percent and generally 15-20 percent or more of a polymeric nature to provide toughness in the cured composition. Preferred polymers include polychloroprene, chlorosulfonated polyethylene, blends of chlorinated polyethylene with sulfonyl chlorides, polybutadiene, butadiene copolymers, and polyacrylate rubbers. There is no particular preference for the choice of these polymers as to whether or not an unsaturated polyester resin is present.
    U.S. Patent 3,321,351 discloses compositions containing unsaturated polyester resins, vinyl monomers and their polymers (specifically methyl methacrylate and polymers thereof, styrene monomer and polymers thereof), polychloroprene rubber and polyvinyl ethers. The specification generally discloses 10-85% vinyl monomer, 0-50% vinyl polymer, 0-80% unsaturated polyester, and 0-40% polyvinyl indinyl ether. However, in the examples, when methyl methacrylate is included in the compositions and no neoprene is included, no more than 15 percent polyester resin is included. When both methylmethacrylate and neoprene are present, not more than 1 percent of unsaturated polyester is included. In no case does the amount of neoprene exceed 3 percent of the composition.
    U.S. Patent 4,548,992 discloses methacrylate adhesive compositions containing a modified carboxyl containing nitrile rubber and an alkali metal or amine salt of an unsaturated polyester resin. The carboxyl-containing nitrile rubber is modified by reaction with a methacrylated phosphate ester. The free carboxyl groups of the polyester resin are neutralized by a metal compound, ammonia or an amine to produce a modified polyester resin containing an ionic bond. The ionic bond-containing polyester resin is said to promote adhesion to oily metal surfaces and improve the storage stability of the methacrylate adhesive composition.
    SUMMARY OF THE INVENTION
    The essential feature of this invention is the use of unsaturated polyester resins or vinyl ester resins to modify the curing behavior, bonding capabilities and physical properties of polymerizable acrylate or methacrylate compositions. The acrylate or methacrylate compositions are solutions of mixtures of one or more elastomers with one or more partially thermoplastic polymers in acrylate or methacrylate monomers which polymerize when mixed with a catalyst.
    The preferred polyester resins and vinyl ester resins are commercial products that are typically supplied as liquids that are catalyzed with peroxides and promoters and used for a variety of applications, including laminated and molded parts and structural components, coatings, adhesives, and repair materials.
    The preferred polymers are blends of one or more elastomers with one or more partially thermoplastic polymers. The preferred monomers are low molecular weight acrylate and methacrylate monomers. The most preferred monomer is methyl methacrylate.
    The invention provides a polymerizable adhesive or filler composition for large assemblies comprising from 5 to 75% by weight of a mixture of one or more elastomers with one or more partially thermoplastic polymers selected from the group consisting of core / shell Toughening modifiers, polychloroprene elastomers and elastomeric polymers, from 0.5 to 35% by weight of an unsaturated polyester resin or vinyl ester resin, and from 20 to 80% by weight of an alkyl acrylate or methacrylate monomer, and wherein the partially thermoplastic polymers are crosslinked to make them insoluble or only partially soluble in the monomer, and wherein the elastomers are completely soluble in the monomers.
    The invention further relates to the use of the polymerizable adhesive or filling composition of the present invention in adhesive, coating, filling or repair applications.
    The compositions of the invention have better control of the exothermic curing and dimensional changes associated with adhesive and filling compositions. As a result, they can be applied in thicker masses and can be used to bind and fill large areas and gaps, with greatly reduced tendency to gas or boil, exhibit read-through or print-through or other effects of exothermic conversion, with freedom from negative effects of undercuring on the surface or in thin sections or films.
    DETAILED DESCRIPTION OF THE INVENTION
    The polyester and vinyl ester resins utilized in this invention are well known to those skilled in the art. The resins and their applications are described in detail in a number of publications, including the "Handbook of Composites," Second Edition, S.T. Peters, Ed., Edited by Chapman and Hall, which is incorporated herein by reference.
    Unsaturated polyesters are condensation reaction products of polybasic acids or anhydrides with polyhydric alcohols. After the condensation reaction is complete, the resulting resin, generally a solid or semi-solid, is diluted with an unsaturated monomer to establish the desired viscosity, reactivity, and end-use properties.
    Preferred unsaturated monomers include styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylsytrol, 1,3-divinylbenzene, 1 , 4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and the like, and mixtures comprising at least one of the foregoing alkenyl aromatic monomers. Preferred aromatic alkenyl monomers further include styrenes having from 1 to 5 halogen substituents on the aromatic ring and mixtures comprising at least one such halogenated styrene. The monomer mixture may also contain an acrylate or methacrylate monomer such as methyl methacrylate. The monomer is generally present in an amount of 30 to 60 parts per 100 parts resin.
    Specific examples of unsaturated polybasic acids which can be used to form the unsaturated polyester resins include maleic acid, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, nadic acid, tetrahydrophthalic acid, endo-methylene tetrahydrophthalic acid, hexachloro-endomethylenetetrahydrophthalic acid, and other unsaturated di and trihydrous acids polybasic acids, as well as their corresponding esters and anhydrides. Preferred unsaturated acids include maleic acid and fumaric acid and their corresponding esters and anhydrides.
    Polyfunctional saturated and aromatic acids are used in conjunction with the polybasic unsaturated acids to reduce the density of ethylenic unsaturation and provide desired chemical and mechanical properties for specific applications. Examples of saturated and aromatic polybasic acids include succinic, adipic, sebacic, azelaic, dodecanedioic, eiconic, phthalic, isophthalic, terephthalic, cyclohexanedicarboxylic (CHDA) and the like, halogenated acids such as tetrabromophthalic acid, as well as their esters and anhydrides. Preferred aromatic polybasic acids include phthalic acid, terephthalic acid and isophthalic acid and their corresponding esters and anhydrides. Polyester resins which they employ are termed "orthophthalic", "isophthalic", or "ortho" or "iso" resins, respectively.
    Examples of useful polyhydric alcohols include ethylene glycol, propylene glycol, 1,2-propanediol, 2-methyl-1,3-propanediol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , Neopentyl glycol, glycerol, triethylene glycol, pentanediol, hexylene glycol, hydrogenated bisphenol A, bisphenol A-alkylene oxide adducts, tetrabromobisphenol A-alkylene oxide adducts, and the like. Preferred polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, and neopentyl glycol. Triols, when used, are used in a very limited amount relative to diol to control and limit chain branching and its effect on molecular weight and viscosity. Preferred triols include glycerol and trimethylolpropane.
    Recently, dicyclopentadiene (DCPD) monomer has been used to synthesize polyester resins which can be included in higher proportions in styrenic monomer to produce "low styrenic" resins Such resins are generally referred to as "DCPD" resins. They are used to reduce styrene emissions from the processes and equipment they use.
    Vinyl ester resins are described in a number of U.S. patents, including 3564074, 4151219, 4347343, 4472544, 4483963, 4824919, 3548030 and 4197390, which are incorporated herein by reference. Vinyl ester resins typically comprise a vinyl ester terminally unsaturated resin, generally derived from polyepoxide, and at least one copolymerizable monomer, generally styrene. The terminally unsaturated vinyl ester resins are prepared by reacting about equivalent amounts of a polyepoxide such as a bisphenol A / epichlorohydrin adduct with an unsaturated monocarboxylic acid such as acrylic or methacrylic acid. The resulting resin has terminal, polymerizable unsaturated groups. The resins may also include halogenated polyester and vinyl ester resins.
    While any of the polyester or vinyl ester resins referred to above or mixtures thereof may be used to advantage in the compositions of the invention, specific combinations of polyester or vinyl ester resins, methacrylate monomers and polymers may be formulated to provide specific and significant performance benefits and improvements over the prior art. For example, any number of the polyester or vinyl ester resins described above can be used to gas or boil compositions having reduced propensity of the composition as the adhesive cures. This can be accomplished with either a relatively short or long open arming time. When the working time is relatively short, for example from 10 to 30 minutes, the adhesive has the unique advantage of providing relatively fast cure with the ability to provide thick cross-sections or cavities with reduced exotherm and without gas evolution or boiling. Fully cured, void-free bonds can be achieved in about 15 to about 60 minutes in thicknesses of up to about one and a half inches (3.81 cm). Adhesives of the prior art with similar cure times are prone to develop or boil gas in thicknesses of one and a half inches (3.81 cm) or less.
    When the open time is long, for example, from about 45 to about 90 minutes, the adhesive has the ability to cure with a hard, tack-free surface, as well as the unique ability to thin in thin sections or in a thin film Bonds of cure delay and lingering odor resulting from unreacted, air-blocked monomer cure. Additionally, void-free bonds can be obtained in thicknesses of up to three inches (7.62 cm) within about 90 minutes to about three hours. Generally, long time adhesives of the prior art do not cure well in thin cross-sections or in thin films and tend to evolve and boil in thicknesses greater than about one inch (2.54 cm).
    [0039] In contrast to the above-mentioned technique of employing styrene monomer or substituted styrene monomers alone as separate additives, the polyester resins provide multiple benefits without adversely affecting the cure of the composition and, in fact, even improve the final stage of cure of the compositions , Other benefits may include improved adhesion and physical properties such as tensile strength and tensile elongation.
    The choice of resin may affect application, cure and performance characteristics in varying degrees depending on the specific formulation involved. For example, with constant other variables, compositions containing orthophthalic acid and isophthalic resins generally achieve a better final stage of cure than those containing DCPD resins when benzoyl peroxide is used as the catalyst. However, DCPD resins provide compositions with significantly less exotherm and shrinkage or dimensional change than orthophthalic or isophthalic resins. To advance the curing stage when choosing a DCP-D resin, particular attention must be paid to the choice of peroxide and promoter levels and to the choice of inhibitor package.
    Compositions containing vinyl ester resins or halogenated vinyl ester resins or mixtures thereof tend to have greater exotherm and dimensional change than those containing polyester resins, but their rate of cure, final cure stage and heat resistance, defined as a proportion of room temperature strength, are maintained high temperatures, are superior. If exotherm and dimensional change are not an issue, very strong, fast-setting bonds can be obtained with little tendency to gas evolution and boiling with vinyl ester resins.
    The resin used can be either accelerated or non-accelerated. Many commercial polyester and vinyl ester resins contain amines and / or organometallic compounds as well as inhibitors added by the manufacturer to impart a desired level of reactivity when a peroxide initiator is added just prior to use. Such resins are called accelerated or pre-accelerated resins. Because the resins used in this invention are additives in reactive methacrylate compositions that have specific catalytic requirements, it may be preferable in some instances that the polyester and vinyl ester resins contain no catalytic species. The modified methacrylate compositions of the invention utilizing such non-accelerated resins can then be formulated with the desired level of preferred catalytic species for the desired application characteristics.
    The unsaturated polyester and vinyl ester resins of this invention are available from a number of suppliers in U.S. Pat. and commercially available worldwide. U.S. suppliers include Alpha Owens Corning (AOC), Ashland Chemical, Cook Composites (CCP), Eastman Chemical, Inter-plastic Corporation, and Reichhold. Vinyl ester resins are from AOC, Ashland, Eastman, Inter-plastic. Reichhold and Dow Chemical available. Worldwide suppliers include Dianippon Chemical in Asia and DSM in Europe. The resins are sold under a number of brand names in different markets. The following is a summary of the resins and their brand names from the various local suppliers:
    SUPPLIER HARZTYP TRADING NAME
    Alpha Owens Ortho PE, DCPD Altek®, H300, H500, H800
    Corning
    Isophthalic PE Pultru, Vipel
    Terephthalic PE Pultru, Vipel
    Vinylester Hydropel, Vipel
    Ashland PE, DCPD, VE AME, Aropol, Hetron
    Dow Vinylester Derakane
    Eastman Ortho / Iso / Tere PE Verimac DCPD vinyl ester
    Interplastic PE, vinylester CoREZYN
    Reichhold Ortho / Iso / Tere / DION, Polylite DCPD polyester
    Vinyl Ester Hydrex, Atlac, DION PE = Polyester, VE = Vinyl Ester Preferred unsaturated polyester resins of this invention are unsaturated orthophthalic, isophthalic, terephthalic DCPD halogenated polyester resins and mixtures thereof. Preferred orthophthalic and DCPD resins include the Altek 500 and 800 series of AOC, the Polylite 31000, 32000, 33000 and 44000 series from Reichhold and similar resins from other manufacturers. Preferred isophthalic resins include Vipel F737 from AOC and similar resins sold under the tradename DION, ATLAC and Polylite from Reichhold. Preferred DCPD resins include the Altek H800 series from AOC and Polylite 44383, 44006 and 44285 from Reichhold.
    Resin manufacturers generally produce un-accelerated "base" versions of the above polyester resin types and vinyl ester resins which are blended with other resins to obtain a desired set of properties Within a given family of resins, grades with varying reactivity and flexibility characteristics become high solids manufactured, generally up to about 70 percent.
    The most preferred orthophthalic resins are unaccelerated, low to moderate reactivity flexibilized versions such as Polylite 31008 from Reichhold and Verimac 711-1530 from Eastman. The most preferred isophthalic and terephthalic resins are unaccelerated, low to moderate reactivity flexibilized versions such as AOC T750-70, Polylite 31830 from Reichhold and Verimac 126-0863 from Eastman. The most preferred DCPD resins are non-accelerated base resins such as CoREZYN 61AA340 from Interplastics and Polylite 44-006 from Reichhold.
    Preferred vinyl ester resins, halogenated vinyl ester resins or mixtures thereof include Derakane 411-350 from Dow, Hetron 922 from Ashland, CoREZYN VE8300 from Interplastic, DION and Atlac 9100 from Reichhold and Verimac 785-8430 from Eastman. The most preferred vinyl ester resins include Derakane 411-350 from Dow and DION / Atlac 9100 from Reichhold.
    The vinyl ester or polyester resins can be used individually or in combination to achieve the optimum effects in terms of curing behavior and physical properties of the cured composition. Virtually any combination of unsaturated polyester resin and methacrylate adhesive composition may be used, but to retain the beneficial properties of the methacrylate adhesive composition, the methacrylate portion should comprise at least 20 percent of the total mixture. The compositions of the invention preferably comprise a combination of from 0.5 percent to 35 percent, preferably from 1 percent to 25 percent and most preferably from 2 percent to 20 percent of an unsaturated polyester resin, a vinyl ester resin or a combination thereof.
    The polymers of this invention are a blend of one or more elastomers with one or more partially thermoplastic polymers selected from the group consisting of core / shell impact modifiers, polychloroprene elastomers and elastomeric polymers wherein the partially thermoplastic polymers are crosslinked, to make them insoluble or only partially soluble in the monomer, and wherein the elastomers are completely soluble in the monomers.
    As used herein, the term partially thermoplastic refers to polymers, elastomers or elastomer-containing polymers that have some degree of crosslinking in their structure. An example of such a polymer is a core / shell impact modifier wherein the core, which is typically a butadiene based or acrylic acid based rubber, is crosslinked to some degree to provide the desired impact modifying properties or other specific properties. Another example is Neoprene AG, a polychloroprene elastomer sold by duPont Dow Elastomers. In this case, the polychloroprene, which is normally thermoplastic and soluble, is specifically modified with an agent that gives easy cross-linking to provide unique, gel-like properties that will beneficially modify the rheology of the solutions or rubber compounds that contain it. Additional examples include elastomeric polymers that are crosslinked to modify them for use as impact modifiers or modifiers of other properties in formulated rubber, plastic or other resin compositions. Specific examples include Chemigum, a cross-linked butadiene-acrylonitrile elastomer, and Sunigum, a cross-linked acrylate terpolymer, both sold by Eliokem. In all these cases, the crosslinking included to modify the properties of the polymers renders them insoluble or only partially soluble in the monomers of this invention, while completely thermoplastic or elastomeric polymers are completely or substantially soluble in the monomers.
    Preferred thermoplastic, partially thermoplastic, and substantially soluble polymers and elastomers and blends thereof include, but are not limited to, diene-based polymers including those based on butadiene or isoprene, such as copolymers and multipolymers, which include acrylonitrile, styrenic, and styrene contain acrylic monomers; thermoplastic block copolymers, multipolymers and toughening modifiers based on butadiene, isoprene, ethylene-propylene and ethylene-butylene in combination with styrene, acrylonitrile and acrylic acid monomers; Acrylonitrile butadiene styrene (ABS) resins and impact modifiers, methacrylate butadiene styrene (MBS) and MABS impact modifiers and polymers, chlorinated polymers such as polychloroprenes, chlorinated polyolefins and copolymers, chlorosulfonated polyethylenes, polyolefins and copolymers thereof, polyepichlorohydrins and copolymers, vinyl chloride containing polymers, and acrylic acid based elastomers and impact modifiers , The preferred polymers are those which impart toughness and elastic properties and enhance adhesion of the compositions to bonded substrates. Other polymers that improve adhesion but not toughness can be used to advantage in the compositions of the invention. Examples include polymers, copolymers and multipolymers of styrene, acrylonitrile, vinyl chloride and acrylic monomers. Liquid reactive and non-reactive elastomers and low molecular weight oligomers may also be used to advantage in the compositions of this invention. Examples include liquid vinyl reactive butadiene polymers and copolymers with acrylonitrile and acrylate monomers sold by Noveon and Ricon Resins, and a number of other reactive liquid polymers and oligomers sold commercially by Sartomer, Radcure and others.
    The most preferred elastomers and polymers include polychloroprenes such as
    Neoprene AD-5, AD-10 and AG, chlorinated polyethylenes such as Tyrin 3611, 3615 and 4211, and chlorosulfonated polyethylenes such as Hypalon 20, 30, 40 and 48 sold by DuPont Dow elastomers, nitrile elastomers such as Nipol 401LL, 1201, DN -4555 and 1401 LG, sold by Zeon Chemical, crosslinked nitrile elastomers such as Zealloy 1422, sold by Zeon and Chemi-gum P-83 sold by Eliokem, liquid nitrile elastomers such as Hycar 1300X33, sold by Noveon, styrene-butadiene-styrene (SBS) , Styrene-isoprene-styrene (SIS), styrene-ethylene-propylene (SEP) and styrene-ethylene-butadiene-styrene (SEBS) block copolymers sold by Kraton Polymers, acrylic elastomers such as Hytemp 4051 and 4054, sold by Zeon, Ethylene acrylic elastomers such as Vamac D and G sold by DuPont, core / shell impact modifiers such as Paraloid BTA 753 (MBS) sold by Rohm and Haas, Blendex 338 (ABS) sold by GE Plastics, FM-10 (U.S. all acrylic) sold by Kaneka, and based on ethylene-propylene Impact modifiers such as Royaltuf 372P20 sold by Crompton Chemical.
    Preferred monomers are low molecular weight CrCe acrylate and methacrylate monomers. The most preferred monomers include methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, hydroxypropyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, propyl acrylate, hydroxypropyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl methacrylate, and mixtures thereof. More preferred monomers are methyl methacrylate and ethyl methacrylate. The most preferred monomer is methyl methacrylate. Other monofunctional or polyfunctional acrylate monomers and high molecular weight oligomers may be used in amounts of up to about 25 percent of the composition to crosslink the cured compositions or to reduce certain desirable application and performance characteristics such as reduced odor, improved wetting and adhesive properties for certain substrates Tendency to dissolve sensitive plastic surfaces including incompletely cured polyester resin surfaces, and to impart improved flexibility or other mechanical properties.
    A more complete understanding of the specific benefits provided by the various acrylate and methacrylate compositions and polyester and vinyl ester resins will become apparent from the examples that follow.
    The compositions of this invention comprise a combination of from 5 percent to 75 percent, preferably from 7 percent to 60 percent, and most preferably from 10 percent to 50 percent of a thermoplastic or partially thermoplastic polymer or elastomer, from 0.5 percent to 35 percent, preferably 1 percent to 25 percent, and more preferably 2 percent to 20 percent of an unsaturated polyester resin or vinyl ester resin, and 20 percent to 80 percent of at least one acrylate or methacrylate monomer, preferably from 30 to 80 percent, and more preferably from 40 to 70 percent ,
    Preferred compositions of this invention comprise a combination of from 5 percent to 75 percent, preferably 7 percent to 60 percent and most preferably 10 percent to 50 percent of a mixture of at least two polymers, 0.5 percent to 35 percent, preferably 1 percent to 30 percent and more preferably 2 percent to 20 percent of an unsaturated polyester resin or a vinyl ester resin, and 20 percent to 80 percent of at least one acrylate or methacrylate monomer, preferably from 30 to 80 percent and most preferably from 40 to 70 percent.
    More preferred compositions comprise a combination of from 5 to 75 percent, preferably from 7 percent to 60 percent, more preferably from 10 percent to 50 percent by weight of a blend of at least two elastomeric polymers or at least one elastomeric polymer and at least one thermoplastic polymer, From 0.5 percent to 35 percent, preferably from 1 percent to 25 percent, and most preferably from 2 percent to 20 percent of an unsaturated polyester resin or vinyl ester resin, and from 20 percent to 80 percent of at least one acrylate or methacrylate or monomer, preferably from 30 to 80 percent, and more preferably from 40 to 70 percent.
    In another preferred embodiment, the compositions of the invention comprise a combination of from 5 to 75 percent, preferably from 7 percent to 60 percent, more preferably from 10 percent to 50 percent by weight of a blend of at least one elastomer and at least one elastomeric modified thermoplastic polymer or an elastomer-containing core / shell impact modifier, 0.5 percent to 35 percent, preferably 1 percent to 25 percent and most preferably 2 percent to 20 percent of an unsaturated polyester resin or a vinyl ester resin, and 20 percent to 80 percent of at least one methacrylate monomer, preferably from 30 to 80 percent, and more preferably from 40 to 70 percent.
    In a particularly preferred embodiment, the compositions of the invention comprise a combination of from 5 to 75 percent, preferably from 7 percent to 60 percent, more preferably from 10 percent to 50 percent by weight of a blend of polymers containing at least one chlorinated polymer and at least one nitrile elastomer or thermoplastic acrylonitrile polymer as disclosed in US Pat. No. 6,602,958, 0.5 percent to 35 percent, preferably 1 percent to 25 percent and most preferably 2 percent to 20 percent of an unsaturated polyester resin or vinyl ester resin, and 20 percent to 80 percent of at least one methacrylate monomer, preferably from 30 to 80 percent and most preferably from 40 to 70 percent.
    To promote adhesion to various substrates, including metallic substrates, the compositions may also contain from 0.01 to 20 percent, preferably from 0.1 to 15 percent of a polymerizable organic acid monomer or oligomer. These include vinyl reactive carboxylic acid monomers well known to those skilled in the art. Preferred polymerizable carboxylic acid monomers are acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid. Other preferred polymerizable acid monomers or oligomers include the vinyl-functional derivatives of phosphoric acid disclosed in the aforementioned U.S. Patents 4,223,115 and 4,293,665. Specific preferred examples are the mixed mono- and disubstituted phosphate esters derived from hydroxyethyl methacrylate sold under the trade names Light Ester P-1M and P-2M by Kyo-eisha Chemical Co., LTD, Japan.
    The choice of acid monomer or oligomer or mixture thereof will depend on the anticipated substrate binding requirements and other effects imparted by the polymerizable acid employed. For example, methacryic acid is preferred in many instances because it increases the cure rate of the adhesive composition and improves adhesion to Baustahi. The partially substituted phosphated esters are preferred when improved adhesion and durability to unprepared aluminum and epoxy substrates are required. However, the acid functionalities of phosphate esters can retard the cure rate of certain formulations. Maleic acid is shown to increase adhesion to difficult-to-bind substrates such as nylon in U.S. Patent 4,714,730. In some cases, mixtures of acidic monomers and oligomers may be used to advantage when adhesion to a variety of substrates is required. The exact choice and effects of the mixed acids is influenced by other components in the formulation and the acceptable performance tradeoffs for a given application.
    Various viscosity control agents such as organopolysilicates, fumed silica or the like can be added in amounts ranging from 0.1 to 10 percent based on the system weight to control the viscosity of the adhesive. Additional fillers may be added in significantly larger amounts to reduce the cost of the adhesive or to modify certain physical properties. In this case, the amount of filler or diluent separately as an additive to the base polymer and monomer composition would be considered as described above. Common particulate fillers or extenders such as clay, talc, calcium carbonate, silica and
    Alumina trihydrate may be added by weight up to about 50 percent or more of the composition to achieve specific economic, application or bond related characteristics. Inorganic or organic microspheres or microballoons can be used to reduce the density and cost of the adhesives as well as to improve their abrasive or surface treatment characteristics when used as repair materials such as body repair products.
    A number of available and well-known catalyst combinations can be chosen to cause the polymerization and curing of the compositions of the present invention. Some of the terms used to describe the various components of the curing system (catalysts, initiators, reducing agents, activators, promoters) are often used interchangeably, and thus the terminology used below may differ from other descriptions used in the art. The primary catalytic species for initiating the polymerization of the vinyl monomers of this invention are peroxide or hydroperoxide initiators. Examples are benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, tert-butyl peroxyacetate, tert-butyl perbenzoate and the like. The peroxide initiators are used in amounts ranging from 0.01 to 10 weight percent based on the weight of the adhesive composition. Preferably, the initiators will be used in the amount of 0.05 to 5 wt%.
    To prevent premature polymerization of the methacrylate adhesive compositions, including the compositions of the invention, one or more free radical inhibitors or antioxidant stabilizers may be required in the formulation. The selection and use of such additives is well known to those skilled in the art. The methacrylate monomers used in the compositions contain inhibitors, generally phenolic compounds, which are added to the monomers to stabilize them during storage. Many of the polymers used in the formulations contain thermal stabilizers which protect the polymers during processing and storage. The polyester resins of the compositions of the invention may also contain inhibitors. The most common inhibitors and stabilizers are phenols, quinones and their derivatives, and many can be used interchangeably in said raw materials. In some cases, the inhibitors present in these raw materials are sufficient to stabilize the formulated adhesives, and in some cases additional materials may need to be added to ensure stability. Because of the variety of raw materials (with in situ inhibitors) that can be selected and the variety of catalyst systems that can be chosen to make a composition, the choice of the complete inhibitor package is generally the last step in the formulation process. The choice is specific to any formulation beyond the scope of this invention and is generally the property of those skilled in the art.
    In addition to the free radical inhibitors or stabilizers, a chelating agent can be used to further stabilize the methacrylate compositions. Chelating agents are used as scavengers for metal contaminant traces that can destabilize the reactive methacrylate formulations. The use and function of these additives are disclosed in U.S. patents 4038475 and 4374940.
    A reducing agent is used to effect the room temperature decomposition of the peroxide or hydroxy peroxide initiator at ambient or room temperature. The most common reducing agents for this purpose are well known to those skilled in the art and include tertiary aromatic amines and aldehyde amine reaction products. Useful tertiary amines include N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-diethyltoluidine, N, N-bis (2-hydroxyethyl) toluidine, and other similar aromatic amines which are known for this Purpose are used, which are well known in the art. Aldehyde-amine reaction products include such compositions as butyraldehyde-aniline and butyraldehyde-butylamine derivatives whose active ingredient is a dihydropyridine (DHP) formed from condensation of three moles of aldehyde with one mole of amine. Recently, DHP-enriched versions of these compositions have been made available. One such material is Reillcat ASY-2, available from Reilly Industries, Inc. This catalyst or initiator system is most commonly used in combination with sulfonyl chloride compound and a hydroperoxide as described in U.S. Patents 3,890,407 and 4,168,644. The reducing agents are used in amounts of up to 5% by weight based on the weight of the adhesive. Preferred amounts are 0.01 to 5 percent.
    Transition metal salts, including organometallic compounds such as cobalt, nickel, manganese or iron naphthenate, copper octoate, copper acetylacetonate, iron hexoate or iron propionate, and other well-known metallic compounds function as promoters for the polymerizable compositions of the invention. Promoters whose effects vary widely from system to system are used in amounts up to 1-2% by weight, preferably 1 part per million to 0.5% by weight. The most preferred amounts range from 5 parts per million to 0.5 wt%. Metallic promoters can be used with certain peroxide initiators as primary initiating species or in combination with tertiary amine or amine aldehyde reducing agents to increase the rate of polymerization.
    Most preferred free radical initiation systems include (1) a tertiary amine which reacts with benzoyl peroxide or other peroxide, (2) a DHP derivative in combination with a sulfonyl chloride compound and a hydroperoxide or other peroxide or (3) an organometallic compound such as cobalt naphthenate in combination with a hydroperoxide, all three combinations being capable of effecting the free radical curing process at room temperature. Combinations of amine or amine aldehyde and metallic species can be used to advantage in any of the above systems. The precise choice and distribution of the initiating and inhibiting components for a given composition will depend on their specific intended application, which is subject to the formulation principles well known to those skilled in the art.
    The adhesive compositions of the invention are characterized by their ability to polymerize in large masses or thick cross-sections without forming voids, and their ability to cure with a tack-free surface or in thin films with little residual odor, especially when formulated to have a long open-time application involving large parts or assemblies. The compositions are also capable of curing in thick bonds or relatively large masses without exhibiting objectionable read-through or print-through on exposed cosmetic surfaces. They also have improved physical properties and adhesive bonding capabilities. Such improvements include obtaining higher tensile strength without sacrificing tensile strain, and the ability to bond a variety of composites, including certain difficulty in bonding composites with or without surface preparation, as well as a variety of other materials alone or in combination.
    The compositions of this invention have been primarily developed to improve the properties of adhesives. However, the improvements discovered thereby make these products more useful than previous products of their class for repair materials, coatings, bulk casting and a number of other applications beyond adhesives.
    EXAMPLES
    IN EXAMPLES, MATERIALS AND COMPONENTS USED
    Trade name or description or source or
    Name Function Supplier
    Neoprene Polychloroprene Elastomer DuPont Dow Elastomers
    Nipol® Nitrile Elastomer Zeon Chemicals MMA Methyl Methacrylate Monomer Lucite PARALOID® MBS Impact Modifier Rohm & Haas Co. BTA 753 MAA Methacrylic Acid Monomer Lucite DMPT N, N-Dimethyl-p-toluidine First Chemical
    HET Hydroxyethyltoluidine Bayer AG 55% BPO Paste Benzoyl peroxide (55%) in Elf Atochem copyright Akzo Nobel
    plasticizer mixture
    Derakane® vinyl ester (VE) resin Dow Chemical
    Vamac® ethylene acrylic acid elastomer duPont LMA lauryl methacrylate monomer Sartomer
    Tyrin® chlorinated polyethylene DuPont Dow Elastomers
    Hycar® Reactive Liquid BD / An-Noveon, Inc.
    polymer
    Kraton® Styrene / Butadiene Block Copolymer Kraton Polymers
    HyTemp® polyacrylate elastomer Zeon Chemicals
    Hypalon® Chlorosulfonated polyethylene DuPont Dow Elastomers NOVA NAS-30 Styrene acrylic acid copolymer NOVA-Chemicals
    Chemigum® crosslinked nitrile rubber Eliochem
    Hycar® liquid nitrile polymer Noveon
    Reillcat ™ ASY-2 dihydropyridine derivative Reilly Industries Inc.
    Luperox® CU 90 cumene hydroperoxide (CHP) Alf Atochem ME KP methyl ethyl ketone peroxide Norac EDTA solution 5% solution of tetrasodium Aldrich (Na4EDTA.H20) ethylenediamine tetraacetate hydrate in 50% aqueous ethanol
    Light Ester Mixed Methacryloyloxyethyl Kyoeisha Chemical Co. Phosphate Ester HP 1310 Acrylic Acid Oligomer Hehr International
    Polymers
    PREPARATION OF ADHESIVE COMPOSITIONS
    Unless otherwise indicated, the following procedure using techniques well known in the art to prepare the experimental adhesives: Readily soluble or dispersible elastomers and resins were blended into methyl methacrylate (MMA) monomer in a beaker or a metal can on a laboratory roller mill to form a stock solution. The proportions of polymer and monomer were chosen to provide a convenient working viscosity to allow the addition and mixing of subsequent formulation ingredients. Typical solution concentrations in the MMA of 15-35 wt% polymer were chosen to provide final solvent viscosities in the range of about 50,000 to 500,000 cps. It is generally preferred to prepare the stock solutions in the higher concentration and viscosity ranges in order to be able to make final viscosity adjustments by diluting the final adhesive with MMA monomer. The polymer and monomer were rolled until all of the polymer was dissolved and no lumps or particles of undissolved material were present.
    Experimental adhesives were made in plastic cups in amounts ranging from about 100-600 grams of finished adhesive. Sufficient stock solution or a mixture of stock solutions was added in the required amount to the beaker to provide the desired level of elastomer in the final adhesive.
    When powdered toughening modifiers were added to the formulations, they were added to the polymer in monomer solution along with other non-catalytic liquid ingredients and blended with a high shear laboratory blender until a uniform, sometimes grainy paste consistency was achieved. The impact modifiers do not dissolve in the blend, but rather swell to give the adhesive a gel-like consistency. Generally, two to four hours is required for the toughening modifier to swell and soften sufficiently to be completely dispersed in the mixture. At this time, the adhesive is mixed a second time under high shear to form a smooth paste. At the end of the second mixing, the remaining ingredients are added and mixed thoroughly in the adhesive. Adhesives formulated without an impact modifier were prepared by adding the remaining ingredients directly to the mixture of stock elastomer solution and mixing thoroughly to form the final adhesive.
    Final viscosity adjustments were made by adding MMA monomer to reduce viscosity, or fumed silica or additional toughening modifier to increase viscosity as required.
    ADHESIVE EVALUATION TESTS AND METHOD
    MEASUREMENT OF EXOTHERMER TIME AND TEMPERATURE
    The peroxide and amine containing adhesive ingredients were mixed in the proportions specified in each example.
    The mixed sample was degassed in a vacuum desiccator to remove trapped air and placed in a draft-free, temperature-controlled clear plastic test chamber maintained at 75 ° F +/- 1 ° F (23.9 ° C +/- 0 , 5 ° C). The thermal wire attached to the exothermic recorder was inserted into the center of the adhesive mass to record the peak temperature attained and the time to peak temperature.
    CROPPING MARK OF SHAPED THICK CASTINGS
    To simulate thick bond cure markings, test molds were made from bonded bonded 0.25 inch (0.64 cm) polypropylene sheets to provide a rectangular cavity to form a 8 inch (20.32 cm) test casting. Length times 2 inches (5.08 cm) wide by 1.5 inches (3.81 cm) in height. An adhesive mass (approximately 500-600 grams, depending on specific gravity) was mixed and degassed as noted above and transferred to the test mold using a spatula to fully pack the mold and flatten the top exposed surface level with the top of the mold , The adhesive composition was allowed to cure and the appearance and condition of the cured casting was observed and recorded.
    The presence or absence of voids resulting from gas evolution or boiling was noted. An arbitrary scale of 1 to 4 was used to classify the formulations, where the value 1 represents essentially no gas evolution or "boiling" within the casting or surface, and 4 excessive mass "boiling" and gaseous expansion of the mass and formation represented by surface cavities. The intermediate values represent increasing degrees of internal and superficial cavitation during cure.
    To evaluate the effectiveness of the cure, the hardness of the casting surface and the center (measured in the center of a vertical section through the center of the bead) was measured using a Shore D Durometer.
    GLUE BINDING STRENGTH
    Adhesive bonds with open-formed glass fiber reinforced polyester test coupons were made, tested and reported according to ASTM D5868. The bonds were spread out to provide a nominal thickness of 0.125 inches (0.32 cm). Metal bonds were tested according to ASTM Dl002 using a 0.010 inch (0.025 cm) bond thickness.
    When reporting the overlap shear strength results, the following abbreviations are used throughout the examples for the corresponding failure modes: AF: ADHESIVE FAILURE. The adhesive separates cleanly from the substrate surface.
    CF: COHESION BREAK The defect occurs in the adhesive layer leaving a distinct adhesive layer on each substrate surface.
    TLCF: THIN-LAYER COHESION BREAK. The mistake seems to be of adhesive nature, with the mass of the adhesive on one surface and a thin residue of adhesive on the other.
    FT or DL: FIBER ABRASION OR DELAMINATION of Composite Substrate SF: Fracture failure and separation of the composite substrate at the adhesive bond line without bond separation.
    ADDITIONAL CHARACTERISTICS OF THE ADHESIVE MATERIAL
    Stress-strain properties of the adhesive mass were measured according to ASTM Test Method D638. Test samples were made by mixing a sufficient amount of adhesive to form a uniform flat adhesive film about 6 to 7 inches (15.24 cm to 17.78 cm) in diameter and about 0.0625 inch (0.16 cm) thick ). The adhesive ingredients were combined in the specified proportions by simple hand mixing in a beaker. After the adhesive was thoroughly mixed, the beaker was placed in a vacuum chamber and vacuum was applied intermittently to remove air until the last two applications of vacuum did not produce additional foaming or expansion. The adhesive was then transferred to one of two approximately 12 inch (30.48 cm) diameter glass or plastic plates with a similarly sized layer of Mylar release film on top. The plastic was placed in the center of the film and a matching Mylar sheeting and plate were placed over the adhesive and uniformly pressed down to spread the film. Metal balance pieces were placed around the circumference of the plates to establish the desired film thickness.
    After the films had cured, the plates were removed. Test dumbbells were cut from the films as specified in the test procedure by taking care to cut the samples from the most void-free section of the film. The films were allowed to cure overnight at ambient temperature, followed by thermal post cure at 82 ° C for one hour prior to cutting the dumbbells. Each test number is the average of five individual test patterns. EXAMPLES 1-2 Examples 1 and 2 are comparative examples for Inventive Examples 3-7 and 8-12, respectively. They illustrate that, when the respective invention examples are formulated without the addition of a vinyl ester resin, they experience significant gas evolution and boiling, although they effectively bond open-molded FRP composite in normally thin bonded (0.125 inch, 0.32 cm) cross sections. TABLE 1 EXAMPLE 1 2 MMA monomer 68.60 65.60
    Neoprene AD-10 20,00
    NipolDN4555 - 10.00 BTA753 - 18.00
    Lauryl 5.00 5.00
    Methacrylate HET 0.40 0.40
    Methacrylic acid 1.00 1.00
    Dibutyl phthalate 2.00
    Dow Derakane Vinyl Ester Resin Fumed Silica 3.00 3.00 55% BPO Paste 1.80 1.80 RESULTS Peak Exothermic 39-gram mass
    Time to peak, min. 30.3 44.4
    Temperature, ° C 142.22 135
    Thick Casting Cure Curing Observations 20.32 X 5.08 X 3.81 cm Qualitative Cure Rating (1 = Best, 4 = Worst)
    Surface boiling Overly Yes
    Surface boiling level 4 3 Hardness, Shore D not tested 30-35 (porous)
    Center of the bead n.t. 50-55 (porous)
    Overlap shear strength, PSI open-molded FRP n.t. 569
    Error mode n.t. 100% FT COMPARATIVE EXAMPLES 3 TO 6 AND EXAMPLE 7 Examples 3-7 illustrate the effectiveness of a preferred vinyl ester resin in improving the cure performance of methacrylate formulations containing a range of elastomeric polymers. Unlike Comparative Example 1, the compounds of the invention do not boil or gase to form expansion and undesirable voids in the thick casting bead that simulates a thick bonded cross-section. Example 3 (See) 4 (Comp.) 5 (Comp.) 6 (Comp.) 7 MMA monomer 58.60 58.60 58.60 58.60 58.60
    Nipol DN 4555 20,00 -. , ,
    Vamac D - 20,00
    Kraton D 1102 - - 20,00
    Neoprene AD-10 - - - 20,00
    Tyrin 3615P -. , , 12,00 BTA753 .... 8,00
    Lauryl 5.00 5.00 5.00 5.00 5.00
    Methacrylate HET 0.40 0.40 0.40 0.40 0.40 MAA 1.00 1.00 1.00 1.00 1.00 DBP 2.00 2.00 2.00 2.00 2.00
    Dow Derakane 10.00 10.00 10.00 10.00 10.00 VE Resin 411-350 Fumed Silica 3.00 3.00 3.00 3.00 3.00 55% BPO Paste 1.80 1.80 1.80 1.80 1.80 RESULTS 3 4 5 6 7
    Peak exotherm 39-gram mass
    Time to peak, min. 62.5 9.5 24.2 23.5 24.8
    Temperature, ° C 122.78 150.56 159.44 158.33 152.11
    Thick Casting Cure Curing Observations 20.32 X 5.08 X 3.81 cm Qualitative Cure Rating (1 = Best, 4 = Worst)
    Surface boiling no no no no no no
    Surface Thickening Level 4 1111 Hardness, Shore D 10-15 60-70 60-65 50-55 45-50
    Center of the bead 25-30 65-77 70-75 65-70 65-70
    Overlap shear strength, PSI open-molded FRP 580 755 715 955 820
    Failure Mode 100% FT 100% FT 100% FT 100% FT 100% FT
    It is noteworthy that Example 3, which contains a nitrile elastomer, did not cure as effectively as the other examples in the series. It is believed that this is the result of the antioxidant type and or degree employed in the elastomer as supplied by the manufacturer. As noted in the specification and examples that follow, adjustments in type or degree of amine promoter or level of BPO paste can be used to influence the cure behavior of individual compositions. EXAMPLES 8-12 Examples 8-12 illustrate that alternative catalyst systems can be effectively used to utilize the modification of the cure behavior of the compositions of the invention. A preferred vinyl ester resin and a preferred DCPD resin are used to illustrate this effect in these examples. EXAMPLE 8 9 10 11 12 MMA Monomer 55.60 55.60 55.25 55.00 55.00
    NipolDN4555 10.00 10.00 10.00 7.50 7.50
    Hypalon 30. , , 5.00 5.00
    Lauryl 5.00 5.00 5.00 5.00 5.00
    Methacrylate BTA753 18,00 18,00 18,00 16,00 16,00 MAA 1,00 1,00 1,00 1,00 1,00 HET 0,40 .... DMPT - 0,40 CHP - - 0 , 50 0.50 0.50 p-toluene - - 1.00 -
    sulfonyl
    Dow Derakane 10.00 10.00 10.00 10.00 VE Resin 411-350
    Reichhold 44-006. , - - 10.00 DCPD resin 55% BPO paste 1.80 1.80
    Reillcat ASY-2 - - 1.00 1.00 1.00 RESULTS Peak exotherm 39-gram mass
    Time to peak, min. 33.6 46.3 73.4 35.7 56.8
    Temperature, Ό 131.66 108.33 117.78 155 158.33
    Thick Casting Cure Curing Observations 20.32 X 5.08 X 3.81 cm Qualitative Cure Rating (1 = Best, 4 = Worst)
    Surface boiling no no no no no no
    Surface Thickening Level 11111 Hardness, Shore D 50-55 20 65-70 70-75 60-65
    Center of the bead 60-70 25 70-75 70-75 65-70
    Overlap shear strength, PSI open-molded FRP 490 555 465 455 610
    Failure Mode 100% FT 100% FT 100% FT 100% FT 100% FT
    Examples 8 and 9 illustrate that when other variables are constant, HET may be more effective than DMT in combination with BPO in promoting complete cure of a specific composition as measured by hardness of the cured composition. Examples 10-12 illustrate that a preferred vinyl ester resin and a preferred DCPD resin can be used to very effectively and beneficially modify the cure behavior of compositions employing the chlorosulfonated polyethylene / sulfonyl chloride / DHP cure system. It is well known to those skilled in the art that such cure systems are highly reactive and difficult to control in terms of boiling and gas evolution in other than very thin bonds or small masses.
    Comparative Example 13 and Examples 14 to 17 Examples 13-17 illustrate the effects of four different and preferred modifier resins on the cure properties of a specific and compositionally constant methacrylate formulation compared to a comparative formulation containing no modifier resin. TABLE 4 (comparative) EXAMPLE 13 14 15 16 17 MMA monomer 50.00 50.00 50.00 50.00 50.00
    NipolDN4555 7.50 7.50 7.50 12.00 12.00
    Nova NAS 30 4,80 4,80 4,80 4,80 4,80 LMA 1,50 1,50 1,50 1,50 1,50 HET 0,39 0,39 0,39 0,39 0,39 1.4-NQ 0.003 0.003 0.003 0.003 0.003 MAA 0.75 0.75 0.75 0.75 0.75 DBP 1.00 1.00 1.00 1.00 1.00 BTA 753 20.38 20.38 20.38 20.38 20.38 fumed silica 2.20 2.20 2.20 2.20 2.20
    Paraffin wax 0.50 0.50 0.50 0.50 0.50
    Eastman 711-1530 - 10.00
    Flex Ortho resin
    Eastman 126-0863 - - 10.00
    Flex ISO resin
    Reichhold 44-006 - 10.00 DCPD resin
    Dow Derakane - 10.00 VE resin 411-350 55% BPO paste 1.80 1.80 1.80 1.80 1.80 RESULTS Peak exotherm 39-gram mass
    Time to peak, min. 45.2 46 46 240 26
    Temperature, ° C 137.78 123.33 124.44 92.78 142.78
    Thick Casting Cure Curing Observations 20.32 X 5.08 X 3.81 cm Qualitative Cure Rating (1 = Best, 4 = Worst)
    Surface boiling yes no no no no no
    Surface thickening level 3 1111 hardness, Shore D porous 55-60 60-62 0-10 60-63 surface only) Examples 14 and 15 illustrate that the preferred orthophthalic and isophthalic resins provide similar reactivity as through time to peak Exothermic and peak exothermic temperatures measured. Examples 16 and 17 illustrate that based on the orthophthalic and isophthalic resins, the preferred DCPD resin imparts much lower reactivity and the preferred vinyl ester resin imparts much higher reactivity as measured by time to peak exotherm and peak exotherm temperature. As noted in the description and in the other examples, the reactivity of Examples 16 and 17 would be readily matched with appropriate changes in the amount or type of initiator and promoter. EXAMPLE 18 AND COMPARATIVE EXAMPLE 19 Examples 18-19 show the formulation of an adhesive for bonding class A glass fiber cartridges without read-through by incorporating a polyester flexible resin into the composition. To bond a metal clip to a fiberglass panel A 1 inch by 4 inch by 0.062 inch (2.54 cm by 10.16 cm by 0.16 cm) strip of aluminum was placed on the rough side of a 4 inch by 4 inch by 0.125 inch (10.16 cm by 10 gauge, 16 cm by 0.32 cm) fiberglass panels are bonded to a Class A show surface using a mass of 20 grams of adhesive. Spacers were used to balance the bond at a thickness of 0.375 inches (0.95 cm). The adhesive scented the cure cycle to the peak exotherm followed by cooling to ambient temperature with results as noted at the end of Table 5. EXAMPLE 18 19 (comparative) MMA monomer 57.00 64.60
    Hycar 1300X33 2.00 2.00
    Tyrin 3615P 12,50 12,50 BTA753 18,00 18,00 HET - 0,40 DMPT 0,50
    Methacrylic acid 2.50 2.50
    Flexible orthophthalic 7.50
    Polyester base resin 55% BPO paste 1.80 1.80 RESULTS Peak exotherm 20 grams mass
    Time to peak, min. 20.3 16.8
    Temperature ° C 121.67 138.89
    Print-Through None Print-Through Visibly Observed on Show Surface The comparative print-through was observed through the loose visual technique traditionally used by those skilled in the art. The bonded assembly is positioned with the show surface perpendicular to a strong light source such as a fluorescent lamp and viewed at an oblique, nearly parallel angle. Under such conditions, the presence or absence of print-through is easily apparent. EXAMPLES 20-21 Example 20 illustrates an improved formulation that provides a long open time adhesive that does not boil in a thick bead and provides complete cure without softness or stickiness or lingering odor of unreacted monomer in a thin film. Example 20 is a composition of the invention containing a flexible polyester resin. Example 21 is a comparative example utilizing vinyl toluene to provide extended open time. The examples illustrate that the composition of the invention does not boil when applied in a thick (1 inch, 2.54 cm) bead, but to a hard state in a thin (0.10 inch, 0.25 cm) Film hardens. The comparative example (formulated for slow cure) does not boil in a thick bead, but does not effectively cure in the thin film, as illustrated by the finger hardness test. Importantly, the example of the invention has significantly longer open working time than the comparative example, but completely cures with a lower peak exotherm temperature. When formulated for faster cure, the example of the invention does not boil, but the comparative example does.
    Comparison of Examples 20B and 21B illustrates a significant improvement in the tensile strength and elongation of the composition of the invention containing the polyester resin. EXAMPLE 20 21 MMA monomer 50.00 56.50
    Lauryl methacrylate 1.50 4.00
    Nipol DN 4555 7.50 7.50 NAS-30 4.80 4.80
    Paraloid BTA 753 20,40 18,00
    Flexible orthophthalic 10.00
    Polyester base resin
    Vinyl toluene - 1.25
    Methacrylic acid 0.75 1.75
    Dibutyl phthalate 1.00 2.30 HET 0.39 0.30 1,4-naphthoquinone 0.003 5% EDTA solution 1.00 1.00 fumed silica 2.20 1.90
    Paraffin wax 0.50 0.70 The results marked 20A and 21A were obtained as formulations 20 and 21 in a ratio of 43: 5 by weight with IPS Weld-On® SS 218 HVB activator, a proprietary healing paste [ sic] containing 5.6 percent by weight of benzoyl peroxide were mixed. Results 20B and 21B were obtained with an experimental curing paste containing 7.7 percent benzoyl peroxide. Cure state observations were made four hours after the peak exotherm was reached.
    RESULTS 20A 20B 21A 21B
    Curing behavior, 25 grams of mass
    Open hours, min. 73.6 47.3 53.1 46.0
    Peak exotherm time, min. 93.4 66.4 72.4 61.3
    Peak-Exotherm Temp. ° C 102,22 116,67 117,78 131,11
    Thick bead curing results dimensions of the bead 5.08 inches x 15.24 inches x 2.54 inches
    Surface boiling observed no no no no Hardness, Shore D 55 60 60 55
    Monomer odor no no no no Thin film curing results
    Film dimensions 5.08 cm x 15.24 cm x 0.25 cm
    Surface boiling observed no no no no hardness when touched hard hard soft hard
    Monomer odor no no yes no
    Tensile properties ASTM D638
    Load at break (psi) 3271 2840
    Elongation (%) 198 180 EXAMPLE 22 Example 22 illustrates the improvement in adhesive bonding strength at elevated temperature obtained with the addition of a vinyl ester resin. Example 22B, which contains 10 percent of a preferred vinyl ester resin, has more than twice the bond strength of 121.11X as Comparative Example 22A, which does not contain any additional resin. The fiber tear bond failure mode shown by Example 22B further illustrates the increased strength of the cured adhesive formulation of the invention at elevated temperature.
    EXAMPLE ADHESIVE ACTIVATOR
    22A 22B 22C
    Tyrin 3615P 12,00 .................
    Hycar 1300X33 2.00 ................... PARALOID BTA 753 17, 50 ................ 12, 00 MMA -Moner 58.80 ................. 55.75
    Methacrylic acid 6.00 ...................
    Paraffin wax 0,65 ................... 1,25 fumed silica 0,75 ...................
    Titanium dioxide 22,00 MEKP 0,75 ................... CHP 0,75 ................... 2.4- pentandione 0.80 ................... 12% cobalt octoate - 3.00 DMPT - 6.00 1.4-naphthoquinone 0.005 0.005 0.01
    Total 100,005 100,005 100.01
    MIXED ADHESIVES
    Grams of adhesive 100.00 90.00 VE 9420 Vinylester resin 0 10.00
    Grams of activator 10 10
    RESULTS Overlap shear ASTMD5856 125 270
    Bond strength at 121.11 O, psi
    Error Mode CF (100%) FT (50-100%) EXAMPLE 23 Example 23 illustrates a composition of the invention capable of bonding glass fiber panels with no observable print-through, as well as bonding aluminum without surface preparation. Adhesion to unprepared aluminum is achieved by the addition of a methacryloyloxyethyl phosphate ester. EXAMPLE 23
    Neoprene AD-10 12.5
    Tyrin 3615P 9.0
    Nipol DN 4555 4.0
    Flexible orthophthalic polyester base resin 5,00
    Phosphate ester 1.20
    Methacrylic acid 5.00 HP1310 acrylic acid oligomer 3.80 DMPT 1.4 1.4-naphthoquinone 0.0035 MMA monomer 53.06
    Paraloid BTA 753 5.00 The adhesive was mixed at a ratio of 8.3 to 1 by weight with Weld-On SS 605B Activator, a proprietary paste containing 13.5 percent BPO by weight. Print-through test was performed as in Example 18. RESULTS Peak exotherm 10 grams mass
    Open time, min. 5.1
    Time to peak, min. 9.4
    Temperature ° C 109.44
    Print-through not observed
    Overlap shear R.T. 2638 psi, 100% CF
    Aluminum, ASTM DI002
    Overlap Shear Strength, R.T. 899 psi, 100% FT
    Aluminum / FRP, ASTM 5868 Although the present invention has been described with reference to the preferred embodiment, it will be appreciated that the description has been made for the purpose of understanding the present invention and various changes and modifications may be made without departing to deviate from the scope of the invention.
    权利要求:
    Claims (14)
    [1]
    claims
    A polymerizable adhesive or filler composition for large assemblies comprising from 5 to 75% by weight of a mixture of one or more elastomers with one or more partially thermoplastic polymers selected from the group consisting of core / shell impact modifiers, polychloroprene elastomers and elastomeric polymers, from 0.5 to 35% by weight of an unsaturated polyester resin or vinyl ester resin, and from 20 to 80% by weight of an alkyl acrylate or methacrylate monomer, and wherein the partially thermoplastic polymers are crosslinked to render them insoluble in the monomer or only partially soluble, and wherein the elastomers are completely soluble in the monomers.
    [2]
    2. A polymerizable adhesive or filling composition according to claim 1, which contains from 10 to 60 wt .-%, preferably 15 to 50 wt .-% of the mixture, from 1 to 25 wt .-%, preferably 2 to 20 wt .-% of unsaturated polyester resin or vinyl ester resin and 30 to 80 wt .-%, preferably 40 to 70 wt .-% of the alkyl acrylate or methacrylate monomer.
    [3]
    The polymerizable adhesive or fill composition of claim 1 or 2, wherein the unsaturated polyester or vinyl ester resin is selected from the group consisting of unsaturated orthophthalic, isophthalic, terephthalic and dicyclopentadiene polyester resins, vinyl ester resins, halogenated polyester resins, halogenated vinyl ester resins, and mixtures it.
    [4]
    The polymerizable adhesive or fill composition of any one of claims 1-3, further comprising from 0.01% to 20% by weight of a polymerizable organic acid monomer or oligomer, wherein the polymerizable organic acid monomer is preferably methacrylic acid or acrylic acid or acrylic acid Mixtures thereof comprises or selected from the group consisting of maleic acid, fumaric acid, itaconic acid and mixtures thereof or a vinyl-substituted phosphate ester.
    [5]
    The polymerizable adhesive or fill composition of any one of claims 1-4 further comprising from 0.1 to 10% by weight of a viscosity control agent.
    [6]
    The polymerizable adhesive or fill composition of any one of claims 1-5, further comprising one or more materials selected from the group consisting of catalysts, initiators, reducing agents, activators, promoters, and mixtures thereof.
    [7]
    The polymerizable adhesive or fill composition of any of claims 1-6, further comprising a member selected from the group consisting of a chlorosulfonated polymer, an organic sulfonyl chloride, and a dihydropyridine.
    [8]
    The polymerizable adhesive or fill composition of any of claims 1-7, further comprising a member selected from the group consisting of a hydroperoxide, a dione and other chelating agents, an organometallic salt and an aromatic amine.
    [9]
    The polymerizable adhesive or filling composition of any one of claims 1-8, wherein the one or more elastomer chlorinated polymers includes (s) polymer (s).
    [10]
    The polymerizable adhesive or fill composition of any one of claims 1-9, wherein the one or more elastomeric polychloroprene (s) includes.
    [11]
    The polymerizable adhesive or fill composition of any one of claims 1-8, wherein the one or more elastomer includes chlorinated polyethylene (s).
    [12]
    The polymerizable adhesive or fill composition of any one of claims 1-11, wherein the one or more elastomer includes styrene-butadiene-styrene (SBS) block copolymer (s).
    [13]
    The polymerizable adhesive or fill composition of any one of claims 1-11, wherein the one or more elastomer includes styrene-isoprene-styrene (SIS) block copolymer (s).
    [14]
    Use of a polymerizable adhesive or filling composition according to any one of claims 1-13 in adhesive, coating, filling or repair applications.
    类似技术:
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    同族专利:
    公开号 | 公开日
    US7795351B2|2010-09-14|
    US20050014901A1|2005-01-20|
    HK1101042A1|2007-10-05|
    AU2004284427B2|2011-05-26|
    AT13638U3|2015-01-15|
    AU2004284427A1|2005-05-06|
    AU2004284427A2|2005-05-06|
    ES2463473T3|2014-05-28|
    US7816453B2|2010-10-19|
    WO2005040295A1|2005-05-06|
    JP5391517B2|2014-01-15|
    US20070142556A1|2007-06-21|
    CA2542381C|2012-07-17|
    JP2007508445A|2007-04-05|
    DK1682626T3|2014-05-19|
    EP1682626A1|2006-07-26|
    US20080177004A1|2008-07-24|
    CN1898350A|2007-01-17|
    EP1682626B1|2014-04-30|
    CN1898350B|2012-07-11|
    USRE46269E1|2017-01-10|
    CA2542381A1|2005-05-06|
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    法律状态:
    2014-12-15| MK07| Expiry|Effective date: 20141031 |
    优先权:
    申请号 | 申请日 | 专利标题
    US10/688,441|US20050014901A1|2001-07-10|2003-10-17|Adhesive compositions for bonding and filling large assemblies|
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