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    • 专利摘要:
    heat-curable structural adhesive and method of joining an aluminum member to a second metal member. a thermosetting structural adhesive includes a non-rubber modified epoxy resin, a carboxyl or amine terminated butadiene polymer or copolymer reaction product, and a bisphenol f-based epoxy resin, an elastomeric stiffener containing capped isocyanate groups, one or more epoxy curing agents, a moisture scavenger and a thermoactivatable catalyst comprising a mixture of a solid or liquid tertiary amine compound having a boiling temperature of at least 130°C and a novolac resin. the structural adhesive develops excellent bonding properties when cured at moderate temperatures, especially 120 to 170°C, and furthermore performs very well in the stress environmental aging test. the adhesive is particularly good for bonding aluminum to another metal, or for bonding aluminum to aluminium.
    公开号:BR112014018129B1
    申请号:R112014018129-2
    申请日:2013-03-22
    公开日:2021-07-20
    发明作者:Glenn G. Eagle；Andreas Lutz；Gary L. Jialanella；Dakai Ren
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    technical field
    [001] The present invention relates to a structural adhesive based on epoxy and a process for bonding metal members, especially aluminum. prior technique
    [002] Epoxy-based adhesives are used in the manufacture of fasteners to bond metals to other metals or other materials. In the automotive industry, these adhesives are used to bond structural members together or to other parts of the vehicle. Before suitable adhesives were developed, the main method for assembling these structural members to each other or to other parts was by welding, or, in some cases, by other mechanical means. Structural adhesive totally or partially replaces welding and mechanical fixings.
    [003] A class of structural adhesives was developed for these applications. They are commonly referred to as “crash durable adhesives” or “CDAs” because they are formulated to resist failure during high-strength conditions experienced in crashes. A notable class of CDAs are based on one or more epoxy resin(s) modified with rubber or with an elastomeric “hardener”. Structural adhesives of this type are described, for example, in U.S. Patent Nos. 5,202,390, 5,278,257, Published U.S. Patent Application No. 2005/0070634, Published U.S. Patent Application No. 2005/0209401, Published U.S. Patent Application 2006/0276601, Published U.S. Patent Application No. 2008/0251202, EP-A-0 308 664, EP-A 1 728 825, EP-A 1 896 517, EP-A 1 916 269, EP-A 1 916 270 , EP-A 1 916 272, EP-A 1 916 285, WO 2005/118734 and WO 2012/000171.
    [004] The formulation of most CDAs requires high temperature curing. It is common to integrate this curing step with other steps in the manufacturing process, which also require high temperatures. This represents a significant savings in manufacturing costs. For example, vehicular frame assemblies are typically coated with a protective coating, which requires bake curing. An increasingly common practice is to cure the CDA concurrently with the protective coating. In this process, the CDA is applied to the elements of the structure, which are then assembled together. Part or all of the structure's elements are typically welded together (although they can be temporarily held together using other mechanical means) and the assembly is then coated with the protective coating and baked to cure the coating. CDA cures during the heating step.
    [005] CDAs must meet multiple requirements simultaneously. When cured, the adhesive must also be able to withstand strong mechanical shocks, such as those suffered during a collision. This property can be measured using an impact peel strength test such as the ISO 11343 wedge impact method. Another requirement is that the adhesive bond must be able to withstand mechanical stress even during or after exposure to corrosive materials , such as saline solutions. This property is important as vehicular frame assemblies are routinely exposed to saline solutions, particularly during the winter months when salts are often applied to highways to melt snow and ice. A useful test method for evaluating tensile strength under corrosive conditions is a tensile durability test, such as that described by Dickie, DeBolt and Ward, in “Stress Durability Testing of Adhesively Bonded Steel,” SAE Technical Paper 950128, 1995 The cured adhesive must maintain these properties over a wide range of temperatures.
    [006] In addition, CDA preferably meets the required properties when bonded to various substrates, including cold-rolled steel, galvanized steel, and, notably, aluminum. Aluminum bonding often poses a specific challenge, especially with regard to durability under stress and resistance to impact peeling. Many CDAs do not meet the stress durability requirements when used to bond aluminum.
    [007] Some CDAs can meet impact peel strength requirements if cured at temperatures above 170°C. However, it has been found that impact peel strength is highly dependent on the cure temperature, and even a small drop in the cure temperature, such as up to 160°C or so, often leads to poor performance of impact peeling. Unfortunately, inadequate curing temperatures are very often seen in industrial furnaces, especially large furnaces that can accommodate large structures such as automotive frame assemblies. This is due to several factors. In terms of energy and cost, manufacturers prefer to operate at the lowest possible temperatures. When the adhesive is cured simultaneously with a coating bake step, the temperature is often selected to meet the coating bake requirements rather than those of the adhesive. Also, heat distribution can be far from uniform in large ovens, which leads to large differences in temperature in various parts of the oven. Solid parts also act as heat sinks that often remain cooler than the oven's nominal temperature, so an adhesive layer that holds these parts together does not reach the full oven temperature. For these reasons, the adhesive may not reach the curing temperature necessary to fully develop its impact peel strength. It would therefore be desirable to provide a CDA that develops adequate impact peel strength even when cured at temperatures of 150-170°C, with the adhesive also having other necessary properties, such as good overlap shear strength and good tensile strength .
    [008] In one aspect, the present invention consists of a thermosetting structural adhesive comprising: A) at least one epoxy resin not modified with rubber; B) a reaction product of a polymer or copolymer of butadiene with carboxyl or amine termination and a bisphenol-based epoxy resin F; C) at least one elastomeric stiffener containing capped isocyanate groups; D) one or more epoxy curing agents; E) from 0.5 to 10 percent by weight of a moisture scavenger, with based on the total weight of the heat-curable structural adhesive; and F) a thermally activated catalyst comprising a mixture of a solid or liquid tertiary amine compound having a boiling temperature of at least 130°C and a novolac resin, the elastomeric stiffener and rubber portion of the epoxy resin modified with rubber together make up 15 to 25% of the total weight of the heat-curable adhesive.
    [009] The invention exhibits excellent impact shear strength, storage modulus at 50 °C, with the exception of environmental aging under stress, even when cured at slightly lower temperatures, such as 120 to 170 °C, and especially at 150 to 170°C. The invention also exhibits excellent moisture modulus and a surprisingly high creep apparent activation energy. The ability to develop these properties and moderate cure temperatures is an important advantage in automotive production scenarios where curing is conducted in conjunction with the back-cure of an automotive coating.
    [010] In some embodiments, the structural adhesive, when cured:
    [011] a) exhibits an impact shear strength of at least 20N/mm, measured in accordance with ISO 11343 wedge impact method on 2mm thick 6111 aluminum alloy substrates, after curing at 160°C for 10 minutes,
    [012] b) exhibits a storage module of at least 900 MPa at 50°C, measured through mechanical dynamic analysis, in accordance with ASTM E2254-09; and/or
    [013] c) withstands at least 45 cycles of thermal aging under the stress test described below, after curing for 10 minutes at 160°C.
    [014] The invention is also a method for bonding an aluminum member to a second metallic member, comprising forming a heat-curable structural adhesive layer between and in contact with the aluminum member and the second metallic member and then heating the structural adhesive to a temperature of at least 120°C to 170°C to cure the structural adhesive and form an adhesive bond between the aluminum member and the second metallic member, the thermosetting structural adhesive comprising: A) at least one unmodified epoxy resin with rubber; B) a reaction product of a carboxyl or amine terminated butadiene polymer or copolymer and bisphenol-based epoxy resin F; C) at least one elastomeric stiffener containing capped isocyanate groups; D) one or more curing agents epoxy;E) from 0.5 to 10 percent by weight of a moisture scavenger, based on the total weight of the heat-curable structural adhesive; and F) a thermally activated catalyst including a mixture of a solid or liquid tertiary amine compound having a boiling temperature of at least 130°C and a novolac resin, the elastomeric stiffener and the rubber portion of the modified epoxy resin with rubber together constitute 15 to 25% of the total weight of the heat-curable adhesive.
    [015] The heat-curable structural adhesive contains at least one non-rubber modified epoxy resin, which means an epoxy resin that is not (before curing) chemically bonded to a rubber. The non-rubber modified epoxy resin will preferably constitute at least about 25 percent by weight of the thermosetting structural adhesive, more preferably about at least 30 percent by weight. The non-rubber modified epoxy resin may constitute up to about 55 percent by weight of the heat-curable structural adhesive, more preferably up to about 50 percent by weight and most preferably up to 45 percent by weight. Such amounts include any free epoxy resin contained in a rubber modified epoxy resin composition, as described below, as well as any free epoxy resin in which core-shell type rubber particles are dispersed, also as described below.
    [016] The unmodified epoxy resin or resins preferably have an average epoxy equivalent weight of 170 to 600, more preferably 170 to 500 and even more preferably 170 to 400.
    [017] A wide range of epoxy resins can be used as the non-rubber modified epoxy resin, including those described in column 2 line 66 to column 4 line 24 of U.S. Patent No. 4,734,332, incorporated herein by reference. The non-rubber modified epoxy resin or resins should have on average at least 2.0 epoxy groups per molecule.
    [018] A preferred type of non-rubber modified epoxy resin is a diglycidyl ether of a polyhydric phenolic compound, such as resorcinol, catechol, hydroquinone, biphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)- 1-phenyl ethane), bisphenol F, bisphenol K and tetramethylbiphenol. Resins such as these may have average epoxy equivalent weights from about 170 to 2000, preferably from 225 to 400. Examples of epoxy resins of this type include bisphenol A diglycidyl ethers, such as those supplied by Dow Chemical under the DER® resin designations 330, DER® 331, DER® 332, DER® 383, DER® 661, DER® 662, and DER® 667. An especially preferred unmodified epoxy resin is a mixture of at least one diglycidyl ether of a polyhydric phenol, preferably bisphenol A or bisphenol F, having an epoxy equivalent weight of 170 to 299, especially 170 to 225, and at least one second phenol diglycidyl ether, again preferably bisphenol A or bisphenol F, this having an epoxy equivalent weight of at least 300, preferably from 310 to 2000. Such an especially preferred unmodified epoxy resin blend with rubber may include up to 20%, more preferably up to 10% by weight of another type of epoxy resin as described. below.
    [019] Other useful non-rubber modified epoxy resins (any of which can be used alone or in admixture with one or more of the others) include, for example, diglycidyl ethers of aliphatic glycols and polyether glycols, such as diglycidyl ethers of alkylene glycols C2-24 and polyethylene oxide and polypropylene oxide (including those supplied by Dow Chemical as DER® 732 and DER® 736); polyglycidyl ethers of phenol-formaldehyde novolac resins (epoxy novolac resins), including those supplied as D.E.N.® 354, D.E.N.® 431, D.E.N.® 438 and D.E.N.® 439 by Dow Chemical; alkyl substituted phenol-formaldehyde resins; phenol-hydroxybenzaldehyde resins; cresol-hydroxybenzaldehyde resins; dicyclopentadiene-phenol resins; cycloaliphatic epoxides, including (3,4-epoxycyclohexyl-methyl)-3,4-epoxy-cyclohexane carboxylate, bis-(3,4-epoxycyclohexyl)adipate, vinylcyclohexene monoxide, as well as others as described in U.S. Patent No. 3,686 .359; oxazolidone-containing compounds as described in U.S. Patent No. 5,112,932; dicyclopentadiene substituted phenolic resins; and advanced epoxy-isocyanate copolymers, such as those commercially supplied as D.E.R. 592 and D.E.R. 6508 (Dow Chemical).
    [020] The thermosetting structural adhesive includes at least one rubber-modified Bisphenol F-based epoxy resin. A rubber-modified bisphenol-based epoxy resin is a reaction product of a carboxyl- or amine-terminated liquid butadiene polymer or copolymer (the liquid rubber) with a bisphenol F-based epoxy resin. F is a bisphenol F diglycidyl ether, which can be partially advanced. The bisphenol F epoxy resin may have an equivalent weight of 157 to 2000, preferably 170 to 350 and more preferably 170 to 220. The resulting material has reactive epoxy groups which allow it to react further when the thermosetting structural adhesive is cured . It is preferred that at least a portion of the liquid rubber has a glass transition temperature (Tg) of -30°C or less, especially -40°C or less. The Tg of rubber can be as low as -100°C or even lower.
    [021] Liquid rubber is a homopolymer or copolymer of butadiene, especially a copolymer of butadiene and a nitrile monomer. The preferred nitrile monomer is acrylonitrile. The rubber preferably contains from about 1.5, more preferably from about 1.8 to about 2.5, more preferably up to about 2.2 epoxide-reactive terminal amino or carboxyl groups per molecule, on average. Carboxy-terminated butadiene polymers and copolymers are preferred. The molecular weight (Mn) of the butadiene polymer or copolymer is from about 2000 to about 6000, more preferably from about 3000 to about 5000.
    [022] Butadiene and butadiene/acrylonitrile copolymers with carboxyl functionality are marketed by Noveon under the brands Hycar® 2000X162 - carboxyl terminated butadiene homopolymer, Hycar® 1300X31, Hycar® 1300X8, Hycar® 1300X13, Hycar® 1300X9 and Hycar® 1300X18 - carboxyl-terminated butadiene/acrylonitrile copolymers. A suitable amine terminated butadiene/acrylonitrile copolymer is sold under the trade name Hycar® 1300X21.
    [023] Rubber-modified epoxy resin is formed by reacting butadiene polymer or copolymer with excess bisphenol F epoxy resin. Sufficient epoxy resin is provided to react with substantially all of the epoxy-reactive amino or carboxyl groups over rubber and to provide free epoxide groups in the resulting adduct without significantly advancing the adduct to form high molecular weight species. A ratio of at least two equivalents of epoxy resin per equivalent of epoxy-reactive groups on rubber is preferred. More preferably, more than two equivalents of epoxy resin per equivalent of epoxy-reactive groups are provided in the rubber as this forms a mixture of the rubber-modified epoxy resin and some free (unreacted) epoxy resin and also helps to minimize advance . The presence of free epoxy resin tends to reduce product viscosity. Any such free epoxy resin in the mixture counts as part of the unmodified epoxy resin content of the adhesive.
    [024] A preferred rubber-modified epoxy resin is a reaction product of an amine- or carboxyl-terminated butadiene homopolymer or copolymer with a bisphenol F diglycidyl ether, which after reaction may be diluted with another epoxy resin, such as a diglycidyl ether of a bisphenol, such as bisphenol A or bisphenol F and having an epoxy equivalent weight of about 170 to 2000. Diluting the rubber-modified epoxy resin can reduce its viscosity to a useful level. The epoxy resin used to dilute the rubber-modified epoxy resin, along with any unreacted bisphenol diglycidyl ether, will form part of the un-rubber-modified epoxy resin.
    [025] The elastomeric stiffener is a liquid or low-melting elastomeric material that contains urethane and/or urea groups and end block isocyanate groups. Blocking isocyanate groups have been reacted with a compound that has one or more functional groups that can reversibly react with an isocyanate group to form the blocking group.
    [026] The elastomeric stiffener preferably contains up to 6, more preferably up to four such block isocyanate groups. Stiffeners of this type are described, for example, in U.S. Patent Nos. 5,202,390, 5,278,257, Published US Patent Application No. 2005/0070634, Published US Patent Application No. 2005/0209401, Published US Patent Application No. 2006/0276601, Published US Patent Application No. 2008/ 0251202, EP-A- 0 308 664, EP-A 1 728 825, EP-A 1 896 517, EP-A 1 916 269, EP-A 1 916 270, EP-A 1 916 272, EP-A-1 916 285, WO 2005/118734 and WO 2012/000171.
    Preferably, the weight average molecular weight of the elastomeric stiffener is about 8,000 or more, and more preferably about 10,000 or more. Preferably, the molecular weight of the stiffener is about 70,000 or less, and more preferably about 40,000 or less. Molecular weights, as used herein, are determined by gel permeation chromatography (GPC). The elastomeric stiffener preferably has a viscosity at 45°C not greater than 1000 Pa.s, and more preferably not greater than 800 Pa.s.
    [028] The stiffener is preferably linear, branched or at most lightly crosslinked, preferably containing a screen density of about 2 or less and preferably of about 1 or less. Screen density is the number of bonds between polymer chains.
    [029] The elastomeric stiffener advantageously includes at least one segment of polyether, polybutadiene or polyester having a molecular weight of 300 to 3000. The segment(s) of polyether, polybutadiene or polyester may be part of a polyurethane and/or polyurea main chain.
    [030] The stiffener is prepared by forming a prepolymer with isocyanate termination by reacting an excess of a polyisocyanate with one or more materials reactive with isocyanate and then blocking the terminal isocyanate groups by reacting with the blocking agent. Isocyanate-reactive materials preferably include at least one polyether, polybutadiene or polyester segment having a molecular weight of 300 to 3000 and isocyanate-reactive groups. Isocyanate-reactive materials can also include one or more crosslinking compounds and/or low molecular weight chain extenders.
    [031] The polyisocyanate is preferably an aliphatic polyisocyanate such as isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated methylene diphenylisocyanate (H12MDI) and the like.
    [032] Suitable blocking agents include those that form non-reactive blocking groups, and those that form reactive blocking groups.
    [033] Blocking agents that form non-reactive blocking groups have a group reactive with simple isocyanate, and no other groups reactive with epoxy groups. Examples of this type of blocking agents include monophenolic compounds, monoamine compounds, such as primary or secondary aliphatic, cycloaliphatic or aromatic monoamines, monothiol compounds, benzylamines, and the like. Among these, monophenols such as phenol, alkylphenols containing one or more alkyl groups each of which may contain from 1 to 30 carbon atoms, naphthol or a halogenated phenol or naphthol, are preferred.
    [034] Blocking agents that form reactive blocking groups have at least one group reactive with isocyanate, and, in addition, at least one other group reactive with epoxy resins (and which may also be reactive with isocyanate groups). Among the blocking agents of this type are polyphenolic and aminophenolic compounds. Examples of suitable polyphenols include resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenyl ethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol and o,o '-dialyl-bisphenol A, as well as its derivatives. Aminophenol blocking agents contain at least one primary or secondary amino group and at least one phenolic hydroxyl group. The amino group is preferably attached to an aromatic ring carbon atom. Examples of suitable aminophenols include 2-aminophenol, 4-aminophenol, various aminonaphthols and the like.
    [035] The stiffener in addition to the weight of the rubber included in the rubber-modified epoxy resin and the core-shell type rubber constitutes from 15 to 25%, more preferably from 16 to 25% and even more preferably from 16 to 22% of the total weight of the thermosetting structural adhesive. The rubber included in the rubber-modified epoxy resin, in some embodiments, constitutes from 2 to 10 percent, preferably from 4 to 8 percent, of the total weight of the structural adhesive. The stiffener preferably constitutes at least 5 percent of the adhesive composition, more preferably at least 8 percent by weight and even more preferably at least 10 percent by weight thereof, up to 20 percent by weight and more preferably up to 16 percent. by weight.
    [036] The structural adhesive also contains a curing agent. The curing agent is selected along with any catalyst(s), so that the adhesive cures rapidly when heated to a temperature of 80°C or more, preferably 120°C or more, and even more preferably 140°C, although it cures very slowly, if possible, at room temperature (°C) and temperatures up to at least 50°C. Suitable curing agents include materials such as boron trichloride/amine and boron trifluoride/amine complexes, dicyandiamide, melamine, diallylmelamine, guanamines such as acetoguanamine and benzoguanamine, aminotriazoles such as 3-amino-1,2,4- triazole, hydrazides such as adipic dihydrazide, stearic dihydrazide, isophthalic dihydrazide, semicarbazide, cyanoacetamide, and aromatic polyamines such as diaminodiphenylsulfones. The use of dicyandiamide, isophthalic acid dihydrazide, adipic acid dihydrazide, and/or 4,4'-diaminodiphenylsulfone is particularly preferred.
    [037] The curing agent is used in an amount sufficient to cure the composition. Typically, a sufficient amount of the curing agent is provided to consume at least 80% of the epoxide groups present in the composition. A large excess beyond that amount needed to consume all the epoxide groups is generally not necessary. Preferably, the curing agent constitutes about at least 1.5 percent by weight of the structural adhesive, more preferably about at least 2.5 percent by weight, and even more preferably at least 3.0 percent by weight. The curing agent preferably constitutes up to about 15 percent by weight of the structural adhesive composition, more preferably up to about 10 percent by weight, and most preferably up to about 8 percent by weight.
    [038] The structural adhesive contains 0.5 to 10 percent, preferably 2 to 5 percent by weight of a moisture scavenger. It was found that the presence of the moisture eliminator greatly increases the opening time of the structural adhesive at temperatures below 80°C. The moisture scavenger binds (chemically or physiochemically) to the free water present in the thermosetting structural adhesive and more preferably does not release the bound water until it is heated to a temperature of at least 160°C, preferably at least 200°C. Examples of suitable moisture scavengers include calcium oxide, magnesium oxide, phosphorus pentoxide, various molecular sieves and the like. Calcium oxide is preferred. Calcium oxide is conveniently provided in the form of fine particles (preferably less than 100 micrometers in diameter).
    [039] The thermoactivatable catalyst includes a mixture of a solid or liquid tertiary amine compound having a boiling temperature of at least 130°C, and a novolac resin. Examples of thermoactivatable catalysts of this type include those described, for example, in U.S. Patent No. 4,701,378 and WO 2012/000171. Among the useful tertiary amine compounds are p-chlorophenyl-N,N-dimethylurea (Monuron), 3-phenyl-1,1-dimethylurea (Phenuron), 3,4-dichlorophenyl)N,N-dimethylurea (Diuron), N-(3-chloro-4-methylphenyl)-N',N'-dimethylurea (Chlortoluron),benzyldimethylamine, aminophenols such as 2,4,6-tris(dimethylaminomethyl)phenol, piperidine, various aliphatic urea compounds such as those described in EP 1 916 272; C1-C12 alkylene imidazole or N-arylimidazoles such as 2-ethyl-2-methylimidazole and N-butylimidazole and 6-caprolactam. A preferred catalyst is an aminophenolic compound, such as 2,4,6-tris(dimethylaminomethyl)phenol. The novolac resin can have a molecular weight from 500 to 10,000, preferably from 500 to 30,000 or more. The molecular weight is limited only by the need for the novolac resin to soften or melt at a reasonable temperature so that it can be mixed with the tertiary amine compound to produce the thermoactivatable catalyst. Preferably, the novolac resin softens at a temperature of from about 90 to about 200°C, especially from 130 to 200°C. An especially preferred novolac resin is a phenol-formaldehyde resin, having a weight average molecular weight of 10,000 to 25,000.
    Preferably, the heat activatable catalyst is present in an amount of about at least 0.1 percent by weight of the structural adhesive, and more preferably about at least 0.5 percent by weight. In some embodiments, the heat-activatable catalyst constitutes at least 1 percent by weight of the structural adhesive. Preferably, the catalyst constitutes up to about 4 percent by weight of the structural adhesive, more preferably from about up to 1.5 percent by weight, and most preferably from about to 0.9 percent by weight.
    [041] The thermoactivatable catalyst can be used in combination with one or more other catalysts, which preferably are also thermoactivatable. The other catalysts can include various amine compounds, as described above, which are blocked with a blocking group other than a novolac resin. An example of such other catalysts is a blocked 1-(2-(2-hydroxylbenzamido)ethyl)-2-(2-hydroxylphenyl-2-imidazoline). Another catalyst of this type is an aminophenol, such as 2,4,6-tris(dimethylaminomethyl)phenol in a poly(vinylphenol) matrix. Such other catalyst, when used, is preferably present in an amount less than that of the amine/novolac resin mixture and more preferably in an amount of 0.1 to 0.3 times by weight that of the amine/novolac resin mixture.
    [042] The structural adhesive of the invention may contain several other optional components. A particularly suitable flame retardant is a mixture of alumina trihydrate, zinc borate and melamine or a melamine derivative such as melamine polyphosphate. These components together can constitute at least 10 percent to 25 percent by weight of the weight of the structural adhesive, preferably from 14 to 18 percent by weight.
    [043] At least one filler, rheology modifier and/or pigment is preferably present in the structural adhesive. These can perform various functions, such as (1) desirably modifying the rheology of the adhesive, (2) reducing the total cost per unit weight, (3) absorbing moisture or oils from the adhesive or a substrate to which it is applied, and /or (4) promote cohesive rather than sticky failure. Examples of such materials include calcium carbonate, talc, carbon black, textile fibers, glass particles or fibers, aramid pulp, boron fibers, carbon fibers, mineral silicates, mica, quartz powder, hydrated aluminum oxide, bentonite , wollastonite, kaolin, fumed silica, silica airgel, polyurea compounds, polyamide compounds or metal powders such as aluminum powder or iron powder. Another charge of specific interest is a microballoon with an average particle size of up to 200 microns and density of up to 0.2 g/cc. The particle size is preferably from about 25 to 150 microns and the density is preferably from about 0.05 to about 0.15 g/cc. Thermoexpandable microballoons suitable for reducing density include those supplied by Dualite Corporation under the tradename DualiteTM and those sold by Akzo Nobel under the tradename ExpancelTM.
    [044] Fillers, pigment and rheology modifiers are preferably used in aggregate amount of about 2 parts per hundred parts adhesive composition or more, more preferably about 5 parts per hundred parts adhesive composition or more. They are preferably present in an amount of up to about 25 percent by weight of the structural adhesive, more preferably about up to 20 percent by weight, and most preferably about up to 15 percent by weight.
    [045] The speed and selectivity of cure can be increased and adjusted by incorporating a monomeric or oligomeric material, polymerizable by addition, ethylenically unsaturated to the structural adhesive. Such material should have a molecular weight of less than about 1500. Such material should have a molecular weight of less than about 1500. Such material may be, for example, an acrylate or methacrylate compound, an unsaturated polyester, a vinyl ester resin , or an epoxy adduct of an unsaturated polyester resin. A free radical initiator can also be included in the structural adhesive to provide a source of free radicals to polymerize this material. The inclusion of an ethylenically unsaturated material of this type offers the possibility of effecting a partial curing of the structural adhesive through selective polymerization of the ethylenic unsaturation.
    [046] The structural adhesive may also contain other additives, such as dimerized fatty acids, core-shell type rubbers, thinners, plasticizers, thinners, pigments and dyes, flame retardants, thixotropic agents, blowing agents, flow control agents , adhesion promoters and antioxidants. Suitable blowing agents include both physical and chemical type agents. The adhesive may also contain a thermoplastic powder such as polyvinyl butyral or a polyester polyol as described in WO 2005/118734.
    [047] The adhesive composition can be applied by any convenient technique. Can be applied cold or hot if desired. It can be applied by extrusion from a robot in granular form on the substrate, can be applied using mechanical application methods such as caulking guns or any other means of manual application, and can be applied using jet spray methods , such as a continuous flow method or a vortex technique. The substrates are contacted so that the adhesive is located between the substrates to be joined.
    [048] After application, the structural adhesive is cured by heating to a temperature at which the curing agent begins to cure the epoxy resin composition. Generally, that temperature is about 80°C or more, preferably about 140°C or more. Preferably the temperature is about 220°C or less, and more preferably about 180°C or less and especially 150 to 170°C. An advantage of the present invention is that it develops good properties, especially good resistance to impact peeling and durability under stress, when cured at temperatures equal to or less than 170°C, such as 140 to 170°C, and especially 150 to 170°C.
    [049] The adhesive of the invention can be used to bond a variety of substrates including wool, metal, coated metal, aluminum, a variety of plastic and plastic filled substrates, fiberglass and the like. In a preferred embodiment, the adhesive is used to join automotive parts or to bond automotive parts to automobiles. These parts can be steel, coated steel, galvanized steel, aluminum, coated aluminum, plastic substrates or plastic filled.
    [050] An application of specific interest is to connect automotive structure components with each other or with other components. Structural components are often metals such as cold rolled steel, galvanized metals or aluminium. The components that are to be joined to the structural components can also be metals as described, or can be other metals, plastics, composite materials and the like.
    [051] The structural adhesive of the invention is especially suitable for use in a method in which an aluminum member and a second metallic member (which may or may not be aluminum) are joined. By "aluminium" is meant pure aluminum metal or any alloy containing at least 80% by weight of aluminum. In this method, the structural adhesive of the invention is formed into a layer between and in contact with the members, and heated to a temperature of at least 120°C to cure the adhesive and form a structural bond between the members. The curing temperature is preferably from 120 to 170°C and even more preferably from 150°C to 170°C. Preferably, the second metallic member is also aluminum. The aluminum member and the second metallic member may form all or part of a carrier structural assembly. The aluminum member and the second metallic member (including but not restricted to the case where they form all or part of a carrier structural assembly) can be coated with a coating that requires a bake cure, and the structural adhesive can be cured simultaneously with curing by baking the coating. In any of these embodiments of the method of the invention, the aluminum member and the second member may be welded together before the structural adhesive is cured.
    [052] In certain embodiments, the cured structural adhesive of the invention:
    [053] a) exhibits an impact shear strength of at least 20 N/mm measured in accordance with ISO 11343 wedge impact method on 2 mm thick 6111 aluminum alloy substrate after curing at 160°C for 10 minutes.
    [054] b) exhibits a storage module of at least 900 MPa at 50°C, measured by dynamic mechanical analysis, in accordance with ASTM E2254-09; and/or
    [055] c) withstands at least 45 stress environmental aging test cycles after curing for 10 minutes at 160°C.
    [056] The cured adhesive preferably meets all three of these characteristics.
    [057] The environmental stress aging test is described in Dickie, DeBolt and Ward in “Stress Durability Testing of Adhesively Bonded Steel,” SAE Technical Paper 950128, 1995. Samples are formed by applying a 0.15mm layer thickness of structural adhesive between two clean 6111 aluminum alloy specimens 2mm thick to form a ^" (12.7mm) and 1" (25.4mm) width glue/bond overlap and cured for 30 minutes at 180°C. A load of 2400N is applied to the cured assembly, which is then subjected to repeated cycles of 15 minutes immersion in a 5% by weight NaCl solution in water at approximately 25°C, 105 minutes air drying at 25°C and ambient humidity and 22 hours at 50°C and 90% relative humidity. After five cycles of this type, the set is kept for another two days at 50°C and 90% relative humidity, so that five cycles are carried out in each calendar week. The cycle proceeds according to the mentioned scheme until the adhesive bond fails.
    [058] The cured adhesive also preferably exhibits a water absorption of at most 2.2% by weight, measured by curing 3mm thick plates of the adhesives, punching 8mm plate diameter discs, weighing each disc , immersion of the discs separately in deionized water at room temperature, removal of the discs and removal of free water from the discs and new weighing of each disc. The discs are again immersed and weighed until they reach constant weight. The weight reached to equilibrium divided by the initial weight of the sample is the water absorption. The average of five samples is reported.
    [059] The following examples are provided to illustrate the invention, although they are not intended to restrict its scope. All parts and percentages are by weight unless otherwise indicated.Examples 1-2 and Comparative Samples A-D
    [060] Examples 1-2 and Comparative Samples AD of one-component heat-curable structural adhesive are prepared by mixing the components listed in Table 1.
    Rubber-modified epoxy resin A is a bisphenol A diglycidylether marketed by The Dow Chemical Company as DERTM 331. It has an epoxy equivalent weight of about 186. 2Rubber-modified Bisphenol A-based epoxy resin is a reaction product of 60% by weight of a bisphenol A diglycidyl ether blend of ~180 epoxy equivalent weight with 40% by weight of a carboxyl terminated butadiene/acrylonitrile rubber sold by Noveon as Hycar®1300X8.33 Epoxy resin B base of rubber modified bisphenol A is a reaction product of 60% by weight of a diglycidyl ether mixture of bisphenol A with epoxy equivalent weight of ~180 with 40% by weight of a carboxyl terminated butadiene/acrylonitrile rubber sold by Noveon as Hycar®1300X13.4 Rubber modified bisphenol F epoxy resin A is a reaction product of 70.2% by weight of a bisphenol F diglycidyl ether mixture with ~180 epoxy equivalent weight with 19.6 % by weight of a carboxyl terminated butadiene/acrylonitrile rubber sold by Noveon as Hycar®1300X13, which is also diluted with 10.2% of a solid bisphenol A diglycidyl ether having an epoxy equivalent weight of 1600-2000 sold by The Dow Chemical Company as DER®667.5 Hardener A is an isocyanate terminated polyurethane prepolymer prepared with a polyether polyol and an aliphatic diisocyanate in which the isocyanate groups are capped with o,o-dialyl bisphenol A, and prepared as described in Example 13 of EP 308 664.6 Hardener B is similar to Hardener A, except that the capping groups are phenol instead of o,odiallylbisphenol A.
    [061] Duplicate specimens are prepared and evaluated for the shear strength in overlapping according to DIN EN 1465, using aluminum alloy 6111 with 2mm thickness, coated with lubricant DC290. The test is conducted at a test speed of 10mm/minute and at 23°C. Test samples are prepared using each patch. Duplicate specimens are cured for 30 minutes at 180°C. The results are shown in Table 2.
    [062] The impact peel test is conducted in accordance with ISO 11343 wedge impact method. The test is conducted using an Instron Dynatup 8250 device operated at 2 mm/sec. The specimens measure 100mm x 20mm with a bonded area of 20 x 30mm. The substrate is 0.8 mm thick cold rolled steel that has been cleaned with acetone prior to application of the adhesive. A 0.15mm x 10mm wide Teflon tape is applied to the specimens to define a bonding area of 20 x 30mm. The impact peel test is conducted on samples cured for various periods and temperatures as indicated in Table 2. In some cases, the impact peel test is also conducted on samples cured for 10 minutes at 160°C. The results are shown in Table 2.
    [063] Stress Aging Aging test is conducted as described above. The initial cure temperature is measured using differential scanning calorimetry.

    ND = not determined
    [064] In tables 1 and 2, Comparative Sample A represents a reference case. Without catalyst, as required in the present invention, the values of peeling on impact are observed at cures at lower temperatures, and especially at a cure temperature of 160°C. Furthermore, the environmental aging results under stress at 160°C for Comparative Sample A are more unsatisfactory than those whose curing was conducted at a higher temperature. The most unsatisfactory stress aging and impact peeling results are correlated with a higher initial cure temperature for this sample, which is 167°C. Sample does not cure well at the lowest cure temperature.
    [065] Comparative Samples B and C show the effect obtained by replacing the rubber modified Bisphenol F-based epoxy resin by a rubber-modified bisphenol A-based epoxy resin. Stressed environmental aging results dropped dramatically with this change in the rubber-modified epoxy resin, even when calcium oxide was present and, as in Comparative Example C, the amount of rubber was increased.
    [066] Comparative Sample D demonstrates the effect obtained by increasing the amount of rubber and stiffener. This increases impact peel strength at a cure at 180°C, but not significantly with a cure at 160°C. The initial cure temperature is 167°C (same as Comparative Sample A) and inadequate cure is observed at a cure temperature of 160°C.
    [067] In Examples 1 and 2, the selection of catalyst, rubber-modified epoxy resin type (of bisphenol F type instead of bisphenol A as in Comparative Samples B and C) and presence of calcium oxide leads to an adhesive with excellent overlap shear strength, excellent impact peel strength even at a cure temperature of 160°C, also exhibiting excellent performance under the stress environmental aging test, even when cured at a temperature of only 160°C. Surprisingly, the environmental stress aging values after curing at 160°C are even higher than those obtained with curing at 180°C.
    权利要求:
    Claims (15)
    [0001]
    1. Thermocurable structural adhesive, characterized in that it comprises: A) at least one non-rubber-modified epoxy resin; B) a reaction product of a carboxyl- or amine-terminated butadiene polymer or copolymer and a bisphenol-based epoxy resin F;C) at least one elastomeric stiffener containing capped isocyanate groups; D) one or more epoxy curing agents; E) from 0.5 to 10 percent by weight of a moisture scavenger, based on the total weight of the structural adhesive thermosetting; and F) a thermally activated catalyst comprising a mixture of a solid or liquid tertiary amine compound having a boiling temperature of at least 130°C and a novolac resin, and further being the elastomeric stiffener and the rubber portion of the resin Rubber-modified epoxy together make up 15-25% of the total weight of the heat-curable adhesive.
    [0002]
    2. Adhesive according to claim 1, characterized in that component (A) has an average equivalent weight of epoxy from 170 to 600 and includes at least one diglycidyl ether of a polyhydric phenolic compound.
    [0003]
    3. Adhesive according to any one of claims 1 or 2, characterized in that the elastomeric stiffener and the rubber portion of the rubber-modified epoxy resin together constitute 16 to 22% of the total weight of the heat-curable adhesive.
    [0004]
    4. Adhesive, according to any one of claims 1 to 3, characterized in that the elastomeric stiffener constitutes from 5 to 10% 16% of the total weight of the heat-curable adhesive.
    [0005]
    5. Adhesive according to any one of claims 1 to 4, characterized in that the novolac resin is a phenol-formaldehyde resin that softens at a temperature of 130 to 200°C.
    [0006]
    6. Adhesive, according to any one of claims 1 to 5, characterized in that the moisture eliminator is calcium oxide, and is present in an amount of 2 to 5% of the total weight of the structural adhesive.
    [0007]
    7. Adhesive according to any one of claims 1 to 6, characterized in that it contains at least 0.5% by weight of component (F).
    [0008]
    8. Adhesive according to any one of claims 1 to 7, characterized in that the isocyanate groups of the elastomeric stiffener are capped with a monophenolic compound, a primary or secondary aliphatic, cycloaliphatic or aromatic monoamine, a monothiol compound or a benzylamine.
    [0009]
    9. Adhesive according to any one of claims 1 to 7, characterized in that the isocyanate groups of the elastomeric stiffener are capped with a polyphenol or an aminophenol.
    [0010]
    10. Method for joining an aluminum member to a second metallic member, characterized in that it comprises: forming a layer of thermosetting structural adhesive as defined in any one of claims 1 to 9, contacting and contacting the aluminum member and the second metallic member to form an assembly and then heat the assembly including the structural adhesive to a temperature of at least 120°C to 170°C to cure the structural adhesive and form an adhesive bond between the aluminum member and the second member. metallic.
    [0011]
    11. Method according to claim 10, characterized in that the second metallic member is welded to the aluminum member after the heat-curable structural adhesive layer is formed and before the structural adhesive is cured.
    [0012]
    12. Method according to any one of claims 10 or 11, characterized in that a coating is applied to the assembly before the structural adhesive is cured.
    [0013]
    13. Method according to claim 12, characterized in that the structural adhesive and the coating are cured simultaneously.
    [0014]
    14. Method according to any one of claims 10 to 13, characterized in that the second metallic member is aluminum.
    [0015]
    15. Method according to any one of claims 10 to 14, characterized in that the set comprises all or part of the vehicle structure.
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    同族专利:
    公开号 | 公开日
    KR102099305B1|2020-04-10|
    JP6173424B2|2017-08-02|
    US20150001281A1|2015-01-01|
    US9840070B2|2017-12-12|
    US20170197397A1|2017-07-13|
    KR20140138760A|2014-12-04|
    CN104144959B|2018-03-09|
    EP2828308B1|2016-05-04|
    CN104144959A|2014-11-12|
    WO2013142750A3|2014-07-17|
    JP2015517001A|2015-06-18|
    WO2013142750A2|2013-09-26|
    EP2828308A2|2015-01-28|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-04-07| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-05-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-13| B09X| Decision of grant: republication|
    2021-07-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261614543P| true| 2012-03-23|2012-03-23|
    US61/614,543|2012-03-23|
    PCT/US2013/033408|WO2013142750A2|2012-03-23|2013-03-22|Crash-durable adhesive with enhanced stress durability|
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