one-part structural adhesive and method of applying structural adhesive

专利摘要:
STRUCTURAL ADHESIVE OF A PART AND METHOD OF APPLICATION OF STRUCTURAL ADHESIVE.Structural adhesives are prepared from an extended chain elastomeric hardener that contains urethane and / or urea groups and has terminal isocyanate groups that are protected with a phenolic, polyphenolic or aminophenolic compound. The adhesives have good storage stability and cure to form adhesives that have good resistance to shearing and peeling impact.
公开号:BR112013010668A2
申请号:R112013010668-9
申请日:2011-11-30
公开日:2021-03-23
发明作者:Andreas Lutz；Daniel Schneider；Christof Braendli；Irene Maeder
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

"PART STRUCTURAL ADHESIVE AND STRUCTURAL ADHESIVE APPLICATION METHOD" Field of the invention This invention relates to an epoxy-based structural adhesive containing an extended chain elastomeric hardener having terminal isocyanate groups blocked with a phenolic, polyphenolic or aminophenolic compound.
Background of the invention 10 Adhesives based on epoxy resin are used in many applications.
In the automotive industry, epoxy resin adhesives are used in many bonding applications, including metal-to-metal bonding to the main structure and other structures in automobiles.
Some of these adhesives 15 must strongly resist failure during vehicle collision situations.
Such adhesives are often referred to as "durable collision adhesives", or "CDA". In order to obtain a good balance of properties that are necessary to satisfy the performance requirements of automobiles, epoxy adhesives are often formulated with different rubbers and / or "hardeners". The hardeners blocked functional groups that, under the conditions of the curing reaction, could become unblocked and react with an epoxy resin.
Such hardeners are described, for example, in the U.S. Patent
No. 5,202,390, U.S. Patent
No. 5,278,257, WO 2005/118734, U.S. Published Patent Application
No. 2005/0070634, U.S. Published Patent Application
No. 30 2005/0209401, Published Patent Application US 2006/0276601, EP-A-0308664, EP-A 1728825, EP-A 1896517, EP-A 1916269, EP-A 1916270, EP-A 1916272, and EP- 1916285. Various types of groups have been suggested to block isocyanate groups from the prepolymer.
Among these are 35 various phenols, polyphenols and aminophenols, as described, for example, in USP 5,278,257 for Mulhaupt.
EP-A 1916269 describes a hardener containing both epoxy and phenol blocking groups.
Phenolic, polyphenolic and aminophenolic materials constitute a very suitable class of protecting groups, because cured adhesives produced using hardeners 5 protected with these groups tend to have very good properties.
As described in U.S. Published Patent Application
No. 2005/0209401, adhesives containing such hardeners often exhibit very good resistance to peeling impact at low temperatures when cured.
A problem with hardeners protected with these groups is that the composition of the adhesive that contains them is not sufficiently stable in storage.
See, for example, EP 1498441 A1 and WO 2007/003650. These adhesives prematurely begin to advance in molecular weight.
Because of this, the adhesive can thicken or even become a gel to the point that it cannot be dispensed correctly, does not adhere well to the substrate or forms a strong cured adhesive layer, or is no longer usable in any other way.
Since these adhesives are generally packaged up to several months before they are finally used, the lack of storage stability represents a very serious practical problem.
It is desirable to provide an adhesive of one part that contains a hardener covered with phenolic, polyphenolic or aminophenolic groups, an adhesive that has good storage stability and maintains good adhesive properties.
Summary of the invention This invention is a one-part structural adhesive comprising: A) at least one epoxy resin; B) a reactive elastomeric hardener containing protected isocyanate groups; and C) one or more epoxy curing agents; 35 in which the elastomeric hardener is formed by a) reacting an excess of a polyisocyanate with a polyol of equivalent weight of 300-3000 or with a mixture of a polyol of equivalent weight of 300-3000 and a branching agent, to form an isocyanate-terminated prepolymer; b) reaction of the isocyanate-terminated prepolymer with a chain extender to produce an extended-chain isocyanate-terminated prepolymer, and c) protection of at least 90% of the terminal isocyanate groups of the isocyanate-terminated prepolymer extended with a protective agent selected 10 from a monophenol, a polyphenol or an aminophenol.
Surprisingly, the adhesive of the invention is significantly more stable in storage than an otherwise similar adhesive containing a non-extended chain phenolic, polyphenolic or aminophenolic hardener.
The cured adhesive has very good properties, namely good resistance to shear and peeling impact.
The shear strength and peeling impact is often, and unexpectedly, significantly higher than when the hardener has no extended chains.
The invention is also a method comprising applying the previous structural adhesive to the surfaces of two elements, and curing the structural adhesive to form an adhesive bond between the two elements.
At least one and 25 preferably both elements are metals.
The hardener of the invention is elastomeric, contains urethane and / or urea groups and has terminal isocyanate groups, at least 90% of which are protected with a phenolic, polyphenolic or aminophenolic compound. Preferably, at least 95% and more preferably at least 98% of the isocyanate groups in the hardener or reactive hardeners are protected with a phenolic, polyphenolic or aminophenolic compound.
All isocyanate groups can be protected with the phenolic, polyphenolic or aminophenolic compound.
Up to 10%, preferably not more than 5% and even more preferably not more than 2% of the isocyanate groups can be protected with another protective agent.
If you prefer that essentially none (such as 1% or less) of these isocyanate groups are protected with a functional epoxy protecting group, (ie, a protecting group that gives the protected prepolymer 5 epoxy functionality), or a ketoxime protection group.
Less than 5%, preferably less than 1% of the isocyanate groups can remain unprotected.
The hardener is produced by a process that includes the 10 steps of forming an isocyanate-terminated prepolymer, extending the prepolymer chains and then protecting the prepolymer from extended chains.
The prepolymer is formed by reacting an excess of a polyisocyanate with a polyol with a weight equivalent to 15 300-3000 or with a mixture of a polyol with a weight equivalent to 300-3000 and a branching agent, so to form an isocyanate-terminated prepolymer.
The polyol having a weight equivalent to 300-3000 is preferably a polyether polyol or a hydroxyl-terminated butadiene homopolymer or copolymer.
The polyol preferably has 2-3, more preferably 2, hydroxyl groups per molecule.
The branching agent, for the purposes of this invention, is a polyol or polyamine compound having a molecular weight of up to 599, preferably 50 to 500, and at least three hydroxyl groups, primary amino and / or secondary amino per molecule.
If used, branching agents generally constitute not more than 10%, preferably not more than 5% and still more preferably not more than 2% of the combined weight of the branching agent and polyol of a weight equivalent to 300-3000 . Examples of branching agents include polyols such as trimethylolpropane, glycerin, trimethylolethane, ethylene glycol, diethylene glycol, propylene glycol, 35 dipropylene glycol, sucrose, sorbitol, pentaerythritol, triethanolamine, diethanolamine and the like, as well as alkoxylates of these even having a molecular weight
599, especially up to 500. The polyisocyanate may be an aromatic polyisocyanate, but is preferably an aliphatic polyisocyanate, such as isophorone diisocyanate, 1,6-5 hexamethylene diisocyanate, diisocyanate of hydrogenated toluene, hydrogenated methylene diphenylisocyanate (H12MDI), and the like.
An excess of polyisocyanate compound is used, so that essentially all reactive groups with 10 isocyanate polyol of a weight equivalent to 300-3000 and the branching agent (if any) are consumed and the resulting prepolymer is terminated in isocyanate groups.
It is generally preferred to combine at least 1.5 equivalents of polyisocyanate per equivalent of the 15 reactive materials with isocyanate (i.e., the 300-3000 molecular weight polyol and the branching agent, if any), as this ratio minimizes the formation of materials that are advanced in molecular weight.
More preferably, 1.5 to 2.5 equivalents 20 of the polyisocyanate are provided per equivalent of the isocyanate-reactive materials.
The prepolymer formation reaction is carried out by mixing the starting materials and heating them, preferably in the presence of a catalyst for the reaction of isocyanate groups with hydroxyl groups.
The reaction mixture will normally be 60 to 120ºC, and the reaction is continued until a constant isocyanate content is obtained, indicating that all isocyanate reactive groups in the starting materials have been consumed. The resulting prepolymer preferably has an isocyanate content of 0.5 to 7% by weight, more preferably 1 to 6% by weight and even more preferably 1.5 to 5% by weight.
In terms of isocyanate equivalent weight, a preferred range is 700 to 8400, a more preferred range is 840 to 4200, and an even more preferred range is 1050 to 2800. The prepolymer suitably contains, on average, from about 1.5, preferably from about 2.0, to about 4, preferably about 3, and more preferably about 2.5 isocyanate groups per molecule.
The prepolymer is then reacted with a 5-chain extender to produce an extended-chain isocyanate-terminated prepolymer.
Chain extenders, for the purposes of this invention, are polyol or polyamine compounds having a molecular weight of up to 749, preferably 50 to 500, and two hydroxyl groups, primary amino 10 and / or secondary amino per molecule.
Examples of suitable chain extenders include aliphatic diols, such as ethylene glycol, diethylene glycol, methylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexane-diol, cyclohexanedimethanol and the like; aliphatic or aromatic diamines such as ethylenediamine, piperazine, aminoethylpiperazine, phenylenediamine, diethyltoluenediamine and the like, and compounds having two phenolic hydroxyl groups such as resorcinol, catechol, hydroquinone, bisphenol, 20 bisphenol A, bisphenol AP (1,1-1,1 hydroxyphenyl) -1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol and o, o'-diallyl-bisphenol A, and the like.
Among these, compounds having two phenolic hydroxyl groups are preferred. The chain extension reaction is carried out in the same general way as the prepolymer formation reaction.
Sufficient prepolymer is mixed with the chain extender to provide at least two equivalents of isocyanate groups per equivalent of reactive groups with 30 isocyanate contributed by the chain extender.
Up to 4 or more, preferably up to 3, and more preferably up to 2.5 equivalents of isocyanate groups can be provided per equivalent of isocyanate reactive groups contributed by the chain extender.
An especially preferred amount is 2 to 2.25 equivalents of isocyanate groups per equivalent of isocyanate reactive groups contributed by the chain extender.
As before, the reaction is preferably carried out at an elevated temperature (such as 60 to 120 ° C) until a constant isocyanate content is reached (indicating that all reactive groups with isocyanate 5 have been consumed). The extended chain prepolymer is terminated with isocyanate groups.
The extended chain prepolymer will include molecules that correspond to a conjugation of the starting prepolymer with the chain extender.
If 10 react more than 2 prepolymer equivalents per chain extender equivalent, the extended chain prepolymer will also contain some amount of prepolymer molecules that have not been extended.
The extended chain prepolymer may also contain a small amount of higher molecular weight reaction products.
The extended chain prepolymer preferably has an isocyanate content of 0.25 to 3% by weight, more preferably from 0.5 to 2.5% by weight and most preferably 0.75 to 2% by weight. Weight.
In 20 terms of isocyanate equivalent weight, a preferred range is 1400 to 17000, a more preferred range is 1680 to 8500, and an even more preferred range is 2100 to 5700. The extended chain prepolymer contains suitably, on average about 1.5, preferably about 2.0, to about 6, preferably about 4, more preferably about 3, and most preferably about 2.5, isocyanate groups per molecule.
An especially preferred prepolymer contains an average of 1.9 to 2.2 isocyanate groups per molecule. At least 90% of the extended chain prepolymer isocyanate groups are then protected by reaction with a monophenol, a polyphenol or an aminophenol to form the hardener.
Examples of suitable monophenolic compounds include, for example, phenol, alkylphenols which contain one or more alkyl groups which may each contain 1 to 30 carbon atoms, naphthol, or a halogenated phenol or naphthol.
Suitable polyphenols contain two or more, preferably two, phenolic hydroxyl groups per molecule.
Examples of suitable polyphenols include resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis (4-hydroxyphenyl) -1-phenyl) ethane), 5 bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol and o , o'-diallyl-bisphenol A, as well as halogenated derivatives thereof.
Suitable aminophenols are compounds that contain at least one primary or secondary amino group and at least one phenolic hydroxyl group.
The amino group is preferably attached to a carbon atom in an aromatic ring.
Examples of suitable aminophenols include 2-aminophenol, 4-aminophenol, various aminonaphthols, and the like.
Sufficient phenolic, polyphenolic or aminophenolic compound 15 is provided to protect at least 90%, preferably at least 95%, more preferably at least 98%, up to 100% of the extended chain prepolymer isocyanate groups.
It is possible to use a mixture of the phenolic, polyphenolic or aminophenolic compound with up to 20 mole% of another protective agent, such as a monoamine, a ketoxime, a functional epoxy compound, and the like.
However, it is preferred not to employ such another protective agent.
The protection reaction can be carried out under the general conditions already described in relation to the reactions of prepolymer formation and chain extension, that is, through the combination of materials in the indicated ratios and heating up to 60-120ºC, optionally at presence of a catalyst for the reaction of isocyanate groups with phenolic and / or amino groups, as the case may be.
The reaction is continued until the isocyanate content is reduced to a constant value, which is preferably less than 0.1% by weight.
The resulting hardener suitably has a numerical average molecular weight of at least 3000, preferably at least 4000, at about 35000, preferably at about 20000 and still more preferably at about 15000, measured using GPC, taking into account only peaks representing molecular weights of 1000 or more.
The polydispersity (ratio between the weighted average molecular weight 5 and the numerical average molecular weight) is suitably from about 1 to about 4, preferably from about 1.5 to 2.5. The hardener suitably contains, on average, about 1.5, preferably about 2.0, about 6, preferably about 10 4, more preferably about 3 and even more preferably about 2.5, isocyanate groups protected by molecule.
An especially preferred prepolymer contains an average of 1.9 to 2.2 isocyanate groups protected per molecule. 15 The hardener must make up at least 5 percent by weight of the adhesive composition.
Best results are typically seen when the amount of hardener is at least 8 percent by weight or at least 10 percent by weight.
The hardener can comprise up to 45 per cent by weight thereof, preferably up to 30 per cent by weight and most preferably up to 25 per cent by weight.
The amount of hardener that is necessary to provide good properties, particularly good properties at low temperature, in any particular adhesive composition 25 may depend in some way on other components of the composition, and may depend in some way on the molecular weight of the hardener.
The structural adhesive contains at least one epoxy resin.
It is preferable that at least a portion of the epoxy resin 30 is not modified with rubber, which specifically means that the epoxy resin is not chemically bonded to a rubber.
An unmodified rubberized epoxy resin can be added to the structural adhesive as a separate component, that is, as something other than a component of a rubber modified epoxy resin product or a part of a core-coating rubber dispersion, as described below.
In some embodiments of the invention, a core-coated rubber product is used, which can be dispersed in a certain amount of epoxy resin.
Some amount of unmodified epoxy resin with rubber 5 can be brought into the structural adhesive in this way.
In other embodiments, a rubber-modified epoxy resin product used as a component of the structural adhesive may contain a certain amount of epoxy resin that is not reacted with the rubber (and thus is not modified with rubber). Some unmodified epoxy resin with rubber can also be brought into the adhesive in this way.
A wide variety of epoxy resins can be used as an unmodified rubber epoxy resin, including those described in column 2 row 66 to column 4 row 24 of U.S. Patent 4,734,332, incorporated herein by reference.
The epoxy resin should have an average of at least 2.0 epoxide groups per molecule.
Suitable epoxy resins include diglycidyl ethers 20 of polyhydric phenolic compounds, such as resorcinol, catechol, hydroquinone, biphenol, bisphenol A, bisphenol AP (1,1-bis (4-hydroxyphenyl) -1-phenyl) ethane), bisphenol F, bisphenol K, and tetramethylbiphenol; diglycidyl ethers of aliphatic glycols and polyether glycols such as C2-24 alkylene glycol diglycidyl ethers and poly (ethylene oxide) or poly (propylene oxide) glycols; polyglycidyl ethers of novolac phenol-formaldehyde resins (novolac epoxy resins), 30-alkyl substituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins and substituted phenolic dyes; and any combination of any two or more of these. 35 Suitable epoxy resins include bisphenol A diglycidyl ether resins, as sold by Dow Chemical under the designations D.E.R.® 330,
D.E.R.® 331, D.E.R.® 332, D.E.R.® 383, D.E.R. 661 and D.E.R.® 662. Commercially available polyglycol diglycidyl ethers that are useful include those sold as D.E.R.® 732 and D.E.R.® 736 by Dow Chemical.
Novolac epoxy resins can be used.
These resins are commercially available as D.E.N.® 354, D.E.N.® 431, D.E.N.® 438 and D.E.N.® 439 from Dow Chemical.
Other suitable epoxy resins not modified with rubber 10 are cycloaliphatic epoxides.
A cycloaliphatic epoxide includes a saturated carbon ring having an epoxy oxygen atom attached to two neighboring atoms of the carbon ring, as illustrated by the following structure III:
15 where R is an aliphatic, cycloaliphatic and / or aromatic group and n is a number from 1 to 10, preferably from 2 to 4. When n is 1, cycloaliphatic epoxide is a mono-epoxide.
Di- or polypoxides are formed when n is 2 or more.
Mixtures of mono, di and / or polyepoxides can be used.
Cycloaliphatic epoxy resins as described in the U.S. Patent
No. 3,686,359, incorporated herein by reference, can be used in the present invention.
The cycloaliphatic epoxy resins of particular interest are (3,4-epoxycyclohexyl-methyl) -3,4-epoxy-25-cyclohexane carboxylate, bis- (3,4-epoxycyclohexyl) adipate, vinylcyclooxide -hexene and mixtures of these.
Other suitable epoxy resins include compounds containing oxazolidone, as described in the U.S. Patent
No. 5,112,932. In addition, an advanced epoxy isocyanate copolymer, 30 such as those sold commercially as D.E.R. 592 and D.E.R. 6508 (Dow Chemical) can be used.
The unmodified rubberized epoxy resin is preferably a bisphenol-type epoxy resin or a mixture thereof with up to 10 weight percent of another type of epoxy resin. The most preferred epoxy resins are bisphenol-A based epoxy resins and bisphenol-F based epoxy resins. These may have epoxy equivalent average weights of about 170 to 600 or more, preferably 225 to 400. An especially preferred unmodified rubberized 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 a second diglycidyl ether of a polyhydric phenol, again preferably bisphenol-A 15 or bisphenol -F, that having an epoxy equivalent weight of at least 300, preferably from 310 to 600. The proportions of the resins are preferably such that the mixture has an average epoxy equivalent weight of 225 to
400. The mixture may also optionally contain up to 20%, preferably 20% up to 10%, of one or more other epoxy resins not modified with rubber. An unmodified epoxy resin with rubber will preferably constitute at least about 25 weight percent of the structural adhesive, more preferably at least 25 about 30 weight percent, and even more preferably at least about 35 weight percent . The rubber-modified epoxy resin can make up to about 70 weight percent of the structural adhesive, more preferably up to about 50 weight percent. These amounts include any unmodified rubberized epoxy resin that can be brought into the composition with other components that contain an epoxy resin such as, for example, an unreacted diluent or excess reagent. 35 The structural adhesive also contains a curing agent. The curing agent is selected together with any catalyst so that the adhesive will cure quickly when heated to a temperature of 80ºC or more, preferably 140ºC or more, but cure very slowly, if curing, at room temperature (22ºC) and temperatures up to at least 50ºC.
Suitable curing agents include 5 materials such as boron / amine trichloride and boron / amine trifluoride complexes, dicyandiamide, melamine, diallymelamine, 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 diaminodiphenyl sulfones.
The use of dicyandiamide, isophthalic acid dihydrazide, adipic acid dihydrazide and / or 4,4'-15 diaminodiphenylsulfone is particularly preferred.
The curing agent is used in an amount sufficient to cure the composition.
Typically, enough of the curing agent is provided to consume at least 80% of the epoxide groups present in the composition.
A large excess in relation to the amount needed to consume all epoxide groups is generally not necessary.
Preferably, the curing agent constitutes at least about 1.5 weight percent of the structural adhesive, more preferably at least about 2.5 weight percent and still more preferably at least 3.0 weight percent. Weight.
The curing agent preferably constitutes up to about 15 weight percent of the structural adhesive composition, more preferably up to about 10 weight percent, and most preferably up to about 8 weight percent. The structural adhesive will, in most cases, contain a catalyst to promote curing of the adhesive, i.e., the reaction of epoxy groups with reactive groups with epoxide in the curing agent and other components of the adhesive.
The catalyst is preferably encapsulated or otherwise a latent type that becomes active only after exposure to elevated temperatures.
Preferred catalysts include urea such as p-chlorophenyl-N, N-
dimethylurea (Monuron), 3-phenyl-1,1-dimethylurea (Phenuron), 3,4-dichlorophenyl-N, N-dimethylurea (Diuron), N- (3-chloro-4-methyl-phenyl) -N ', N'-dimethylurea (Chlortoluron), tert-acryl- or alkylene-amines such as 5-benzildimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, piperidine or derivatives thereof, various aliphatic urea compounds as described in EP 1 916 272; C1-C12 alkylene imidazole or N-arylimidazoles, such as 2-ethyl-2-methylimidazole or N-butylimidazole and 6- 10 caprolactam.
A preferred catalyst is 2,4,6-tris (dimethylaminomethyl) phenol integrated in a poly (p-vinylphenol) matrix (as described in European patent EP 0 197 892), or 2,4,6-tris (dimethylaminomethyl) phenol integrated in a novolac resin, including those described in US 15 4,701,378. Preferably, the catalyst is present in an amount of at least about 0.1 weight percent of the structural adhesive, and more preferably at least about 0.5 weight percent.
Preferably, the catalyst consists of up to about 4 weight percent of the structural adhesive, more preferably up to about 1.5 weight percent, and more preferably up to about 0.9 weight percent.
The structural adhesive of the invention can include at least one rubber-modified liquid epoxy resin.
A rubber modified epoxy resin for the purposes of this invention is a reaction product of an epoxy resin with at least one liquid rubber that has reactive groups with epoxide, such as amino groups or preferably carboxyl groups.
The resulting adduct has reactive groups with epoxide that allow the adduct to react further when the structural adhesive is cured.
It is preferable that at least part of the liquid rubber has a glass transition temperature (Tv) of -40ºC or below, 35 especially -50ºC or below.
Preferably, each of the rubbers (when more than one is used) has a glass transition temperature of - 25ºC or less. THE
Rubber tv can be as low as -100ºC or even lower. The liquid rubber is preferably a homopolymer or copolymer of a conjugated diene, especially a diene / nitrile copolymer. The conjugated diene rubber is preferably of butadiene or isoprene, but butadiene is especially preferred. The preferred nitrile monomer is acrylonitrile. Preferred copolymers are butadiene-acrylonitrile copolymers. The rubbers 10 preferably contain, in total, not more than 30 weight percent of polymerized unsaturated nitrile monomer, and preferably no more than about 26 weight percent of polymerized nitrile monomer. The rubber contains, on average, preferably from about 15 1.5, preferably from about 1.8 to about 2.5, more preferably about 2.2, of epoxide-reactive end groups per molecule. Carboxyl-terminated rubbers are preferred. The molecular weight (Mn) of the rubber is suitably from about 2000 to about 20,000, more preferably from about 3000 to about 20,000
5000. Suitable butadiene and butadiene / functional carboxyl acrylonitrile rubbers are commercially available from Noveon under the trademarks 25 registered Hycar® 2000X162 for carboxyl-terminated butadiene homopolymer, Hycar® 1300X31, Hycar® 1300X8, Hycar® 1300X13, Hycar® 1300X9 and Hycar® 1300X18 for carboxyl-terminated butadiene / acrylonitrile copolymers. A suitable amine-terminated butadiene / acrylonitrile 30 copolymer is sold under the trademark of Hycar® 1300X21. Other suitable rubber materials include amine-terminated polyethers, fatty acids (which can be dimerized or oligomerized), and elastomeric polyester. 35 The rubber is formed in an epoxy-finished adduct by reacting with an excess of an epoxy resin. Sufficient epoxy resin is provided to react with substantially all reactive groups with epoxide in the rubber and 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 reactive groups with epoxy in the rubber is preferred.
More preferably, sufficient epoxy resin is used so that the resulting product is a mixture of the adduct and some free epoxy resin; any 10 free epoxy resin counts for the unmodified rubberized epoxy resin content of the adhesive.
Typically, the rubber and an excess of the polyepoxide are mixed together with a polymerization catalyst and heated to a temperature of about 100 to about 15 250 ° C to form the adduct.
Suitable catalysts include those described above.
Preferred catalysts for the formation of the rubber-modified epoxy resin include phenyl-dimethyl-urea and triphenyl-phosphine.
A wide variety of epoxy resins can be used 20 to produce the rubber modified epoxy resin, including any of those described above.
The epoxy resin can be the same or different from that used to prepare the rubber modified epoxy resin.
Preferred polyepoxides are liquid glycidyl ethers 25 or solids of a bisphenol such as bisphenol A or bisphenol F.
Halogenated resins, particularly brominated, can be used to impart flame retardant properties, if desired.
Liquid epoxy resins (such as DERTM 330 and DERTM 331 resins, which are bisphenol A diglycidyl ethers available from The Dow Chemical Company) are especially preferred for ease of handling.
The rubber-modified epoxy resin or resins, if present, may constitute about 1 weight percent of the structural adhesive or more, preferably at least about 2 weight percent.
The rubber-modified epoxy resin can constitute up to about 25 weight percent of the structural adhesive, more preferably up to about 20 weight percent, and most preferably up to about 15 weight percent.
The structural adhesive of the invention may contain one or more 5 core-coating rubbers.
Core-coated rubber is a particulate material having a rubber core.
The rubber core preferably has a Tv of less than -20 ° C, more preferably less than -50 ° C and still more preferably less than -10 ° C.
The rubber core TV may be well below -100ºC.
The core-coating rubber also has at least a portion of the coating that preferably has a Tv of at least 50 ° C.
By "core" is meant an inner portion of the core-coating rubber.
The core may form the center of the core-coating particle, or a coating or internal domain of the core-coating rubber.
A liner is a portion of the core-liner rubber that is external to the rubber core.
The coating portion (or portions) typically form the outermost portion of the core-coating rubber particle.
The coating material is preferably grafted onto the core or is cross-linked or both.
The rubber core can make up 50 to 95%, especially 60 to 90%, of the weight of the core-coating rubber particle.
The core of the core-coating rubber can be a polymer or copolymer of a conjugated diene such as butadiene, or a lower alkyl acrylate such as n-butyl-, ethyl-, isobutyl- or 2-ethylhexylacrylate.
The core polymer can, in addition, contain up to 20% by weight of other copolymerized monounsaturated monomers such as styrene, vinyl acetate, vinyl chloride, methyl methacrylate, and the like.
The core polymer is optionally cross-linked.
The core polymer optionally contains up to 5% of a copolymerized graft-binding monomer with two or more unsaturation sites of unequal reactivity, such as dialyl maleate, monoalkyl fumarate, allyl methacrylate, and the like, at least one of the sites reactive being unconjugated. 5 The core polymer can also be a silicone rubber.
These materials often have glass transition temperatures below -100ºC.
Core-coated rubbers having a silicone rubber core include those commercially available from Wacker 10 Chemie, Munich, Germany, under the GenioperlTM trademark.
The coating polymer, which is optionally chemically grafted or cross-linked with the rubber core, is preferably polymerized from at least one lower alkyl methacrylate such as methyl, ethyl or t-butyl methacrylate.
Homopolymers of such methacrylate monomers can be used.
In addition, up to 40% by weight of the coating polymer can be formed from other monovinylidene monomers such as styrene, vinyl acetate, vinyl chloride, methyl acrylate, ethyl acrylate, butyl acrylate, and the like.
The molecular weight of the grafted coating polymer is generally between 20000 and 500000. 25 A preferred type of core-coating rubber has reactive groups in the coating polymer that can react with an epoxy resin or an epoxy resin hardener.
Glycidyl groups, such as those provided by monomers such as glycidyl methacrylate, are suitable.
A particularly preferred type of core-coated rubber is of the type described in EP 1 632 533 A1. Core-coating rubber particles as described in EP 1 632 533 A1 include a crosslinked rubber core, in most cases it is a butadiene crosslinked copolymer, and a coating which is preferably a styrene copolymer, methyl methacrylate , glycidyl methacrylate and optionally acrylonitrile.
The core-coating rubber is preferably dispersed in a polymer or an epoxy resin, also as described in EP 1 632 533 A1. 5 Preferred core-coating rubbers include those sold by Kaneka Corporation under the name Kaneka Kane Ace, including Kaneka Kane Ace MX 156 core-coating rubber dispersions and Kaneka Kane Ace MX 120. The products contain rubber particles 10 of core-coating pre-dispersed in an epoxy resin, at a concentration of approximately 25%. The epoxy resin contained in these products will form all or part of the unmodified rubberized epoxy resin component of the structural adhesive of the invention. 15 The core-coating rubber particles can make up 0 to 15 weight percent of the structural adhesive.
The total rubber content of the structural adhesive of the invention can vary from as little as 0 weight percent by 20 to as high as 30 weight percent.
A preferred rubber content for a collision-resistant adhesive is 1 weight percent to as much as 20 weight percent, preferably 2 to 15 weight percent and most preferably 4 to 15 weight percent. The total rubber content is calculated for the purposes of the invention by determining the weight of the core-coating rubber (if any), plus the weight contributed by the liquid rubber portion of any rubber-modified epoxy resin, as may be used. 30 No part of the elastomeric hardener is taken into account when calculating the total rubber content.
In each case, the weight of unreacted epoxy resins (not modified with rubber) and / or other carriers, diluents, dispersants or other ingredients that may be contained in a core-coated rubber product or modified epoxy resin with rubber, it is not included.
The weight of the coating portion of the core-coating rubber is counted as part of the total rubber content for the purposes of this invention.
The structural adhesive of the invention can contain several optional components. 5 The speed and selectivity of the cure can be increased and adjusted through the incorporation in the structural adhesive of a monomeric or oligomeric material, polymerizable by addition, ethylenically unsaturated.
This material should have a molecular weight of less than about 1500. This material can be, for example, an acrylate or methacrylate compound, an unsaturated polyester, a vinyl ester resin, or an epoxy adduct from 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 that material.
The inclusion of such an ethylenically unsaturated material provides the possibility of partially curing the structural adhesive through selective polymerization of the ethylenic unsaturation. At least one filler, rheology modifier and / or pigment is preferably present in the structural adhesive.
These can perform various functions, such as: (1) modifying the adhesive rheology in a desirable way, (2) reducing the total cost per unit of weight, (3) absorbing moisture or oils from the adhesive or a substrate to which it is applied, and / or (4) promoting cohesive, rather than adhesive, failure.
Examples of such materials include calcium carbonate, calcium oxide, talc, soot, textile fibers, glass particles or fibers, aramid pulp, boron fibers, carbon fibers, mineral silicates, mica, quartz powder, aluminum oxide hydrated, bentonite, wollastonite, kaolin, fumed silica, silica airgel, polyurea compounds, polyamide compounds or metal powders, such as aluminum powder or iron powder.
Another filler of particular interest is a microbalance having an average particle size of up to 200 micrometers and a density of up to 0.2 g / cm3. The particle size is preferably about 25 to 150 micrometers and the density is preferably about 0.05 to about 0.15 g / cm3. Heat expandable microbalions that are suitable for reducing density include those commercially available from Dualite Corporation under the trade name DualiteTM, and those sold by Akzo Nobel under the trade name ExpancelTM.
The fillers, pigment, and rheology modifiers are preferably used in a total amount of about 2 parts per hundred parts of the adhesive composition or more, more preferably about 5 parts per hundred parts of the adhesive composition or more.
They are preferably present in an amount of up to about 15-25 weight percent of the structural adhesive, more preferably up to about 20 weight percent, and most preferably up to about 15 weight percent.
The structural adhesive can also contain other additives such as dimerized fatty acids, thinners, plasticizers, extenders, pigments and dyes, fire retardants, thixotropic agents, expansion agents, flow control agents, adhesion promoters and antioxidants.
Suitable blowing agents include physical and chemical agents.
The adhesive may also contain a thermoplastic powder such as polyvinyl butyral or a polyester polyol, as described in WO 2005/118734. The adhesive composition of the invention is surprisingly storage-stable.
The viscosity of the newly formulated adhesive composition is generally slightly higher than what is observed when the curing agent is not stretched.
However, the adhesive composition of the invention thereafter increases viscosity at a significantly slower rate during storage.
The rate of increase in viscosity is generally such that, after several weeks of storage, the viscosity of the adhesive of the present invention is often equal to or even less than that of the conventional adhesive containing the non-stranded chain hardener.
The amount of time that the adhesive of the invention can be aged and still be usable will generally exceed that of an otherwise similar adhesive, which contains a non-extended chain hardener.
This advantage is observed despite the known tendency (as described, for example, in EP 1 498 441 and WO 2007/003650) of adhesives containing 10 hardeners protected with phenol, polyphenol or aminophenol to have poor storage stability.
The adhesive composition can be applied using any convenient technique.
It can be applied cold or warm if desired.
It can be applied by extruding it from a robot in the form of a droplet on the substrate, it can be applied using mechanical application methods such as a caulking gun, or any other means of manual application, 20 and it can also be applied using jet spray methods, such as a flow method or a whirlpool technique.
The whirlpool technique is applied using an apparatus well known to a person skilled in the art, such as pumps, control systems, assemblies of metering guns, remote metering devices and application guns.
Preferably, the adhesive is applied to the substrate using a jet spray or flow process.
Generally, the adhesive is applied to one or both of the substrates.
The substrates are placed in contact so that the adhesive is located between the substrates to be joined.
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, this temperature is about 80 ° C or higher, preferably about 140 ° C or more.
Preferably, the temperature is about 220 ° C or less, and more preferably about 180 ° C or less.
The adhesive of the invention can be used to bond a variety of substrates together, including wood, metal, coated metal, aluminum, a variety of plastic substrates and filled with plastic, fiberglass and the like.
In a preferred embodiment, the adhesive is used to connect car parts to each other, or to connect car parts to cars.
Such parts can be steel, coated steel, galvanized steel, 10 aluminum, coated aluminum, plastic substrates and filled with plastic.
One application of particular interest is the connection of automotive frame components to each other or to other components.
The components of the structure are often metals such as cold rolled steel, galvanized metals or aluminum.
The components that are intended to be connected to the structural components can also be metals as described above, or they can be other metals, plastics, composite materials and the like.
The elements of the assembled car structure are generally coated with a coating material that requires a firing cure.
The coating is typically baked at temperatures that can range from 140ºC to over 25ºC at 200ºC.
In such cases, it is often convenient to apply the structural adhesive to the components of the structure, then apply the coating, and cure the adhesive, at the same time as the coating is baked and cured. 30 The adhesive composition, once cured, preferably has a Young's modulus, at 23ºC, of about 1000 MPa as measured according to DIN EN ISO 527-1. Preferably the Young's modulus is about 1200 MPa or more, more preferably at least 1500 MPa.
Preferably, the cured adhesive demonstrates a tensile strength at 23 ° C of about 20 MPa or more, more preferably about 25 MPa or more, and most preferably about 35 MPa or more.
Preferably, the shear strength of a 1.5 mm thick cured adhesive layer in cold rolled steel (CRS) and a galvanized steel coated at 23 ° C is about 15 MPa or 5 more, more preferably about 20 MPa or more, and even more preferably about 25 MPa or more, measured according to DIN EN 1465. The peel impact resistance at 23ºC on these substrates is preferably at least 20 N / mm, more preferably at least 30 10 N / mm, and even more preferably at least 40 N / mm, when measured according to the ISO 11343 wedge impact method. The cured adhesive of the present invention demonstrates excellent adhesive properties (such as resistance to shear strength and resistance to peeling impact). Description of Embodiments of the Invention The following examples are provided to illustrate the invention but are not intended to limit the scope thereof. 20 All parts and percentages are by weight unless otherwise stated.
Example 1 and Comparative Sample AO Hardener 1 is prepared by heating up to 60ºC, under nitrogen, 71.5 parts of a polytetrahydrofuran of 25 molecular weight of 2900, and mixing the polyol heated to 60ºC with 8.3 parts of diisocyanate of 1, 6-hexamethylene.
After mixing for 2 minutes, 0.06 parts of dibutyl tindilaurate are added and the mixture is allowed to react under nitrogen at 85ºC for 45 minutes. 30 The resulting prepolymer has an isocyanate content of 2.6%. The prepolymer is then mixed with 3.8 parts of o, o'-diallylbisphenol A and allowed to react for 40 minutes at 85 ° C, again under nitrogen, to form an extended chain prepolymer having an isocyanate content of 1 ,two%. The extended chain prepolymer is then mixed with 16.3 parts of o, o'-diallybisphenol A under nitrogen.
The mixture is left to stir at 85 ° C for 25 minutes to protect the remaining isocyanate groups in the extended chain prepolymer.
The isocyanate content is reduced to zero.
The resulting hardener (Hardener 1) is degassed under vacuum.
It has a numerical average molecular weight (Mn) of 10200 and a weighted average molecular weight (Mw) of 24000. Hardener A is prepared by heating at 10 60ºC under nitrogen, 72.8 parts of a polytetrahydrofuran of molecular weight of 2900, and mixing the polyol heated to 60ºC with 7.6 parts of 1,6-hexamethylene diisocyanate.
After mixing for 2 minutes, 0.06 parts of dibutyl tindilaurate are added and the mixture is allowed to react under nitrogen at 85 ° C for 45 minutes.
The resulting prepolymer has an isocyanate content of 2.0%. The prepolymer is then mixed with 19.6 parts of o, o'-diallylbisphenol A under nitrogen.
The mixture is left at 20 ° C to stir at 85 ° C for 20 minutes to protect the remaining isocyanate groups in the extended chain prepolymer.
The isocyanate content is reduced to zero.
Hardener A has an Mn of 8700 and an Mw of 17500. Adhesive Example 1 and Comparative Sample A are 25 prepared by mixing the ingredients as shown in Table 1: Table 1 Component Parts by Ex Weight. 1 Sample Comp .
A Mixture of epoxy resins1 55.6 55.6 Epoxy-finished rubber2 13.2 13.2 Hardener 1 14.0 Hardener A 0 14.0 Versatile acid mono-epoxy ester3 1.2 1.2 Fillers / Dyes 5.5 5.5 Pyrogenic Silica 5.2 5.2 Accelerator4 1.0 1.0 Diciandiamide 4.3 4.3 1 A mixture of 63: 37.0 by weight of liquid diglycidyl ethers of bisphenol A having an epoxy equivalent weight of about 182-187 and a solid reaction product of epichlorohydrin and bisphenol A having an epoxy equivalent weight of 475-550. 2A butadiene-acrylonitrile rubber adduct finished in
TM 5 carboxyl (Hycar X13), epoxy resin based on bisphenol A and cashew nut oil. 3CarduraTM E10, available from Christ Chemie. 4Tris (2,4,6-dimethylaminomethyl) phenol in a poly (vinylphenol) matrix. Stability during storage is assessed by storing duplicate samples of each of Adhesive Example 1 and Comparative Sample A in nitrogen sealed containers for various periods of time, at various temperatures from about 40 ° C to 60 ° C. Viscosity measurements are made at the beginning of the tests and after storage at the specified temperatures for the indicated periods of time. The test is performed on a Bohlin CS-50 rheometer and a 4/20 mm plate / cone system. The samples are conditioned at 45ºC for five minutes. Keeping the sample at that temperature, the shear rate is increased from 0.1 / second to 20 / second over five minutes, and then decreased again to 0.1 / second at the same rate. Viscosity is measured at a shear rate of 10 / second at ascent. The results are 25 as indicated in Table 2. Table 2 Visco-Visco-Ratio Conditions,% Storage w / w Viscosity Au- (Temperature, Initial, Final, Pa * S Final / ment ** * time) Pa S ( 10 / s) (10 / s) Initial 40ºC, 12 weeks Ex. 1 220 342 1.55 55% Sample Comp. A * 154 451 2.93 193% 50ºC, 6 weeks Ex. 1 220 516 2.35 135% Sample Comp. A * 154 622 4.04 304% 60ºC, 3 weeks Ex. 1 220 1355 6.16 516% Sample Comp. A * 154 1437 9.33 833% * It is not an example of the invention. ** Calculated as 100% X
[(final viscosity - initial viscosity) / initial viscosity]. As shown by the data in Table 2, the adhesive of the invention has a slightly higher initial viscosity than that of Comparative Sample A, but is much more storage-stable at each of the temperatures tested. In all cases, the viscosity of Comparative Sample A increases at a much faster rate than that of Example 1, and in all cases it reaches a higher absolute value at the end of the test period. These results indicate that Adhesive Example 1 has a longer validity over a temperature range than Comparative Sample A, despite having a higher initial viscosity. 15 Example 2 and Comparative Sample BO Hardener 2 is prepared by heating up to 60ºC, under nitrogen, 82.2 parts of a 2900 molecular weight polytetrahydrofuran, and mixing the polyol heated to 60ºC with 9.5 parts of 1-isocyanate, 6-hexamethylene. 20 After mixing for 2 minutes, 0.06 parts of dibutyl tindilaurate are added and the mixture is allowed to react under nitrogen at 85ºC for 45 minutes. The resulting prepolymer has an isocyanate content of 2.6%. 25 The prepolymer is then mixed with 4.4 parts of o, o'-diallylbisphenol A and allowed to react for 40 minutes at 85 ° C, again under nitrogen, to form an extended chain prepolymer having an isocyanate content of 1 ,two%. 30 The extended chain prepolymer is then mixed with 3.8 parts of o-allylphenol under nitrogen. The mixture is allowed to stir at 85 ° C for 25 minutes to protect the remaining isocyanate groups in the extended chain prepolymer. The isocyanate content is reduced to zero. The resulting hardener (Hardener 2) is degassed under vacuum. Hardener 2 has a Mn of 9800 and an Mw of
22800.
Hardener B is prepared by heating up to 60ºC, under nitrogen, 85.2 parts of a 2900 molecular weight polytetrahydrofuran, and mixing the polyol heated to 60ºC with 8.7 parts of 1,6-hexamethylene diisocyanate. 5 After mixing for 2 minutes, 0.06 parts of dibutyl tindilaurate are added and the mixture is allowed to react under nitrogen at 85 ° C for 45 minutes.
The resulting prepolymer has an isocyanate content of 2.0%. 10 The prepolymer is then mixed with 6.1 parts of o-allylphenol under nitrogen.
The mixture is allowed to stir at 85 ° C for 20 minutes to protect the remaining isocyanate groups in an extended chain prepolymer.
The isocyanate content is reduced to zero.
Hardener B has a 15 Mn of 7100 and a Mw of 13500. One part heat-activated adhesive formulations are prepared from each of Hardener 2 and Hardener B.
The formulation for Example 2 is the same as that shown in Table 1 for Example 1, except that Hardener 1 is replaced by an equal amount of Hardener 2. Comparative Sample B is the same as Comparative Sample A, except that Hardener A is replaced by an equal amount of Hardener B.
Storage stability for Example 2 and Comparative Sample B is assessed in the same manner as described above, with results as shown in Table 3.
Table 3 Viscosity Conditions Viscosity Ratio,% of Initial Storage, Final, Pa * S Viscosity Increase ** (Temperature, Pa * S (10 / s) (10 / s) Final / Initial time) 40ºC, 12 weeks Ex. 2 152 281 1.85 85% Sample Comp. 96 213 2.22 122% B * 50ºC, 6 weeks Ex. 2 152 384 2.53 153% Sample Comp. 96 280 2.92 192% B * 60ºC, 3 weeks Ex. 2 152 720 4.74 374% Sample Comp. 96 604 6.29 529% B * * It is not an example of the invention. ** Calculated as 100% X [(final viscosity - initial viscosity) / initial viscosity]. 5 At each temperature tested, Example 2 becomes more viscous more slowly than Comparative Sample B.
Example 3 and Comparative Sample C Hardener 3 is prepared by heating up to 60ºC, under nitrogen, 67.6 parts of a polytetrahydrofuran of 10 molecular weight of 2900, and mixing the heated polyol with 0.4 trimethylolpropane until homogeneous.
At 60 ° C, 9.3 parts of 1,6-hexamethylene diisocyanate are added.
After mixing for 2 minutes, 0.06 parts of dibutyl tindilaurate are added and the mixture is left to react under nitrogen at 85 ° C for 45 minutes.
The resulting prepolymer has an isocyanate content of 3.0%. The prepolymer is then mixed with 4.3 parts of o, o'-diallylbisphenol A and allowed to react for 40 minutes at 20 85 ° C, again under nitrogen, to form an extended chain prepolymer having an isocyanate content of 1 , 4%. The extended chain prepolymer is then mixed with 18.4 parts of o, o'-diallybisphenol A under nitrogen.
The mixture is left to stir at 85 ° C for 25 minutes to protect the remaining isocyanate groups in the extended chain prepolymer.
The isocyanate content is reduced to zero.
The resulting hardener (Hardener 3) 5 is degassed under vacuum.
Hardener 3 has a Mn of 10900 and an Mw of 30750. Hardener C is prepared by heating up to 60ºC, under nitrogen, 70.9 parts of a 2900 molecular weight polytetrahydrofuran, and mixing the heated polyol 10 with 0.5 parts trimethylolpropane until homogeneous.
At 60 ° C, 8.2 parts of 1,6-hexamethylene diisocyanate are added.
After mixing for 2 minutes, 0.06 parts of dibutyl tindilaurate are added and the mixture is allowed to react under nitrogen at 85ºC for 45 15 minutes.
The resulting prepolymer has an isocyanate content of 2.0%. The prepolymer is then mixed with 20.3 parts of o, o'-diallylbisphenol A under nitrogen.
The mixture is allowed to stir at 85 ° C for 20 minutes to protect the remaining 20 isocyanate groups in the extended chain prepolymer.
The isocyanate content is reduced to zero.
Hardener C has a Mn of 9700 and an Mw of 27200. Heat-activated adhesive formulations, on the one hand, are prepared from each of Hardener 25 3 and Hardener C.
The formulation for Example 3 is the same as that shown in Table 1 for Example 1, except that Hardener 1 is replaced by an equal amount of Hardener 3. Comparative Sample C is the same as Comparative Sample A, except that Hardener A is replaced by an equal amount of Hardener C.
Storage stability is assessed for each of these as before, the results being as indicated in Table 4.
Table 4 Viscosity Conditions Viscosity Ratio,% of Initial Storage, Final, Pa * S Viscosity Increase ** (Temperature, Pa * S (10 / s) (10 / s) Final / Initial time) 40ºC, 24 weeks Ex. 3 274 1275 4.65 365% Sample Comp. 199 1704 8.56 756% C * 50ºC, 8 weeks Ex. 3 274 875 3.19 219% Sample Comp. 199 1273 6.40 540% C * 60ºC, 3 weeks Ex. 3 274 1279 4.67 367% Sample Comp. 199 1822 9.16 816% C * * It is not an example of the invention. ** Calculated as 100% X [(final viscosity - initial viscosity) / initial viscosity]. As shown by the data in Table 4, the adhesive of the invention has a slightly higher initial viscosity, but is much more stable to storage at each of the tested temperatures.
In all cases, the viscosity of the Comparative Adhesive increases at a much faster rate than that of Example 3, and in all cases it reaches a higher absolute value at the end of the test period.
Example 4 and Comparative Sample D Hardener 4 is prepared by heating up to 60ºC, under 15 nitrogen, 79.2 parts of a 2900 molecular weight polytetrahydrofuran, and mixing the heated polyol with 0.5 parts of trimethylolpropane until homogeneous.
At 60 ° C, 10.9 parts of 1,6-hexamethylene diisocyanate are added.
After mixing for 2 minutes, 0.06 20 parts of dibutyl tindilaurate are added and the mixture is allowed to react under nitrogen at 85 ° C for 45 minutes.
The resulting prepolymer has an isocyanate content of 3.0%. The prepolymer is then mixed with 5.0 parts of o, o'-
diallybisphenol A and allowed to react for 40 minutes at 85 ° C, again under nitrogen, to form an extended chain prepolymer having an isocyanate content of 3.0%. 5 The extended chain prepolymer is then mixed with 4.4 parts of o-allylphenol under nitrogen. The mixture is allowed to stir at 85 ° C for 25 minutes to protect the remaining isocyanate groups in the extended chain prepolymer. The isocyanate content is reduced to zero. The resulting hardener (Hardener 4) is degassed under vacuum. Hardener 4 has an Mn of 8700 and an Mw of
27100. Hardener D is prepared by heating up to 60ºC, under nitrogen, 83.6 parts of polytetrahydrofuran, and 15 mixing the heated polyol with 0.6 parts of trimethylolpropane until homogeneous. At 60 ° C, 9.7 parts of 1,6-hexamethylene diisocyanate are added. After mixing for 2 minutes, 0.06 parts of dibutyl tindilaurate are added and the mixture is allowed to react under nitrogen at 85 ° C for 45 minutes. The resulting prepolymer has an isocyanate content of 2.0%. The prepolymer is then mixed with 6.1 parts of o-allylphenol under nitrogen. The mixture is allowed to stir at 25 85 ° C for 20 minutes to protect the remaining isocyanate groups in the extended chain prepolymer. The isocyanate content is reduced to zero. One-part heat activated adhesive formulations are prepared from each of Hardener 4 and Hardener D. The formulation for Example 4 is the same as shown in Table 1 for Example 1, except that the Hardener 1 is replaced by an equal amount of Hardener 4. Comparative Sample D is the same as Comparative Sample A, except that Hardener A is replaced by an equal amount of Hardener D. Hardener D has a Mn of 7600 and a 19700 Mw. Storage stability is assessed for each of these as before, the results being as shown in Table 5. Table 5 Viscosity Conditions Viscosity Ratio,% of Initial, Final Storage, Pa * S Viscosity Increase ** ( Temperature, Pa * S (10 / s) (10 / s) Final / Initial time) 40ºC, 24 weeks Ex. 4 188 642 3.41 241% Sample Comp. 110 798 7.25 625% C * 50ºC, 12 weeks Ex. 4 188 1424 7.57 657% Sample Comp. 110 1690 15.36 1436% C * 60ºC, 4 weeks Ex. 4 188 1540 8.19 719% Sample Comp. 110 Gelled SS SS C * * It is not an example of the invention. ** Calculated as 100% X 5 [(final viscosity - initial viscosity) / initial viscosity]. SS - meaningless, since the aged adhesive has solidified.
As shown by the data in Table 6, the adhesive of the invention has a slightly higher initial viscosity, but is much more stable to storage at each of the tested temperatures.
In all cases, the viscosity of Comparative Adhesive D increases at a much faster rate than that of Example 4, and in all cases it reaches a higher absolute value at the end of the test period.
Examples 5-7 Hardener 5 is prepared by heating up to 60ºC, under nitrogen, 76.1 parts of a 2000 molecular weight polytetrahydrofuran, and mixing the polyol heated to 20 60ºC with 12.8 parts of 1.6 diisocyanate - hexamethylene.
After mixing for 2 minutes, 0.06 parts of dibutyl tindilaurate are added and the mixture is allowed to react under nitrogen at 85ºC for 45 minutes.
The resulting prepolymer has an isocyanate content of
3.6%. The prepolymer is then mixed with 5.9 parts of o, o'-diallylbisphenol A and allowed to react for 40 minutes at 85 ° C, again under nitrogen, to form an extended chain prepolymer having an isocyanate content of 1 , 7%. The extended chain prepolymer is then mixed with 5.2 parts of o-allylphenol under nitrogen. The mixture is allowed to stir at 85 ° C for 25 minutes to protect the remaining 10 isocyanate groups in the extended chain prepolymer. The isocyanate content is reduced to zero. The resulting hardener (Hardener 5) is degassed under vacuum. Hardener 5 has a Mn of 7600 and an Mw of
18200. 15 Hardener 6 is produced in the same way as Hardener 5, using 63.4 parts of the polyol, 10.7 parts of the isocyanate, 0.06 parts of the catalyst, 4.9 parts of o, o'-diallybisphenol A in the chain extension step, and 21.0 parts of o, o'-diallybisphenol A in the protection step 20. Hardener 6 has a Mn of 5900 and an Mw of
13700. Hardener 7 is prepared by heating up to 60ºC, under nitrogen, 60.1 parts of a 2000 molecular weight polytetrahydrofuran, and mixing the heated polyol 25 with 0.4 parts of trimethylolpropane until homogeneous. At 60 ° C, 11.6 parts of 1,6-hexamethylene diisocyanate are added. After mixing for 2 minutes, 0.06 parts of dibutyl tindilaurate are added and the mixture is allowed to react under nitrogen at 85ºC for 45 30 minutes. The resulting prepolymer has an isocyanate content of 4.0%. Hardener 7 has an Mn of 7200 and an Mw of 23800. The prepolymer is then mixed with 5.3 parts of o, o'-diallylbisphenol A and allowed to react for 40 minutes at 35 85ºC, again under nitrogen, to form an extended chain prepolymer having an isocyanate content of 1.9%.
The extended chain prepolymer is then mixed with 22.6 parts of o, o'-diallybisphenol A under nitrogen.
The mixture is allowed to stir at 85 ° C for 25 minutes to protect the remaining isocyanate groups in the extended chain prepolymer.
The isocyanate content is reduced to zero.
The resulting hardener (Hardener 7) is degassed under vacuum.
One-part heat-activated adhesive formulations are prepared from each of Hardener 5-7. The 10 formulations for Examples 5-7 are the same as shown in Table 1 for Example 1, except that Hardener 1 is replaced with an equal amount of Hardener 5-7, respectively.
Storage stability is assessed for each 15 of these as before, with results as shown in Table 6. Table 6 Viscosity Conditions Viscosity Ratio,% of Initial, Final Storage, Pa * S Increase Viscosity ** (Temperature, Pa * S (10 / s) (10 / s) Final / Initial time) 40ºC, 8 weeks Ex. 5 170 250 1.47 47% Ex. 6 173 234 1.35 35% Ex. 7 220 252 1.15 15% 50ºC, 6 weeks Ex. 5 170 324 1.91 91% Ex. 6 173 450 2.60 160% Ex. 7 220 532 2.42 142% ** Calculated as 100% X [(final viscosity - initial viscosity ) / initial viscosity]. SS - meaningless, since the aged adhesive has solidified.
The data in Table 6 shows that the benefit of better storage stability is seen through a variety of hardener compositions.
The peeling impact test is performed for the 25 Adhesive Examples 1-7, and for two commercially available adhesive products (Comparative Adhesives E and F). The substrate is 1.5 mm 14O3 steel.
The peeling impact test is carried out according to the ISO 11343 wedge impact method. The test is carried out at an operating speed of 2 m / s.
The peeling impact test is carried out at 23ºC, and the resistance is measured in N / mm. 5 The specimens for the peeling impact test are 90 mm × 20 mm with a bonded area of 30 × 20 mm.
The samples are prepared by cleaning them with acetone.
Teflon tape is applied to the specimens to define the bonding area.
The structural adhesive is then applied to the bonding area of one specimen and squeezed over the other specimen to prepare each test specimen.
The adhesive layer is 0.2 mm thick.
Duplicate samples are cured for 30 minutes at 180ºC. 15 Duplicate specimens are prepared and evaluated for shear strength in accordance with DIN ISO 1465. The substrate is 1.0 mm BCO4 cold rolled steel.
The test is performed at a test speed of 10 mm / minute.
The test is carried out at 20 to 23ºC.
Test samples are prepared using each adhesive.
The bonded area in each case is 25 × 10 mm.
The adhesive layer is 0.2 mm thick.
Duplicate test specimens are cured for 30 minutes at 180ºC. 25 The glass transition temperature of a sample of the cured adhesive is measured by DSC.
The glass transition temperature (Tv) and the results of the peel impact and shear strength test are as shown in Table 7.
Table 7 Tv, Resistance to impact force of ºC shear, peeling, TA, N / mm, MPa energy (J) Ex. 1 90 35.5 56 (21) Ex. 2 97 30.2 47 (17) Ex. 3 93 36.7 57 (22) Ex. 4 93 32.4 54 (20) Ex. 5 89 35.5 60 (22) Ex. 6 88 37.6 54 (21) Ex. 7 86 38.2 55 (20) Adhesive 94 32.1 57 (22) Comparative E Adhesive 87 31.5 44 (16) Comparative F The data in Table 7 indicate that the adhesives according to the invention have, when cured, properties comparable with, or better whereas, 5 commercially available adhesives.
In particular, the resistance to shear and peeling impact is significantly increased in many cases.

权利要求:
Claims (13)
[1]
1. Structural adhesive of one part, characterized by the fact that it comprises: A) at least one epoxy resin; 5 B) a reactive elastomeric hardener containing protected isocyanate groups; and C) one or more epoxy curing agents; wherein the elastomeric hardener is formed by: a) reacting an excess of a polyisocyanate with a polyol of a weight equivalent to 300-3000 or with a mixture of a polyol of a weight equivalent to 300-3000 and an agent of branching, to form an isocyanate-terminated prepolymer; b) reaction of the isocyanate-terminated prepolymer with a chain extender to produce an extended-chain isocyanate-terminated prepolymer, and c) protection of at least 90% of the terminal isocyanate groups of the isocyanate-terminated prepolymer extended with a protective agent selected from a monophenol, a polyphenol or an aminophenol.
[2]
2. Structural adhesive according to claim 1, characterized in that the polyol weighing 300-3000 is a polyether, a hydroxyl-terminated polybutadiene or a mixture of a polyether and a hydroxyl-terminated polybutadiene.
[3]
Structural adhesive according to claim 1 or 2, characterized in that the chain extender contains two phenolic hydroxyl groups.
[4]
4. Structural adhesive according to any one of the claims 1 to 3, characterized in that the protective agent is a monophenol.
[5]
Structural adhesive according to any one of claims 1 to 3, characterized in that the protective agent is a polyphenol. 35
[6]
Structural adhesive according to any one of claims 1 to 3, characterized in that the protective agent is an aminophenol.
[7]
Structural adhesive according to any one of claims 1 to 6, characterized in that the epoxy resin includes at least one diglycidyl ether of a polyhydric phenol. 5
[8]
Structural adhesive according to any one of claims 1 to 7, characterized in that it contains at least one liquid rubber terminated in epoxide.
[9]
9. Structural adhesive, according to any of the 10 claims 1 to 8, characterized by the fact that it also comprises a latent catalyst that becomes active only after exposure to high temperatures.
[10]
Structural adhesive according to claim 9, characterized by the fact that the latent catalyst is 15 2,4,6-tris (dimethylaminomethyl) phenol integrated in a matrix of poly (p-vinylphenol) or 2,4,6-tris (dimethylaminomethyl) phenol integrated in a novolac resin.
[11]
Structural adhesive according to any one of claims 1 to 10, characterized in that the curing agent includes one or more of a boron / amine trichloride complex, a boron / amine trifluoride complex, dicyandiamide , melamine, diallymelamine, acetoguanamine and benzoguanamine, 3-amino-1,2,4-triazole, 25 adipic dihydrazide, stearic dihydrazide, isophthalic dihydrazide, semicarbazide, cyanoacetamide, and diaminodiphenylsulfones.
[12]
Structural adhesive according to any one of claims 1 to 11, characterized in that it further comprises one or more of calcium carbonate, calcium oxide, talc, soot, textile fibers, particles or glass fibers, pulp of aramid, boron fibers, carbon fibers, a mineral silicate, mica, quartz powder, hydrated aluminum oxide, bentonite, 35 wollastonite, kaolin, fumed silica, silica airgel, polyurea compound, polyamide compound, or powder aluminum, iron powder or microbalions having an average particle size of up to 200 micrometers and a density of up to 0.2 g / cm3.
[13]
13. Method of applying structural adhesive, as defined in any one of claims 1 to 12, 5 characterized by the fact that it comprises the application of the structural adhesive of any of the preceding claims on the surfaces of two elements, and curing of the structural adhesive for form an adhesive bond between the two elements.

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JP2010530472A|2010-09-09|Impact resistant epoxy adhesive with very low sensitivity to temperature changes

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JP2010536953A|2010-12-02|Two-component impact-resistant epoxy adhesive

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WO2009094295A1|2009-07-30|Structural epoxy resin adhesives containing epoxide-functional, polyphenol-extended elastomeric tougheners

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EP3585854B1|2021-10-13|One-component toughened epoxy adhesives containing a mixture of latent curing agents

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US11274236B2|2022-03-15|One-component toughened epoxy adhesives containing a mixture of latent curing agents

同族专利:

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公开号 | 公开日

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KR101981715B1|2019-05-23|

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US20130263995A1|2013-10-10|

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EP2655516B1|2018-12-26|

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JP6035247B2|2016-11-30|

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US9181463B2|2015-11-10|

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CN103180400A|2013-06-26|

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EP2655516A2|2013-10-30|

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KR20130141617A|2013-12-26|

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CN103180400B|2016-08-17|

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WO2012091842A3|2012-08-23|

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US20160017192A1|2016-01-21|

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WO2012091842A2|2012-07-05|

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JP2014505761A|2014-03-06|

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法律状态:
2021-04-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2021-04-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-08-24| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-12-07| B09B| Patent application refused [chapter 9.2 patent gazette]|

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2022-02-22| B09B| Patent application refused [chapter 9.2 patent gazette]|Free format text: MANTIDO O INDEFERIMENTO UMA VEZ QUE NAO FOI APRESENTADO RECURSO DENTRO DO PRAZO LEGAL |

优先权:

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申请号 | 申请日 | 专利标题

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US201061427192P| true| 2010-12-26|2010-12-26|

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US61/427,192|2010-12-26|

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PCT/US2011/062491|WO2012091842A2|2010-12-26|2011-11-30|Structural epoxy resin adhesives containing chain-extended elastomeric tougheners capped with phenol, polyphenol or aminophenol compounds|

---