WO1996011240A1 - Pressure sensitive structural adhesives and sealants based on telechelic/heterotelechelic polymers with dual cure systems - Google Patents
Pressure sensitive structural adhesives and sealants based on telechelic/heterotelechelic polymers with dual cure systems Download PDFInfo
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- WO1996011240A1 WO1996011240A1 PCT/EP1995/004015 EP9504015W WO9611240A1 WO 1996011240 A1 WO1996011240 A1 WO 1996011240A1 EP 9504015 W EP9504015 W EP 9504015W WO 9611240 A1 WO9611240 A1 WO 9611240A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
- C08G18/6208—Hydrogenated polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/243—Two or more independent types of crosslinking for one or more polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J119/00—Adhesives based on rubbers, not provided for in groups C09J107/00 - C09J117/00
- C09J119/006—Rubber characterised by functional groups, e.g. telechelic diene polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/08—Epoxidised polymerised polyenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/40—Compositions for pressure-sensitive adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2190/00—Compositions for sealing or packing joints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
- C08L2666/16—Addition or condensation polymers of aldehydes or ketones according to C08L59/00 - C08L61/00; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
Definitions
- a polymer system comprising from 95 to 15 percent by weight of a telechelic polymer and from 5 to 85 percent by weight of a heterotelechelic polymer wherein at least one of the functionalities on the heterotelechelic polymer is the same as the functionality on the telechelic polymer and
- copolymers of conjugated diolefins are prepared by contacting the monomer or monomers to be polymerized simultaneously or sequentially with an anionic polymerization initiator such as group IA metals, their alkyls, amides, silanolates, napthalides, biphenyls or anthracenyl derivatives.
- an anionic polymerization initiator such as group IA metals, their alkyls, amides, silanolates, napthalides, biphenyls or anthracenyl derivatives.
- an organo alkali metal such as lithium, sodium or potassium
- Particularly effective anionic polymerization initiators are organo lithium compounds having the general formula:
- heterotelechelic polymers There are many types of heterotelechelic polymers which can be used herein. As stated above, one end of the heterotelechelic polymer will have the same functional group as the telechelic polymer. The other end will have a different type of functional group which does not react with its crosslinker under the same conditions used to crosslink the telechelic polymer. Heterotelechelic polymers may include those wherein protected functional initiators and/or protected functional capping agents are included into the polymer. Heterotelechelic polymers can also be made by functionalization reactions on telechelic polymers.
- the polymer system is a combination of hydroxy functional telechelic and heterotelechelic polymers wherein the other functionality on the heterotelechelic polymer is an olefinic epoxy.
- the curing system is an isocyanate for ambient cure and a melamine resin for bake cure after the adhesive has been applied.
- this invention is not restricted to these chemistries.
- the following are some examples of other suitable telechelic and heterotelechelic polymers.
- C C unsaturation
- acrylic unsaturation for free radical cure via peroxide or radiation
- epoxidized olefin for cationic cure via a blocked Lewis acid or for radiation cure or for melamine cure
- glycidyl ether epoxy for acid or anhydride cure or catalytic cure
- the heterotelechelic polymer will also have an acrylic group and another functional group such as hydroxy functionality (for melamine or blocked isocyanate cure) , olefinic unsaturation, glycidyl ether epoxy, or epoxidized olefin functionality. If the telechelic polymer has glycidyl ether functionality (for ambient cure with aliphatic amines), the heterotelechelic polymer will have glycidyl ether epoxy functionality and another functional group such as olefinic unsaturation, epoxidized olefin, or hydroxy functionality. There are many other combinations for functional groups and curing systems and thus there are many possibilities for dual curing systems.
- a saturated, dihydroxy polydiene polymer can also be made using a mono-lithium initiator which contains a hydroxyl group which has been blocked as the silyl ether. Details of the polymerization procedure can be found in U.S. Patent No. 5,376,745.
- a suitable initiator is hydroxypropyllithium in which the hydroxyl group is blocked as the tert-butyl-di ethylsilyl ether.
- This mono-lithium initiator can be used to polymerize isoprene or butadiene, with or without styrene, in hydrocarbon or polar solvent. The molar ratio of initiator to monomer determines the molecular weight of the polymer.
- a and B are polymer blocks which may be homopolymer blocks of conjugated diolefin monomers, copolymer blocks of conjugated diolefin monomers, or copolymer blocks of diolefin monomers and monoalkenyl aromatic hydrocarbon monomers
- S is a vinyl aromatic hydrocarbon block
- Y is a coupling agent
- z is 0 or 1
- n is an integer from 1 to 20.
- the heterotelechelic polymer preferably is an epoxidized monohydroxylated polydiene polymer which is comprised of at least two polymerizable ethenically unsaturated monomers wherein at least one is a diene monomer that yields unsaturation suitable for epoxidation.
- the hydroxylated heterotelechelic polymers are most preferably block copolymers of at least two conjugated dienes, preferably isoprene and butadiene, and, optionally, a vinyl aromatic hydrocarbon wherein a hydroxyl group is attached at one end of the polymer molecule. These polymers may be hydrogenated or unhydrogenated.
- diblock polymers which fall within the scope of formula (I) above.
- the overall molecular weight of such diblocks may range from 1500 to 15000, preferably 3000 to 7000.
- Either of the blocks in the diblock may contain some randomly polymerized vinyl aromatic hydrocarbon as described above.
- I represents isoprene
- B represents butadiene
- S represents styrene
- a slash (/) represents a random copolymer block
- the diblocks may have the following structures:
- triblock copolymers are also preferred for use herein.
- Such triblocks usually include a styrene block or randomly copolymerized styrene to increase the polymers glass transition temperature, compatibility with polar materials, strength, and room temperature viscosity.
- These triblocks include the following specific structures:
- the heterotelechelic hydroxylated polydienes synthesized by anionic polymerization will also have olefinic unsaturation. Although these polymers may be useful as is, the olefinic unsaturation can also be epoxidized.
- Epoxidation of the base polymer can be effected by reaction with organic peracids which can be preformed or formed in situ. Suitable preformed peracids include peracetic and perbenzoic acids. In situ formation may be accomplished by using hydrogen peroxide and a low molecular weight fatty acid such as formic acid. Alternatively, hydrogen peroxide in the presence of acetic acid or acetic anhydride and a cationic exchange resin will form a peracid.
- the cationic exchange resin can optionally be replaced by a strong acid such as sulfuric acid or p-toluenesulfonic acid.
- the epoxidation reaction can be conducted directly in the polymerization cement (polymer solution in which the polymer was polymerized) or, alterna ⁇ tively, the polymer can be redissolved in an inert solvent.
- the molecular weights of linear polymers or unassembled linear segments of polymers such as mono-, di-, triblock, etc., arms of star polymers before coupling are conveniently measured by Gel Permeation Chromatography (GPC) , where the GPC system has been appropriately calibrated.
- GPC Gel Permeation Chromatography
- the polymer is essentially monodisperse (weight average molecular weight/number average molecular weight ratio approaches unity) , and it is both convenient and adequately descriptive to report the "peak" molecular weight of the narrow molecular weight distribution observed. Usually, the peak value is between the number and the weight average.
- the peak molecular weight is the molecular weight of the main species shown on the chromatograph.
- the weight average molecular weight should be calculated from the chromatograph and used.
- materials to be used in the columns of the GPC styrene-divinyl benzene gels or silica gels are commonly used and are excellent materials.
- Tetrahydrofuran is an excellent solvent for polymers of the type described herein.
- a refractive index detector may be used.
- the light scattering measurements are performed as a function of scattering angle, polymer concentration and polymer size using standard procedures.
- the differential refractive index (DRI) of the sample is measured at the same wave length and in the same solvent used for the light scattering.
- Relevant references are: 1. Modern Size-Exclusion Liquid Chromatography, M. W. Yau, J. J. Kirkland, D. D. Bly, John Wiley and Sons, New York, New York, 1979.
- these block copolymers can be partially hydrogenated. Hydrogenation may be effected selectively as disclosed in U.S. Patent Reissue 27,145.
- the hydrogenation of these polymers and copolymers may be carried out by a variety of well established processes including hydrogenation in the presence of such catalysts as Raney Nickel, nobel metals such as platinum and the like, soluble transition metal catalysts and titanium catalysts as in U.S. Patent 5,039,755.
- a particularly preferred catalyst is a mixture of nickel 2-ethylhexanoate and triethylaluminu .
- the polymers may have different diene blocks and these diene blocks may be selectively hydrogenated as described in U.S. Patent 5,229,464.
- the telechelic polydiene polymers of this invention are preferably hydrogenated such that at least 90%, preferably at least 95%, of the carbon to carbon double bonds become saturated. It is preferred that the heterotelechelic polydiene polymers be partially unsaturated in order that the carbon to carbon double bonds can be used as is or can be used for further functionalization such as to make the epoxidized polymers of this invention.
- the level of unsaturation in the heterotelechelic polymers should be from 0.2 to 7.5 meq of double bonds per gram of polymer.
- the amount of the telechelic polymer used in the polymer part of the adhesive or sealant composition may range from 95 to 15% by weight.
- the pressure sensitive adhesive will not have sufficient strength and if more than 95% is used, there will be too little of the heterotelechelic polymer to cure and increase cohesive strength.
- the amount of the dual curing system will depend on the type of functionality in the heterotelechelic polymer and on the particular curing system used. Normally, however, the hydroxyl functional telechelic and heterotelechelic polymers will be cured with a stoichiometric amount of isocyanate. If olefinic unsaturation is the other functionality in the heterotelechelic polymer, then a sulfur-based crosslinking system will be used at from
- the polyisocyanate used in this invention can be an aliphatic or an aromatic polyisocyanate or a mixture of the two. Aliphatic polyisocyanates are generally preferred since they will give sealants and adhesives having lighter color and better durability than aromatic polyisocyanates.
- DESMODUR Z-4370 has been found to be a particularly effective triisocyanate for this invention because it has excellent compatibility with the saturated, hydroxylated polydiene polymers of this invention. It gives clear, colorless sealants and adhesives with excellent tack and peel and should also give excellent durability, even under exposure to sunlight. (MONDUR, MILES and DESMODUR are trademarks) . Although isocyanates having 3 or more NCO groups per molecule will be the major component of the polyisocyanate curing agent, small amounts of diisocyanates and monoisocyanates can also be used.
- the crosslinking agents which are useful in the present invention are amino resins.
- an amino resin is a resin made by reaction of a material bearing NH groups with a carbonyl compound and an alcohol.
- the NH bearing material is commonly urea, melamine, benzoguanamine, glycoluril, cyclic ureas, thioureas, guanidines, urethanes, cyanamides, etc.
- the most common carbonyl component is formaldehyde and other carbonyl compounds include higher aldehydes and ketones.
- the most commonly used alcohols are methanol, ethanol, and butanol.
- Type 2 Type 3
- Y is the material that bore the NH groups
- the carbonyl source was formaldehyde
- R is the alkyl group from the alcohol used for alkylation.
- type 1 amino resins are preferred in the present invention.
- the amino resin must be compatible with both the telechelic and the heterotelechelic polymer.
- a compatible amino resin is defined as one which gives a phase stable blend with the polymers at the desired concentration and at the temperature at which the compositions will be mixed and applied.
- the dual curing system preferably contains an amino resin having an equivalent weight between 50 and 500.
- BEETLE 80 is a urea- formaldehyde resin where R is C4H9 whose ideal monomeric structure is depicted :
- the adhesive and sealant compositions of this invention may consist only of the telechelic and heterotelechelic polymers along with the dual curing system crosslinkers. However, it may be necessary for a formulator to combine a variety of ingredients together with the polymers of the present invention in order to obtain products having the proper combination of properties (such as adhesion, cohesion, durability, low cost, etc.) for particular applications. Although a suitable formulation might contain only the polymers and curing agents, in most adhesive and sealant applications, suitable formulations would also contain various combinations of resins, plasticizers, fillers, solvents, stabilizers and other ingredients such as asphalt. The following are some typical examples of formulating ingredients for adhesives and sealants.
- tackifying resins may be employed wherein the resinous copolymer comprises 20-80 weight percent of piperylene and 80-20 weight percent of 2-methyl-2-butene.
- the resins normally have ring and ball softening points as determined by ASTM method E28 between about 80°C and 115°C.
- Aromatic resins may also be employed as tackifying agents, provided that they are compatible with the particular polymers used in the formulation. Normally, these resins should also have ring and ball softening points between about 80°C and 115°C although mixtures of aromatic resins having high and low softening points may also be used.
- Useful resins include coumarone- indene resins, polystyrene resins, vinyl toluene-alpha methylstyrene copolymers and polyindene resins.
- adhesion promoting resins which are also useful in the compositions of this invention include hydrogenated rosins, esters of rosins, polyterpenes, terpenephenol resins and polymerized mixed olefins, lower softening point resins and liquid resins.
- An example of a liquid resin is ADTAC LV (trademark) resin from HERCULES.
- the tackifying resin be a saturated resin, e.g., a hydrogenated dicyclopentadiene resin such as ESCOREZ 5000 series resin made by EXXON or a hydrogenated polystyrene or polyalphamethylstyrene resin such as REGALREZ.
- the amount of adhesion promoting resin employed varies from 0 to 400 parts by weight per hundred parts polymer (php) , preferably between 20 to 350 php, most preferably 20 to 150 php.
- the selection of the particular tackifying agent is, in large part, dependent upon the specific polymers employed in the adhesive composition.
- fillers and pigments can be included in the formulation. This is especially true for exterior adhesives or sealants in which fillers are added not only to create the desired appeal but also to improve the performance of the adhesives or sealants such as their weatherability.
- a wide variety of fillers can be used. Suitable fillers include calcium carbonate, clays, talcs, silica, zinc oxide, titanium dioxide and the like. The amount of filler usually is in the range of 0 to 800 php depending on the type of filler used and the application for which the adhesive or sealant is intended. An especially preferred filler is titanium dioxide. - 23 - Stabilizers known in the art may also be incorporated into the composition.
- All adhesive and sealant compositions based on this invention will contain some combination of the various formulating ingredients disclosed herein. No definite rules can be offered about which ingredients will be used. The skilled formulator will choose particular types of ingredients and adjust their concentrations to give exactly the combination of properties needed in the composition for any specific adhesive or sealant application. So, beyond the telechelic polymer, the heterotelechelic polymer and the two curing agent systems, the formulator will choose to use or not to use among the various resins, fillers and pigments, plasticizers, oligomers, stabilizers and solvents.
- the key to the concept of the present invention is to make a pressure sensitive adhesive or sealant which can be further cured after it is applied, making it behave as a structural adhesive or sealant.
- the adhesive or sealant is based on a mixture of a telechelic polymer, such as the preferred hydrogenated diol, with a heterotelechelic polymer, such as the preferred epoxidized monohydroxylated diene polymer, and a dual curing system including, for example, an isocyanate and an amino resin.
- a pressure sensitive adhesive composition (or pressure sensitive sealant composition) is formed which can be applied to a substrate and will immediately adhere thereto.
- compositions cure through amino resin curing of the epoxy groups, further increasing the cohesive strength and modulus of the adhesive or sealant composition and making it perform more like a structural adhesive than a pressure sensitive adhesive.
- a specific use for such compositions is to make a free film which is a pressure sensitive adhesive between two layers of release paper. This free film is then used to adhere automobile parts together, such as hood and door reinforcements, with enough strength to hold them in place until the body is baked. Upon baking, the adhesive cures further, giving a structural or at least semi-structural bond holding the parts permanently in place. This use has the additional benefit that the free film of pressure sensitive adhesive between two layers of release paper can be die cut to exactly the size and shape needed for the particular application.
- the telechelic polymer (Polymer A) is a 3500 molecular weight (MW) hydrogenated polybutadiene diol (HO-EB-OH) .
- Three heterotelechelic polymers were used. All three were 6000 molecular weight.
- Polymer C is a 2000 MW polyisoprene block - 2500 MW polystyrene / 1500 MW polybutadiene random copolymer block -OH (I-S/EB-OH) in which the polybutadiene has been selectively hydrogenated and the polyisoprene has been epoxidized to a level of 1.5 meq epoxy/gm.
- Polymer D is a 2000 MW polyisoprene block - 4000 MW polybutadiene block -OH (I-EB-OH) in which the polybutadiene has been selectively hydrogenated and the polyisoprene has been epoxidized to 1.5 meq/gm.
- Polymer E is the same as Polymer D except the polyisoprene has not been epoxidized, but retains 1.5 meq/gm of double bonds.
- Polymer B is a non-heterotelechelic polymer used for comparison with the heterotelechelic polymers. It is a 3000 MW hydrogenated polybutadiene monol (EB-OH) .
- the HO-EB-OH was used with each of the four monols, with and without tackifying resin, by curing them through their hydroxyl groups with a trifunctional isocyanate, DESMODUR Z-4370, to give a polyurethane pressure sensitive adhesive (PSA) which also contained the melamine resin, CYMEL 1156.
- PSA polyurethane pressure sensitive adhesive
- CYMEL 1156 the melamine resin
- the intent was that this PSA could be used as any normal PSA to adhere two substrates together, giving an instantaneous bond under light pressure and having sufficient shear strength to hold the pieces together under modest load.
- the assembly could be heated to accomplish the melamine cure through the epoxy groups and improve the shear strength enough that the adhesive could bear high enough load that it could perform as a structural adhesive.
- formulations 1-4 in the table were prepared, using a 35/65 diol/ onol ratio by weight.
- pbw parts by weight of this diol/monol mixture
- CYMEL 1156 parts by weight of the butylated melamine resin
- CYCAT 600 dodecyl benzene sulfonic acid catalyst
- CYCAT 600 is a 70%w solution of acid in isopropyl alcohol
- This mixture was dissolved at 64%w solids in dry xylene to give the hydroxyl side of the two-component polyurethane.
- DESMODUR Z-4370 was added at a stoichiometric 1/1 NCO/OH ratio (including the alcohol introduced with the CYCAT 600), along with 0.04%w dibutyl tin dilaurate catalyst (DABCO T-12) , to catalyze the isocyanate / hydroxyl reaction.
- DABCO T-12 dibutyl tin dilaurate catalyst
- Holding Power is the time required to pull a standard area 1.77 x 10 " 2 m x 1.77 x 10 ⁇ 2 m ( in. x ⁇ in.) of tape from a standard test surface (steel, Kraft paper) under a standard load 19.614 N (2 kg), in shear at 2° antipeel (Pressure Sensitive Tape Council Method No. 7) . Long times indicate high adhesive strength. 180° peel was determined by Pressure Sensitive Tape Council Method No. 1. Large numbers indicate high strength when peeling a test tape from a steel substrate. Polyken - 27 - probe tack (PPT) was determined by ASTM D-2979. High numbers for PPT indicate aggressive tack.
- PPT Polyken - 27 - probe tack
- Adhesives 1 and 5 are the control adhesives, without and with tackifying resin, in which the monol (Polymer B) used has only the single hydroxyl group and is not heterotelechelic. After ambient cure, these adhesives, have good tack and they fail cohesively in the peel and holding power tests. After baking, holding powers improve, the peel strength of adhesive 5 increases and the failure mechanism in the peel test on adhesive 1 switches from cohesive to adhesive failure. However, the holding power and SAFT of these two formulations after baking are much lower than those of the other formulations.
- Adhesives 2 and 6 have poor tack and high holding power after ambient cure. Peel and holding power do not change upon baking. The high peel, high holding power and high SAFT of adhesive 6 are impressive. This suggests that if higher than normal bonding pressure can be applied to make the assembly to offset the poor tack after ambient cure, adhesive 6 may perform quite well as a structural adhesive when baked.
- Adhesives 3 and 7 used Polymer D. This monol contains no styrene so it should maintain low glass P95/04015
- Tg transition temperature
- adhesive 3 has only fair tack but excellent holding power.
- adhesive 3 continues to have excellent holding power and has excellent SAFT.
- the failure mechanism in the peel test is adhesive failure, suggesting that adhesive 3 has substantial cohesive strength after ambient cure and that its cohesive strength increases upon baking since its peel value drops.
- the presence of tackifying resin in adhesive 7 improves the Polyken probe tack and finger tack in the ambient cured adhesive.
- the bake cured adhesive has excellent holding power and SAFT.
- the change in failure mechanism in the peel test from a partial cohesive failure in the ambient cured adhesive to a purely adhesive failure in the bake cured adhesive suggests that the cohesive strength of the adhesive increased as desired upon baking.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Sealing Material Composition (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9509294A BR9509294A (en) | 1994-10-11 | 1995-10-09 | Sealing and adhesive compositions pressure sensitive structures adhesive and sealant |
JP8512345A JPH10506949A (en) | 1994-10-11 | 1995-10-09 | Pressure sensitive structural adhesives and sealants based on telechelic / heterotelechelic polymers with dual cure systems |
CA 2202279 CA2202279A1 (en) | 1994-10-11 | 1995-10-09 | Pressure sensitive structural adhesives and sealants based on telechelic/heterotelechelic polymers with dual cure systems |
KR1019970702338A KR970706367A (en) | 1994-10-11 | 1995-10-09 | Dual cure systems and telechelic / hetero-telechelic polymers - Basic pressure sensitive structural adhesives and sealants (PRESSURE SENSITIVE STRUCTURAL ADHESIVES AND SEALANTS BASED ON TELECELIC / HETEROTELECHELIC POLYMERS WITH DUAL CURE SYSTEMS) |
DE69510362T DE69510362T2 (en) | 1994-10-11 | 1995-10-09 | PRESSURE SENSITIVE STRUCTURAL ADHESIVES AND SEALANTS BASED ON TELECHELIC / HETEROTELECHELIC POLYMERISATES WITH DOUBLE CURING |
EP95935443A EP0785973B1 (en) | 1994-10-11 | 1995-10-09 | Pressure sensitive structural adhesives and sealants based on telechelic/heterotelechelic polymers with dual cure systems |
MXPA/A/1997/002588A MXPA97002588A (en) | 1994-10-11 | 1997-04-09 | Adhesives and sealants, structural, sensitive to the pressure, based on telekelic / heterotelequelicos polymers with curing systems d |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US32080894A | 1994-10-11 | 1994-10-11 | |
US08/320,808 | 1994-10-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996011240A1 true WO1996011240A1 (en) | 1996-04-18 |
Family
ID=23247953
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1995/004015 WO1996011240A1 (en) | 1994-10-11 | 1995-10-09 | Pressure sensitive structural adhesives and sealants based on telechelic/heterotelechelic polymers with dual cure systems |
Country Status (11)
Country | Link |
---|---|
US (7) | US5576388A (en) |
EP (1) | EP0785973B1 (en) |
JP (1) | JPH10506949A (en) |
KR (1) | KR970706367A (en) |
CN (1) | CN1160416A (en) |
BR (1) | BR9509294A (en) |
DE (1) | DE69510362T2 (en) |
ES (1) | ES2132723T3 (en) |
TW (1) | TW329430B (en) |
WO (1) | WO1996011240A1 (en) |
ZA (1) | ZA958493B (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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DE102011007893A1 (en) * | 2011-04-12 | 2012-10-18 | Henkel Ag & Co. Kgaa | Thermobondingverfahren |
WO2012139974A3 (en) * | 2011-04-12 | 2012-12-06 | Henkel Ag & Co. Kgaa | Impact-modified adhesives |
DE102011007893B4 (en) * | 2011-04-12 | 2015-11-12 | Henkel Ag & Co. Kgaa | Thermobonding method, adhesive film, method for producing an adhesive film and its use |
RU2600740C2 (en) * | 2011-04-12 | 2016-10-27 | Хенкель Аг Унд Ко. Кгаа | Adhesives modified to increase impact resistance |
US9828534B2 (en) | 2011-04-12 | 2017-11-28 | Henkel Ag & Co. Kgaa | Impact-modified adhesives |
Also Published As
Publication number | Publication date |
---|---|
EP0785973B1 (en) | 1999-06-16 |
US5910541A (en) | 1999-06-08 |
MX9702588A (en) | 1997-07-31 |
ZA958493B (en) | 1996-05-09 |
TW329430B (en) | 1998-04-11 |
US5576388A (en) | 1996-11-19 |
US5880217A (en) | 1999-03-09 |
DE69510362T2 (en) | 1999-11-18 |
ES2132723T3 (en) | 1999-08-16 |
US5721318A (en) | 1998-02-24 |
DE69510362D1 (en) | 1999-07-22 |
JPH10506949A (en) | 1998-07-07 |
CN1160416A (en) | 1997-09-24 |
US5948863A (en) | 1999-09-07 |
BR9509294A (en) | 1998-07-07 |
US5910542A (en) | 1999-06-08 |
EP0785973A1 (en) | 1997-07-30 |
US5804657A (en) | 1998-09-08 |
KR970706367A (en) | 1997-11-03 |
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