CN1753963A - Curable bonded assemblies capable of being dissociated - Google Patents
Curable bonded assemblies capable of being dissociated Download PDFInfo
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- CN1753963A CN1753963A CNA028225066A CN02822506A CN1753963A CN 1753963 A CN1753963 A CN 1753963A CN A028225066 A CNA028225066 A CN A028225066A CN 02822506 A CN02822506 A CN 02822506A CN 1753963 A CN1753963 A CN 1753963A
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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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
- C08J2207/00—Foams characterised by their intended use
- C08J2207/02—Adhesive
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
- C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
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Abstract
The present invention relates to an adhesive composition for producing thermoset products, capable of being heated by means of an electric field, a magnetic field, an electromagnetic field or an alternating electromagnetic field, and containing filler particles which are metallic, ferromagnetic, ferrimagnetic, superparamagnetic or paramagnetic. Said adhesive composition can be hardened under the action of heat to form a high-resistance stable adhesive assembly, said resulting adhesive assemblies capable of being likewise dissociated under the action of heat.
Description
Technical field
The present invention relates to binder composition, but it comprises the filler particles of induction heating, also relates to its purposes and curing according to preamble section before the main claim.The invention still further relates to the described curing adhesive method for compositions of bonded composite, thermal separation of the hardened layer that comprises described binder composition and the purposes of this method.
Background technology
Gluing adherend, for example particularly adhint, coating, layered product or cast structural part should be designed to be able to make under mild conditions, and weather resistance is long as much as possible, and has high as far as possible intensity.High strength is meant that when repairing or reclaim, the separation of gluing adherend only can under extreme conditions can realize, for example under powerful and high temperature action.Adhint based on the reinforcement tackiness agent normally can be isolating, but for transferring structure adhint needed heavily stressed be not suitable.The separation of high-strength adhesive joint need use mechanical energy or chemical reagent to realize usually.The use of chemical reagent has following defective: they can cause serious environmental to be polluted, and the chemical reagent infiltration needs the very long time to the glue-line of structure bond joint steady in a long-term.
DE 43 28 108 A have described by micro-wave energy floor covering are separated.For this purpose, need to use the contact-type tackiness agent, this tackiness agent is an electroconductibility, and is filled with copper powder or aluminium powder.These fillers have following defective: particulate is of a size of several microns even bigger, and this causes the non-uniform heating of contact-type tackiness agent.
DE 199 61 940 A1 have described the tackiness agent that is used for separable adhint, and it comprises heat-activatable material, and this material discharges the gasiform compound when decomposing, destroy adhint then.The defective of this method is, is isolated complex, and the part of entire structure part or connection and tackiness agent all must be heated, and this causes high energy expenditure.In addition, can not implementation structure spare or the limited semistall in connection portion.
DE 199 51 599 A1 and DE 199 24 138 A1 disclose tackiness agent that is used for separable adhint and the adhint that makes thus, and described tackiness agent comprises can outside activated Nano filling.The separation of adhint can realize that wherein Nano filling and tackiness agent on every side are heated by described joint is introduced in alternating electric field, magnetic field or the electromagnetic field.But the defective of this method is must the whole tackiness agent of heating, and comprising does not need or do not wish heated place yet, but this is because the activated Nano filling also is included in and does not need to heat the place of separating adhint in tackiness agent or the priming paint.In addition, separate the high-strength adhesive joint and need high temperature, because must disconnect chemical bond with broken mixture.Described method also has following defective: when separating the high-strength adhesive joint, nonspecific thermolysis takes place in tackiness agent and/or priming paint.Therefore, these methods are not suitable for thermosetting material particularly.
The high-strength adhesive joint of manufacturing weather resistance normally carries out under heat or photochemistry condition.But the ordinary method of making gluing adhint has following defective: be cure adhesive, the entire structure part all has to be heated.Consequently, this method is power consumption and time-consuming.
WO 99/03306 and O.Hahn, A.Kaimann have described in " Adh sion-Kleben undDichten, 10/2001, pp.35-38 " and have been used to respond to the method for solidifying adhint.In the case, comprise the tackiness agent that can respond to the activatory filler and be introduced in the electromagnetic field, heating can be responded to the activatory filler thus, and makes the tackiness agent sclerosis around the filler.But these methods have following defective: can respond to the activatory material is not to be evenly distributed in the tackiness agent, and therefore causes the nonuniform heating of tackiness agent.Consequently, the intensity of these adhints is limited.In addition, this method also has following defective: in the induction heating process, back mixing might take place in tackiness agent close, and the distribution of heat-activatable material in tackiness agent becomes more irregular.
Summary of the invention
The objective of the invention is to overcome defective of the prior art, and provide a kind of and can under mild conditions, harden with the binder composition of the high-strength adhesive joint that forms weather resistance.Another object of the present invention provides a kind of method of separating these adhints, but can stand the long durability of this adhint with avoiding.
These purposes can be by according to the binder composition of claim 1 and 11, according to the curing of claim 18, according to the bonded composite of claim 19 and be used for thermal separation curing adhesive method for compositions according to claim 22 and 23.Claim 17 and 24 is specifically related to the application of binder composition and is used to separate the curing adhesive method for compositions.Dependent claims discloses favourable specific embodiments.
Discovery comprises polymkeric substance, polymeric blends or reacting resin and linking agent particulate binder composition can heat by electric field, magnetic field, electromagnetic field, alternating electric field, alternating magnetic field or alternating electromagnetic field.The linking agent particle this by filler particles and chemical bond-linking the linking agent on this filler particles form, described filler particles is metal, ferromagnetic, ferrimagnetic, superparamagnetism or paramagnetic.
Can cause chemical reaction between linking agent unit and polymkeric substance or the polymeric blends by induction heating linking agent particle, form polymer network thus.
Binder composition in the implication of the present invention particularly comprises tackiness agent, lacquer, priming paint, casting composition, sealing agent and lamination resin.Particularly, adhint, painted structural part or have priming paint structural part, the cast structural part, through the sealing structural part or polymer multilayer structure can form by solidifying these binder compositions thus.As the polymkeric substance in the implication of the present invention, polymeric blends and reacting resin, can use all polymkeric substance that are considered to be applicable to above application, polymeric blends and reacting resin.Cross-linked polymer preferably, but especially preferably by the polymkeric substance or the reacting resin of its manufacturing structure or half hitch structure joint.Resins, epoxy, urethane, acrylate, resol, polysulfide or melamine resin are specially suitable.
According to the present invention, the filler particles chemical bond-linking is on the linking agent component.This chemical bond-linking can be ionic, coordination or covalent linkage.For example comprise also that in this term Van-der-Waals interacts.
For producing according to chemical bond-linking of the present invention, advantageously the surface of filler particles is through surface modification, promptly, they carry from the teeth outwards can be easily and the functional group of the unitary functional group reactions of linking agent.The linking agent unit itself carries at least one can crosslinked functional group take place with polymkeric substance, polymeric blends or reacting resin when heating.Heating herein can be by induction mode or also can be realized by conventional methods.The appropriate functional group that crosslinking reaction can take place for example comprises epoxy group(ing), amino, mercaptan, alcohol, acrylate, methacrylic ester or vinyl.
Key be connected on the linking agent unit and can with the chemical group of filling surface reaction particularly organoalkoxysilane, titan-alkoxide acid esters and alkoxy zirconium ester.But these chemical group keys are connected on the normal metal or oxidized surface of filler particles.
Particularly preferred filler particles is, granule interior is to respond to the material that excites, and particle surface mainly is a silicon-dioxide.They can use by the form of sphere or aggregate.Be mainly sphere and have core--filler particles (seeing Figure 1A, Fig. 2 A) of shell structure can be for example reacts by sol-gel processing or by the ferric oxide of nano-scale and water glass and makes, the gathering filler particles (Figure 1B, Fig. 2 B) that has silica sphere preferably prepares by gas phase synthesis method.These particles are hereinafter referred to as composite particles.These composite particles are made up of the aggregate that shows sintering neck (sinter neck) characteristic, and a plurality of inclusion body or domain structure of responding to the material that excites of finding to distribute in the inside of this aggregate, and composite particles mainly is made up of silicon-dioxide from the teeth outwards.
Have silica granules from the teeth outwards and have very high long durability, and can react with above-mentioned chemical group apace with respect to its key between linking agent unit and filler particles surface of moisture.In addition, silicon dioxide layer can be protected and can respond to the chemical attack that the component that excites is resisted composition component.
Can for example be used as the linking agent of Resins, epoxy according to linking agent particle of the present invention.This Resins, epoxy can for example be with diamines hardened dihydroxyphenyl propane diglycidyl ether.By using these linking agent particles can obtain thermosetting material, this thermosetting material can stand high chemistry and thermal stresses.Single linking agent particle with epoxy group(ing) is schematically illustrated among Figure 1A.Shown in Fig. 2 A, this filler particles also can be the form of aggregate.Fig. 2 A has schematically shown the cross section of the ferric oxide particles aggregate in silica matrix.
Binder composition according to the present invention has the following advantages: the distribution of filler particles makes them only be positioned at the place that needs its effect of performance, promptly, in the linking agent particle.Compare with known binder composition, in the case, in those places of their effects of needs performance, filler particles is directly (promptly, molecule or almost molecule) contact.In this way, during induction heating, can avoid the non-specific heating of whole polymkeric substance.Therefore can sensed sclerosis under mild conditions according to binder composition of the present invention.
In addition, binder composition according to the present invention also has the following advantages: also can be separated again sensed and neatly by its adhint that makes, save time and energy, need not to add the isolating material of promotion.At this, also optionally on molecular level the position in break key heat.Its advantage is, damages whole polymkeric substance in the time of can not resembling with welding gun or LASER HEATING.Can avoid the non-selective thermolysis of polymkeric substance thus.
Naturally, compare with separating adhint, crosslinked or curing only needs lower induction output, for example radio-frequency generator of lower output.
According to the present invention, in the specially suitable binder composition, linking agent particulate content is 0.1-80%, and preferably 0.5-40% is preferably 1%-30% especially.By increasing the content of linking agent particle or linking agent, can realize higher degree of crosslinking and higher thus intensity.
Advantageously, linking agent particulate average primary particle size, promptly, average primary particle diameter is less than 1000nm, preferably less than 500nm, and particularly preferably between 2nm and the 100nm.Can realize evenly crosslinked according to binder composition of the present invention in this way.In addition, these small particle size see it is only from the angle of saving the energy.
According to filler particles of the present invention can be the form of aggregate, if dust dispersion quality is not high enough.The linking agent particle preferably comprises at least three functional groups with crosslinked action, and forms thermosetting material thus.If on linking agent key be connected with 3 chemical groups (by polycondensation or polyaddition reaction cured polymer system) or even 2 chemical groups (by polyreaction cured polymer system), can obtain thermosetting material usually.According to the present invention, preferably contain linking agent particulate binder composition, described linking agent particle has 0.00001mmol * m at least in its surface
-2Functional group with crosslinked action.Generally, has the density of group of crosslinked action at 0.1-1mmol/100m
2In the scope of linking agent specific grain surface.Therefore in polymer network, forming the crosslinked center of planet behind the curing reaction according to linking agent particle of the present invention.If the functional group on the linking agent unit for example is an epoxy group(ing), then they can with BF
3Etherate is used as the curing catalysts that is used for crosslinked polyfunctional epoxy resin together.After the curing, then form thermosetting material; If, then can only form the linear polymer that bears slight stress not according to linking agent particle of the present invention.
Preferably comprise the filler particles of surface modification according to binder composition of the present invention, this filler particles is selected from iron, iron alloy and wraps ferruginous metal oxide.The for example suitable filler particles that is based on iron powder, magnetite powder, Superparamagnetic Iron Oxide or manganese-zinc-ferriferous oxide.For example the magnetite powder with silica shell of nano-scale can be by carrying out surface modification or functionalized with the reaction of 3-glycidoxypropyltrime,hoxysilane.If the use sol-gel processing also can carry out the reaction with epoxy radicals silicone hydride simultaneously, this means and to omit a reactions steps.But, go on foot surface modifications for a step or two and also can use other functional silane.This moment, selected silane functional should be able to react with treating crosslinked polymeric system.The appropriate functional group of linking agent component and polymeric system is to for example being that the functional group that lists in the page 4 of DE 197 33 643 A1 is right.For example, if linking agent particle according to the present invention is to carry out surface modification with TSL 8330, then can obtain thermosetting material based on isocyanate prepolymer.By making amino and the isocyanate dimerization reaction, then can form urea coupling as cross-linking part.For acrylate resin, the modification of linking agent particulate is preferably implemented with the silane that comprises acrylate or methacrylate based group, and mercaptan is preferably implemented with epoxy radicals silicone hydride.
Particularly preferably be the binder composition that comprises the filler particles that obtains by flame pyrolysis.
These filler particles can be to have particle or the aggregated particles that diameter is the Superparamagnetic Iron Oxide domain structure of 3-20nm in silica matrix.These particulate preparation method for example is described in the following document: people such as Zachariah, Nanostructured Material 5,383 (1995), perhaps people such as Ehrman, Journal of Material Research 14,4551 (1999).
Special ferric oxide-silica composite granules of preferably in the DE 10140089.6 of application on August 16 calendar year 2001, describing.
Domain structure in the filler particles is interpreted as spatially separated superparamagnetism zone.Because use flame pyrolysis method, these particle major parts are atresias, and comprise free hydroxyl group from the teeth outwards.When applying foreign field, they show the character of superparamagnetism.The ratio of Superparamagnetic Iron Oxide domain structure can be between 1-99.6 weight % in the filler particles.The zone that in this scope, has spatially the Superparamagnetic Iron Oxide domain structure of being separated by non magnetic matrix.The proportional range of superparamagnetism domain structure preferably surpasses 30 weight %, is preferably greater than 50 weight % especially.The magnetic action that can realize of particle also increases along with the ratio in superparamagnetism zone according to the present invention.
In these domain structure, ferric oxide can be even modification or be non-homogeneous modification.
In addition, in particle, also can there be non magnetic modification.They can be the mixed oxides of silicon-dioxide and ferric oxide.For example can be inferior ferric metasilicate (FeSiO
4).Aspect superparamagnetism, the character of these non magnetic components and non magnetic silica matrix is similar.In other words, domain structure is still superparamagnetism, but saturation magnetization descends along with the increase of non magnetic component ratio.
In addition, also can there be the ferric oxide domain structure that does not show superparamagnetism and induce magnetic remanence owing to its size.This causes the increase of volume ratio saturation magnetization.Field according to being applied can make the composite particles that is fit to use.
Particularly preferably be, the ferric oxide domain structure of superparamagnetism is gamma-Fe
2O
3(γ-Fe
2O
3), Fe
3O
4And their mixture.
Except spatially separating the Superparamagnetic Iron Oxide domain structure, silica matrix also plays the effect of the oxidation state of stablizing this domain structure.Therefore, magnetite is for example stabilized to the oxidation iron phase of superparamagnetism by silica matrix.
According to specific embodiment, the carbon content in the filler particles can be less than 500ppm.Particularly preferred content is less than 100ppm.
In addition, filler particles also can have the chloride content of 50-1000ppm, and this is to stem from the particulate manufacturing processed.Obtain particle by flame pyrolysis method, in the method, chloride precursor substance for example reacts in hydrogen/oxygen flame.Formed particle can comprise and come from not the muriate of for example oxychloride form of the reactant of complete reaction and the muriate of hydrochloric acid form.If these compounds are closed in the formed particle, do not destroying under the particulate situation, even the chloride content in the particle also can not be further reduced by pure system step.Chloride content can be reduced to about 50ppm by pure system step.
According to the condition of flame pyrolysis method, filler particles can have different concentration class.Influence character and position that parameter comprises the dividing potential drop and the reaction postcooling step of the residence time, temperature, pressure, compound used therefor.Can obtain the composite particles from main ball to main aggregate form of wide region thus.
The BET surface according to DIN 66131 mensuration of filler particles can be at 10-600m
2Change in the wide region of/g.Particularly preferred scope is at 50-300m
2Between/the g.
In the preferred embodiment of composite particles, closure temperature (blocking temperature) promptly, no longer can detect superparamagnetism when being lower than this temperature, can be no more than 150K.Outside the composition of particle-removing, this temperature also depends on the size and the anisotropy thereof of superparamagnetism domain structure.
The composite particles of Superparamagnetic Iron Oxide and silicon-dioxide as filler particles then from the teeth outwards with for example silane reaction, described silane additionally carry can with the group of adhesive reaction.In this way, obtain to respond to the linking agent particle that excites.
In the present invention's favourable improvement project, filler particles is connected on the linking agent by heat-labile group.These heat-labile groups particularly are azo-group, carbonate group and the substituent ethylidene that has the steric hindrance needs.When heating has the binder composition of these heat-labile groups, bond rupture takes place under specific temperature, in above embodiment, form for example nitrogen or carbonic acid gas thus, perhaps have the carbon-carbon bond fracture in the substituent ethylidene of steric hindrance needs.The filler particles that is connected with linking agent by heat-labile group for example is shown among Figure 1B or Fig. 2 B, and wherein filler particles is the form of aggregate.
In one embodiment, can comprise polymkeric substance, polymeric blends or reacting resin, heat-labile material, linking agent composition and filler particles by the binder composition of electric field, magnetic field, electromagnetic field, alternating electric field, alternating magnetic field or alternating electromagnetic field heating, this filler particles is metal, ferromagnetic, ferrimagnetic, superparamagnetism or paramagnetic.
These binder compositions are particularly suitable for preparation can be by induction heating by isolating sclerosis adhint again.
Binder composition in this embodiment scope is also particularly including tackiness agent, lacquer, priming paint, casting composition, sealing agent and lamination resin.All are applicable to that the polymkeric substance of above application and polymeric blends also can be considered to be in polymkeric substance, polymeric blends and the reacting resin within this embodiment scope.Cross-linked polymer also is preferred for this embodiment, but preferred especially polymkeric substance or reacting resin by its manufacturing structure or half hitch structure joint.Resins, epoxy, urethane, acrylate, resol, polysulfide or melamine resin are specially suitable.
Can respond to the filler that excites can be the form of single nanoparticle or aggregate, or the form of agglomerate.They preferably directly contact with heat-labile material, make optionally to heat in the position of breaking bonds.Therefore particularly preferably be, described heat-labile material key is connected in can be responded on the filler that excites.Further preferably filler particles carries the coating that comprises silicon-dioxide.These particles have secular weather resistance to moisture.
Linking agent carry can with the functional group of polymkeric substance, polymeric blends or reacting resin generation crosslinking reaction, this can finish by induction heating or conventional type of heating.The proper group that crosslinking reaction can take place for example comprises epoxy group(ing), amino, mercaptan, alcohol, acrylate, methacrylic ester or vinyl.
Therefore, the binder composition of this embodiment has the following advantages: after curing, forming can isolating neatly adhint by induction heating, has saved time and energy.If filler particles directly contacts with heat-labile material, then optionally heat in the position of key of the heat-labile material of fracture.Its advantage is, damages whole polymkeric substance in the time of can not resembling for example with welding gun or LASER HEATING.Can avoid the non-selective thermolysis of polymkeric substance thus.
As the heat-labile material that is added in the binder composition, specially suitable is that those median sizes are between the 2nm-100 μ m, preferably between 2nm-1 μ m and particularly preferably in the material between the 2nm-200nm.
But these particle Individual existences or exist with the form of agglomerate.If heating is by solidifying the adhint that these binder compositions obtain, then phase transition perhaps takes place in these heat-labile materials in scissionable bond, and polymer network loses stablely, might disconnect adhint thus.
In a favourable improvement project, heat-labile material is the inflating medium that forms gas under heat effect, and the gas formation temperature is higher than binder composition and begins crosslinked temperature.
Separating the bonded composite that waits binder composition to make thus can realize via the decomposition temperature of inflating medium or inflating medium composition and the thermolysis that is produced by the particle that induction heating is coupled on the inflating medium.Formed gaseous decomposition product " blows bonded composite " to walk.Suitable inflating medium for example comprises material (as aluminum nitrate), organic acid acid (as oxalic acid, pentanedioic acid), azo-compound (as azodicarbonamide, azo diisobutyl nitrile) or the fluorinated hydrocarbons that disconnects crystal water.
Particularly preferred inflating medium is azodicarbonamide and sulfonyl hydrazide, for example particularly toluene sulfonyl hydrazide and oxygen base-two (benzene sulfinyl hydrazine).Generally, the derivative of azodicarbonamide also is suitable.Inflating medium can randomly activate with zinc salt.These inflating mediums have the following advantages: they discharge a large amount of gas, are dissolved in hardly in the organic solvent, decompose down at 180-200 ℃, and promptly, on the decomposition temperature of conventional adhint, and be avirulent.If desired, can reduce decomposition temperature, and be adjustable to thus and desire to make the isolating condition of adhint by extra activator.The low solubility of above-mentioned inflating medium in organic medium has following effect: described inflating medium is not dissolved in the tackiness agent, but and tight contact the in tackiness agent between the filler particles that therefore can keep induction heating and the inflating medium.Can further strengthen the effect of resin combination of the present invention in this way.
In another advantageous embodiment of binder composition according to the present invention, at first form the set particle by inflating medium and filler particles, wherein inflating medium can randomly be combined on the filler particles.Therefore, the set particle should be understood that to comprise the particle of inflating medium and filler particles.
These set particles can or make inflating medium and filler particles and polymer scale is incompatible obtains by precipitation, compression, little encapsulate.These set particulate sizes are subjected to application limitations subsequently simply.These gather particulate advantages, but can make the inflating medium particle of compatible with binder matrix easily induction heating.Therefore, resin system can not discharge inflating medium, but and tight contact the between the filler particles that can keep induction heating and the inflating medium.
Preferably, being used to form set particulate polymkeric substance is expandable polystyrene.Therefore, but the set particle is to comprise the filler particles of induction heating and the polystyrene bead of inflating medium simultaneously, and wherein inflating medium is normally used for making polystyrene to expand.These polystyrene beads preferably have the size of 1 μ m-1mm.If by the sensed heating of bonded composite that the binder composition that comprises these polystyrene beads makes, then can cause the expansion and thereby the separation of bonded composite of granules of polystyrene.
Binder composition according to the present invention is preferred for tackiness agent, lacquer, sealing agent, priming paint, matrix resin or casting resin.
Curing binder composition according to the present invention comprises by electric field, magnetic field, electromagnetic field, alternating electric field, alternating magnetic field or alternating electromagnetic field with the method that forms adhint binder composition induction heating to binder composition is begun crosslinked temperature.The advantage of this method is, the time length of induction heating usually the several seconds to several minutes scope, and be significantly shorter than time of conventional thermal curing method.Therefore, aspect susceptibility, it is particularly suitable for solidifying according to binder composition of the present invention.In addition, this method also is very energy-conservation.
Particularly, curing according to the present invention can be implemented described in following document for the binder composition that comprises the coarse particles filler: Ortwin Hahn, Andrea Kaimann, Adh sion-Kleben und Dichten, 10/2001, pp.35-38.Described in the still undocumented specification sheets of DE 10127704.0, it also is favourable adding curing catalysts and activator.
Solidify the bonded composite that the method according to binder composition of the present invention obtains by being used to and comprise at least one curing adhesive layer according to the present invention.Particularly, these bonded composites can be adhint, cast structural part, seal structural part or polymer multilayer structure.The cure adhesive layer can be enamelled coating or prime coat.
The method of thermal separation by the bonded composite that solidifies binder composition according to the present invention and obtain that be used for according to the present invention is by electric field, magnetic field, electromagnetic field, alternating electric field, alternating magnetic field or alternating electromagnetic field the hardened layer of binder composition to be carried out induction heating to implement.If binder composition comprises according to linking agent particle of the present invention, then the hardened layer of this binder composition is heated to the above temperature of ceiling temperature of cross-linking set in the method according to the invention.If binder composition comprises filler particles and heat-labile material, the temperature that enough ruptures of the sensed thermally labile bond energy that is heated to described heat-labile material or heat-labile group of the hardened layer of this binder composition then.
In the method that is used for thermal separation sclerosis bonded composite according to the present invention, the sensed heating of filler particles, initiating chamical reaction thus, wherein heat-labile material disconnects owing to bond rupture makes the cross-linking set of polymer network, form gas and/or expansion, perhaps owing to the induction heating to filler particles, bond rupture takes place near the cross-linking set place filler particles
Therefore, under the effect of the high-frequency energy that is sent by conventional ruhmkorff coil, the separation of bonded composite of the present invention is optionally carried out.Because the eddy current that produced, particle moving and lagging behind in alternating field lost, according to the present invention be present in metal in the polymer network, ferromagnetic, ferrimagnetic, superparamagnetism or paramagnetic filler particles be heated.Simultaneously, also heat near the polymeric system in environment filler particles.Selected induction voltage should make the heat that is produced be enough to make cross-linking set fracture in the polymer network, and if heat with the inflating medium combination, also can destroy this cross-linking set.Induction frequencies is preferably being counted kHz to the scope of about 35MHz.Equipment under the various situations, parameter and equipment are regulated and are all depended on used filler and the content in polymeric system thereof.Particularly, size distribution, Curie temperature, perviousness, resistance, thermal expansivity and specific heat capacity all are that equipment concrete set the amount that the temperature that will reach will depend on.Separate required temperature and depend on the thermostability of corresponding polymer system and inflating medium.If used filler particles chemical bond-linking is on the cross-linking set of polymeric system, then filler itself is exactly an integral part of polymeric system.Because treat separately chemical bond with respect to the local adjacency of the filler particles of introducing according to the present invention and can sensed heating, it is effective especially separating in the case.
The method that is used to separate bonded composite according to the present invention can be used for separating the adhint of only being made up of tackiness agent itself according to the present invention, but also can be used for based on binder composition according to the present invention and make up the adhesion primer of commercial binder.In the case, the separation selectivity ground of mixture carries out in prime coat.Tackiness agent still is retained on one of two bonding parts.
If binder composition according to the present invention is a paint vehicle of waiting to respond to dipping, then particularly advantageous for binder composition according to the present invention is that filler particles is combined on the linking agent composition.Its advantage is no longer to need the equipment of chemical, costliness and high labor force to consume for dipping.In addition, substrate is specially suitable for susceptibility can to respond to the coating of dipping.For example can exemplify fibre-reinforced composite plastic, wherein base polymer is impregnated damages with chemical, and perhaps fiber might be exposed or be damaged during grinding.These two kinds of phenomenons all cause the unallowable reduction of sensitive structure spare.
The method that being used for according to the present invention responded to dipping is specially adapted to glass fibre enhanced mixture in aircraft carbon fiber reinforced structural part or ship skeleton and the aerogenerator flabellum.
Application Example
Be not limited to its total applicability, below will describe according to binder composition of the present invention in more detail, be used to solidify said composition with the method that forms bonded composite, the separation of this bonded composite by means of Application Example.
Embodiment 1: contain key be connected to the filler particles that responding on the linking agent excite adhint curing with separate
1a) the magnetite of the nano-scale of usefulness coated with silica
43.3g iron(ic) chloride (III) hexahydrate be dissolved in the water of 370ml, remove dissolved oxygen by in solution, feeding nitrogen then.Add iron(ic) chloride (II) tetrahydrate of 15.9g, in nitrogen gas stream, in 2 hours, drip the solution of sodium hydroxide in 100ml water of 25.6g then, stir with accurate glassed agitator simultaneously.Therefore form Fe
3O
4The fine particulate black precipitate.In 30 minutes time, drip the Na of 22g
2Si
3O
7(the annealing loss is 17 weight %) solution in 80ml hot water.Under further stirring, be settled out silicic acid by slow dripping hydrochloric acid (37% hydrochloric acid of 14ml, and water is supplemented to 50ml).Filtering precipitate, and water makes slurries totally 5 times all filters again to separate formed sodium-chlor in each.The material of gained is made up of agglomerant nano particle.The diameter of this primary granule is about 8nm (measuring by transmission electron microscope(TEM)), and the diameter of agglomerate is about 400nm (passing through determination of light scattering).
1b) modification nano-scale, that can respond to the filler particles that excites
That 20g makes according to embodiment 1a and have the magnetite of nano-scale of 40% residual moisture content or the contrast material that obtains from other sources is made slurries with acetone, cumulative volume is 300ml, with the concentrated hydrochloric acid acidifying of 0.3ml, add the epoxy group(ing) cyclohexyl trimethoxy silane of 15g then.Whole material stirred 24 hours with accurate glassed agitator, vacuum-drying in rotatory evaporator then.The filler of surface modification carries the cyclic aliphatic epoxy group(ing) from the teeth outwards, and can play the effect of linking agent in adhesive composition.
1c) filler with surface modification mixes in the tackiness agent
Stir 3 of 10g, 4-epoxy group(ing) cyclohexyl methyl-3, (tolyl cumyl) iodine four (pentafluorophenyl group) boric acid ester of the cyclohexene oxide of 4-epoxy-cyclohexane-manthanoate, 10g, 0.2g and xitix-6-n-Hexadecane acid esters of 0.2g are until forming uniform mixture (according to the basic mixture of undocumented DE10127704.0 still).Use dissolver to mix 4g according to b) carry out the filler of surface modification.Stir after 15 minutes, form uniform thixotropy material, below as tackiness agent.
1d) adhint is by induction solidified bonding and separation again
With according to c) parts to be connected that adhesives 25mm is wide, 4mm is thick that make, these parts are made up of glass fibre enhanced polyester.For this reason, parts to be connected apply the thick binder layer of 0.2mm at connecting zone, and second parts is placed on it, and these two parts are at light pressure (about 0.02N/mm
2) under be fixed together.M230 semi-conductor producer with STS company excites, carry out thus tackiness agent with after fixing.The excitation frequency of this producer is 300kHz.Use 3 around and internal diameter excite as the induction that the coil of 3Gm is used for the adhint tackiness agent.Adhesive surface is placed in the middle of the coil and perpendicular to coil axes.Tackiness agent solidifies under the output of 1000W, and be 5 minutes action time, obtains firm joint thus.Output with producer increases to 3000W then, separates in 60 seconds time thus.In the Comparative Examples that does not comprise the filler particles that can respond to the nano-scale that excites, also can not cure adhesive even under the output of 3000W, act on 10 minutes.
Embodiment 2: can be by responding to the isolating adhint of the inflating medium that excites
2a) the prescription of forming by magnetite powder and inflating medium
With 20g according to 1a) the magnetite powder of the material (residual moisture content in the filter cake is 40%) that makes or the nano-scale that obtained by other sources is suspended in the ethanol of 100nl, the oxygen base-two (benzene sulfinyl hydrazine) that adds 20g then is as inflating medium.Stirring and 70 ℃ of following heated mixt 4 hours, and on rotatory evaporator except that desolvating.Grinding in ball grinder dry formulation 5 minutes, screen then.The particle diameter nominal is used for further experiment less than the part of 63 μ m.
2b) in tackiness agent, mix embodiment 2a) mixture
Stir 3 of 8g, 4-epoxy group(ing) cyclohexyl methyl-3, the polytetrahydrofuran (M of 4-epoxy-cyclohexane-manthanoate, 2g
n=250), (tolyl cumyl) iodine four (pentafluorophenyl group) boric acid ester of 0.1g and xitix-6-n-Hexadecane acid esters of 0.04g, all be dissolved in together (according to the basic mixture of undocumented DE 10127704.0 specification sheetss still) mutually until all the components.Stir the mixture that adds 2 g, this material is the denseness that is similar to dough.In 30 minutes, solidify to form noncohesive polymkeric substance at 90 ℃ of next section samples.
2c) bonding of adapter of plastic with separate again
The polypropylene member that 25mm to be connected is wide, 3mm is thick is carried out pre-treatment according to prior art by fluorination, apply about 0.2mm thick respond to the binder layer that excites, second parts is placed on it, these two parts are at light pressure (about 0.02N/mm
2) under in 90 ℃ stove, solidified 30 minutes.M230 semi-conductor producer with STS company excites, and carries out the separation subsequently of joint thus.The excitation frequency of this producer is 300kHz.Use 3 around and internal diameter excite as the induction that the coil of 3cm is used for the adhint tackiness agent.Adhesive surface is placed in the middle of the coil and perpendicular to coil axes.Under the output of 1500W, be 25 seconds action time, and inflating medium decomposes, and adhint is separated.In the Comparative Examples of the magnetite powder that does not comprise nano-scale, even effect can not make adhint separate in 2 minutes under the output of 3000W.
The analytical data of used ferric oxide-silica composite granules is shown in Table 1 among the embodiment 3-6.These particulate preparations are described among the DE 10140089.6.
The analytical data of table 1: embodiment 3,4,5 and ferric oxide-silica composite granules of 6
| Embodiment | 3，4，5 | 6 | |
| Ferric oxide ( *) | Weight % | 50 | 50 |
| Carbon content | ppm | 70 | ＜10 |
| Chloride content | ppm | 368 | 635 |
| Saturation magnetization | Am 2/kg | 17 | 12.5 |
| γ-Fe 2O 3The xln size | nm | 10.8 | 15.1 |
| Closure temperature (pact) | K | 100 | n.d. |
| The BET surface | m 2/g | 146 | 88 |
*According to Fe
2O
3Calculate; The n.d.=undetermined
Embodiment 3: based on the separation of the bonding glass body that contains the tackiness agent that can respond to the inflating medium that excites
3a) composite particles that makes of flame pyrolysis method and the prescription of tackiness agent
The composite particles (its character is shown in Table 1) of nano-scale that 25g is made by flame pyrolysis method and that be made up of silicon-dioxide and ferric oxide is suspended in the ethanol of 100ml, and the oxygen base-two (benzene sulfinyl hydrazine) that adds 20g then is as inflating medium.This mixture removes on rotatory evaporator and desolvates stirring and 60 ℃ of following heating 5 hours.Grinding in ball grinder dry formulation 3 minutes, screen then.The particle diameter nominal is used for further experiment less than the part of 63 μ m.
3b) in tackiness agent, mix embodiment 3a) prescription and tackiness agent experiment
That in being equipped with Planimax (Molteni) mixing tank of mediating hook, make according to embodiment 3a with 10g and by inflating medium with can respond to the prescription that the Nano filling that excites forms 300g hydraulicity single-component polyurethane adhesive Dinitrol PUR 501 FC (Dinol GmbH) are carried out modification.This mixture was mediated 15 minutes under 1 grade of (150rpm) rotating speed in dry environment.
The tackiness agent that uses modification thus through sandblasting and float glass plate that aluminium flake that degrease is handled and 3mm are thick between make thick layer adherend.Overlap length is 25mm, and the thickness of binder layer is 3mm.After solidifying for 1 week under the condition of 25 ℃ and 50% relative air humidity, excite by induction joint is separated again.M230 semi-conductor producer with STS company excites, and joint is separated.The excitation frequency of this producer is 300kHz.Use 3 around and internal diameter excite as the induction that the coil of 3cm is used for the adhint tackiness agent.Adhesive surface is placed in the middle of the coil and perpendicular to coil axes.Under the output of 3000W, be 2 minutes action time, because the expansion of inflating medium is bonding destroyed.The part of two connections can easily be separated from each other.
Embodiment 4: based on the separable adhint that can respond to isolating tackiness agent priming paint
Stir to add in the Sika of 200g priming paint 206G+P (Sika AG) adhesion primer that 5g makes according to embodiment 3a and by inflating medium with can respond to the prescription that the Nano filling that excites is formed.With priming paint be coated in through sandblasting and aluminium flake that degrease is handled on and cover this aluminium flake.After 1 hour ventilation, carry out the thick beech plywood of pretreated sheet material and 3mm in this way and lump together.Apply Sikaflex 254 (Sika AG) as tackiness agent, thickness is 3mm, and overlap length is 25mm.Relative air humidity 50% and 25 ℃ of following tackiness agent sclerosis in 1 week.Excite by induction joint is separated again.M230 semi-conductor producer with STS company excites, and joint is separated.The excitation frequency of this producer is 300kHz.Use 3 around and internal diameter excite as the induction that the coil of 3cm is used for the adhint tackiness agent.Adhesive surface is placed in the middle of the coil and perpendicular to coil axes.
Under the output of 3000W, be 25 minutes action time, because the expansion of inflating medium, the tackiness agent priming paint that is coated on the aluminium flake side is destroyed.The part of two connections can easily be separated from each other, and tackiness agent still optionally is retained on the glued board.
Embodiment 5-curing elastic tackiness agent is also tested adhesive properties
(Tivoli Hamburg) is polybutadiene-base metal-to-metal adhesive a kind of single component, thermofixation to elastic adhesive Elastosol M83.Based on curing in conventional oven and induction solidified contrast according to the present invention, show with this curing of two types and realized identical adhesion results.In this regard, induction curing takes place sooner.
With being equipped with Planimax (Molteni) mixing tank of mediating hook 25g is incorporated among the tackiness agent Elastosol M83 of 250g according to the ferric oxide-silica composite granules of table 1.At first under 150rpm, mediated 5 minutes, mediated 30 minutes down at 450rpm (3 grades) then.Then under vacuum, continue to mediate mixture 5 minutes so that its degassing (3 grades).The material according to the invention that so obtains is used for the tackiness agent test.
For checking adhesive properties, make stretching/shear sample according to DIN EN 1465, parts to be connected are by the thick aluminium flake coiled material (AlMg of 1.15mm
0.4Si
12) form, and another parts to be connected are by thick the forming through the glass fibre enhanced polypropylene of 4mm.Aluminium stands milled processed and uses the butanone degrease.Polypropylene carries out pre-treatment with air as working gas in low pressure plasma.
At first use modified adhesive according to the present invention to prepare adhesive sample and carry out induction hardening then.M230 semi-conductor producer with STS company excites, and carries out the curing of tackiness agent thus.The excitation frequency of this producer is 300kHz.Use 3 around and internal diameter excite as the induction that the water-cooled pancake coil of 8cm is used for the adhint tackiness agent.Coil is placed on the polyacrylic connection portion, and tackiness agent was cured under the action time of the output of 1000W and 10 minutes.Tackiness agent is when the bonding fracture, and the stretching-shearing resistance of sample is 10.4 ± 0.6Mpa.
For comparing, with the tackiness agent preparation stretching/shear sample that is modified.In the case, tackiness agent is cured in a conventional manner according to the explanation of manufacturers.In stove, under 180 ℃, be cured 30 minutes.Stretching-the shearing resistance of these samples is 10.1 ± 0.4Mpa.
Embodiment 6: the hot-melt adhesive that is used for selective separation adhint
In Brabender duplex forcing machine, in the helix speed of 60rpm and used heating zone, according to the ferric oxide-silica composite granules of table 1 hot-melt adhesive B40166 (Heinrich B ü hnen GmbH) is carried out modification with 7 weight % under 220 ℃ the spiral temperature.The hot-melt adhesive granulating also is coated on the thick beech glued board of 5mm with HB 500 coating units.Second beech glued board is squeezed on the hot-melt adhesive immediately.Joint is firm in 1 minute.Excite by induction joint is separated again.With the M230 semi-conductor producer of STS company and have 3 around and internal diameter be that the water-cooled pancake coil of 8cm makes adhint respond to separation.Coil is placed on the glued board, regulates the output of 3000W at semi-conductor producer place.After 60 seconds action time, two glued boards can be separated, and after carrying out induction heating again, can bond together mutually more again.
Claims (25)
1, is used to prepare the binder composition of thermosetting material, described composition can be heated by electric field, magnetic field, electromagnetic field, alternating electric field, alternating magnetic field or alternating electromagnetic field, and comprise polymkeric substance, polymeric blends or reacting resin and linking agent particle, wherein said linking agent particle comprises that ferromagnetic, ferrimagnetic, superparamagnetism or paramagnetic filler particles and chemistry are connected the linking agent on these filler particles.
2, according to the binder composition of claim 1, it is characterized in that linking agent particulate content is 0.1 weight %-80 weight %, be preferably 0.5 weight %-40 weight %, and be preferably 1 weight %-30 weight % especially.
3, according to the binder composition of claim 1 or 2, it is characterized in that described linking agent particulate average primary particle diameter between 2nm-1000nm, preferably between 2nm-500nm, and particularly preferably between the 2nm-100nm.
4,, it is characterized in that described linking agent particle has 0.00001mmol * m at least with respect to its surface according to the binder composition of one of claim 1-3
-2The functional group with crosslinked action.
5,, it is characterized in that described filler particles is through surface modification according to the binder composition of one of claim 1-4.
6, according to the binder composition of one of claim 1-5, it is characterized in that described filler particles is selected from following group: iron, iron alloy and wrap ferruginous metal oxide.
7,, it is characterized in that described filler particles has core-shell structure, and be the prepared in reaction by sol-gel method or ferric oxide by nano-scale and water glass according to the binder composition of claim 5.
8,, it is characterized in that described filler particles is the ferric oxide-silica composite granules by the superparamagnetism of flame pyrolysis method preparation according to the binder composition of claim 5.
9,, it is characterized in that described linking agent is connected on the filler particles by heat-labile group according to the binder composition of one of claim 1-8.
10,, it is characterized in that described heat-labile group is azo-group, carbonate group or the substituent ethylidene that has the steric hindrance needs according to the binder composition of claim 9.
11,, it is characterized in that additionally comprising heat-labile material according to the binder composition of one of claim 1-8.
12, according to the binder composition of claim 11, the median size that it is characterized in that described heat-labile material is between 2nm-100 μ m, preferably between 2nm-1 μ m, and particularly preferably between the 2nm-200nm.
13, according to the binder composition of claim 11 or 12, it is characterized in that described heat-labile material is the inflating medium that forms gas under heat effect, wherein the gas formation temperature is higher than binder composition and begins crosslinked temperature.
14,, it is characterized in that described inflating medium is selected from following group: azodicarbonamide and sulfonyl hydrazide, particularly toluene sulfonyl hydrazide and oxygen base-two (benzene sulfinyl hydrazine) according to the binder composition of claim 13.
15, according to the binder composition of claim 13 or 14, it is characterized in that comprising the set particle, this particle comprises described inflating medium and filler particles, and can or make inflating medium and filler particles and polymer scale is incompatible obtains by precipitation, compression, little encapsulate.
16,, it is characterized in that described to be used to form set particulate polymkeric substance be expandable polystyrene according to the binder composition of claim 15.
17, be used for the application of tackiness agent, lacquer, sealing agent, priming paint, matrix resin or casting resin according to the binder composition of one of claim 1-16
18, curing is characterized in that according to the method for the binder composition of one of claim 1-16 described binder composition begins crosslinked temperature by the sensed binder composition that is heated to of electric field, magnetic field, electromagnetic field, alternating electric field, alternating magnetic field or alternating electromagnetic field.
19, the bonded composite that comprises at least one binder layer, wherein said at least one binder layer obtains as the described binder composition of one of claim 1-16 by solidifying.
20,, it is characterized in that described at least one binder layer is enamelled coating and prime coat according to the bonded composite of claim 19.
21, according to the bonded composite of claim 19 or 20, it is adhint, cast structural part, seal structural part or polymer multilayer structure.
22, the method that is used for the bonded composite that thermal separation obtains by the binder composition that solidifies according to one of claim 1-8, the hardened layer that it is characterized in that described binder composition is heated to temperature more than the cross-linking set ceiling temperature by electric field, magnetic field, electromagnetic field, alternating electric field, alternating magnetic field or alternating electromagnetic field.
23, the method that is used for the bonded composite that thermal separation obtains by the binder composition that solidifies according to one of claim 9-16, the temperature of fracture takes place in the thermally labile key that the hardened layer that it is characterized in that described binder composition is heated to heat-labile material and/or heat-labile group by electric field, magnetic field, electromagnetic field, alternating electric field, alternating magnetic field or alternating electromagnetic field.
24, according to the application in dipping coating of the method for claim 22 or 23.
25, according to the application of claim 24, it is to be used for aircraft construction and ship construction.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10155614.4 | 2001-11-13 | ||
| DE10155614 | 2001-11-13 | ||
| DE10210661.4 | 2002-03-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1753963A true CN1753963A (en) | 2006-03-29 |
| CN100343355C CN100343355C (en) | 2007-10-17 |
Family
ID=7705530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028225066A Expired - Fee Related CN100343355C (en) | 2001-11-13 | 2002-11-12 | Curable bonded assemblies capable of being dissociated |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100343355C (en) |
| DE (1) | DE10210661A1 (en) |
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| CN111670212A (en) * | 2018-02-02 | 2020-09-15 | 株式会社Lg化学 | Curable composition |
| US11952477B2 (en) | 2018-02-02 | 2024-04-09 | Lg Chem, Ltd. | Curable composition |
| CN112724604A (en) * | 2020-12-30 | 2021-04-30 | 北京理工大学 | Magnetorheological material, preparation method and iron container repairing method |
| CN112724604B (en) * | 2020-12-30 | 2022-07-22 | 北京理工大学 | Magnetorheological material, preparation method and iron container repairing method |
| TWI790849B (en) * | 2021-12-09 | 2023-01-21 | 財團法人工業技術研究院 | Adhesive composition and liquid crystal display and method of disassembling the same |
| US11753568B2 (en) | 2021-12-09 | 2023-09-12 | Industrial Technology Research Institute | Adhesive composition and liquid-crystal display and method of disassembling the same |
| TWI843254B (en) * | 2022-10-26 | 2024-05-21 | 財團法人工業技術研究院 | Adhesive and method for removing the same |
| WO2024157105A1 (en) * | 2023-01-23 | 2024-08-02 | Vulco S.A. | Adhesive composition and/or method of removing elastomer liner from metal substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10210661A1 (en) | 2003-05-28 |
| CN100343355C (en) | 2007-10-17 |
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