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CN-122003473-A - Primer composition capable of thermally debonding

CN122003473ACN 122003473 ACN122003473 ACN 122003473ACN-122003473-A

Abstract

The present invention relates to a thermally debondable primer composition comprising a polyether urethane methacrylate resin, two or more (meth) acrylate monomers, thermally expandable thermoplastic microspheres, and one or more photoinitiators.

Inventors

  • P. Audwell
  • N. Miliao Lei
  • R. Colisteron
  • U. frankenn
  • G. CLARK

Assignees

  • 汉高股份有限及两合公司

Dates

Publication Date
20260508
Application Date
20240912
Priority Date
20231011

Claims (16)

  1. 1. A thermally debondable primer composition, the thermally debondable primer composition comprising: a) Polyether urethane methacrylate resins; b) Two or more (meth) acrylate monomers; c) Thermoplastic microspheres that are thermally expandable, and D) One or more photoinitiators.
  2. 2. The thermally debondable primer composition of claim 1 wherein the polyether urethane methacrylate resin is derived from a polyether polyol, hydrogenated bisphenol a, and toluene 2, 4-diisocyanate having methacrylate functionality.
  3. 3. The heat-debondable primer composition according to claim 1 or 2, wherein the polyether urethane methacrylate resin is present at 30 to 55 wt%, preferably 35 to 50 wt%, and more preferably 37 to 47 wt% of the total weight of the composition.
  4. 4. The heat-debondable primer composition according to any one of claims 1 to 3, wherein the two or more (meth) acrylate monomers are selected from butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, isobutyl (meth) acrylate, isopentyl (meth) acrylate, isohexyl (meth) acrylate, isoheptyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, sec-butyl (meth) acrylate, 1-methyl (meth) acrylate, 1-ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate Cyclic trimethylolpropane methylacrylate, 2-phenoxyethyl (meth) acrylate, alkoxylated nonylphenol acrylate, alkoxylated phenol acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, alkoxylated lauryl acrylate, stearyl (meth) acrylate, isodecyl (meth) acrylate, caprolactone (meth) acrylate, methoxypolyethylene glycol (350) monoacrylate and methoxypolyethylene glycol (550) monoacrylate, polyethylene glycol di (meth) acrylate, tetrahydrofuranyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylic acid, itaconic acid, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, di (pentamethylene glycol) di (meth) acrylate, tetraethylene diethylene glycol di (meth) acrylate, diglycerol tetra (meth) acrylate, tetramethylene di (meth) acrylate, ethylene di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated bisphenol A (meth) acrylate, and mixtures thereof, preferably selected from isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, acrylic acid, itaconic acid, and mixtures thereof, and more preferably selected from isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, acrylic acid, and mixtures thereof, and even more preferably, the two or more (meth) acrylate monomers are isobornyl acrylate, acrylic acid, and hydroxyethyl methacrylate.
  5. 5. The heat-debondable primer composition according to any one of claims 1 to 4, wherein the two or more (meth) acrylate monomers are present at 20 to 50 wt%, preferably 25 to 45 wt%, preferably 27 to 41 wt% and more preferably 30 to 38 wt% of the total weight of the composition.
  6. 6. The thermally debondable primer composition according to any one of claims 1 to 5, wherein the thermally expandable thermoplastic microspheres have a core-shell structure, and wherein the shell is formed of a crosslinked polymer and the core is composed of a foaming agent.
  7. 7. The thermally debondable primer composition according to any one of claims 1 to 6, wherein the thermally expandable thermoplastic microspheres expand when exposed to heat, preferably when exposed to heat of 60 to 200 ℃, preferably 80 to 160 ℃, more preferably 80 to 130 ℃.
  8. 8. The thermally debondable primer composition according to any one of claims 1 to 7, wherein the thermally expandable thermoplastic microspheres have a particle size of 5 to 100 μιη, preferably 8 to 75 μιη, preferably 9 to 50 μιη, more preferably 10 to 30 μιη, more preferably 12 to 20 μιη, and even more preferably 13 to 19 μιη, wherein the particle size is measured by laser diffraction (low angle laser light scattering LALLS).
  9. 9. The thermally debondable primer composition according to any one of claims 1 to 8, wherein the thermally expandable thermoplastic microspheres are present at 5 to 30 wt. -%, preferably 10 to 27 wt. -%, preferably 12 to 25 wt. -%, and more preferably 14 to 22 wt. -%, based on the total weight of the composition.
  10. 10. The thermally debondable primer composition according to any one of claims 1 to 9, wherein the one or more photoinitiators are selected from the group consisting of 1-hydroxycyclohexylphenyl ketone, ethyl (2, 4, 6-trimethylbenzoyl) -phenyl) phosphinate, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-one, 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopro-1-one, 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butanone, a combination of 1-hydroxycyclohexylphenyl ketone and benzophenone, 2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-propane, a combination of 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide and 2-hydroxy-2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, a combination of 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenone and 1-hydroxy-cyclohexylphenyl-ketone, 50% by weight of diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide in combination with 50% by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone, bis (2, 6-dimethoxybenzoyl-2, 4-trimethylpentyl) phosphine oxide in combination with 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis (. Eta. <5> -2, 4-cyclopentadien-1-yl) -bis [2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl ] titanium, 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butanone, dl-camphorquinone, and mixtures thereof, preferably selected from ethyl (2, 4, 6-trimethylbenzoyl) -phenyl) phosphinate, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis (2, 4, 6-trimethylbenzoyl) -phenyl phosphine oxide, 1-hydroxy-phenyl-cyclohexyl-phenyl-ketone, and more preferably mixtures thereof, and mixtures thereof.
  11. 11. The thermally debondable primer composition according to any one of claims 1 to 10, wherein the one or more photoinitiators are present at 0.5 to 10 wt%, preferably 1.25 to 8 wt%, more preferably 1.5 to 5 wt%, based on the total weight of the composition.
  12. 12. The cured heat-debondable primer composition according to any one of claims 1 to 11, wherein the heat-debondable primer composition is cured by photo-curing.
  13. 13. Use of the heat-debondable primer composition according to any one of claims 1 to 11 or the cured product according to claim 12 in bonded structures.
  14. 14. A bonded structure, the bonded structure comprising: a first substrate; a second substrate; a heat-debondable primer composition layer according to any one of claims 1 to 11 or a cured product layer according to claim 12, and The layer of adhesive is formed of a layer of adhesive, Wherein a thermally debondable primer is arranged on the surface of the first substrate and/or on the surface of the second substrate, and wherein the adhesive layer is placed on top of the thermally debondable primer layer.
  15. 15. The bonded structure of claim 14, wherein the adhesive layer is formed from an adhesive selected from the group consisting of epoxy adhesives, acrylic adhesives, polyurethane adhesives, cyanoacrylate adhesives, silicone adhesives, polyimide adhesives, silane modified polymers, butyl rubber, hot melt adhesives, and mixtures thereof.
  16. 16. A method of debonding a bonded structure according to claim 14 or 15, the method comprising the steps of: i) Applying heat, and Ii) debonding the surface of the substrate, Wherein the temperature applied in step i) is preferably 60 to 200 ℃, and the heat is preferably applied for a duration of 2 to 60 minutes.

Description

Primer composition capable of thermally debonding Technical Field The present invention relates to a UV curable and thermally debondable primer composition. Background Adhesive bonding and polymeric coatings are commonly used in the assembly and finishing of manufactured goods. They are used in place of mechanical fasteners (such as screws, bolts and rivets) to provide bonding with reduced machining costs and greater applicability in manufacturing processes. The adhesive bond distributes stress evenly, reduces the likelihood of fatigue, and seals the joint from corrosive substances. While adhesive bonding thus provides many advantages over mechanical fasteners, in practice it is often difficult to disassemble an adhesive-bonded article where it is desired. Removal of the adhesive by mechanical means (e.g., by grit blasting or by wire brush cleaning) is generally precluded, in part, because the adhesive is disposed between the substrates and thus is either difficult to access or difficult to polish without damaging the substrate surface. Disassembly by application of chemicals and/or high temperatures may be effective but can be time consuming and complex to perform, and furthermore, the aggressive chemicals and/or harsh conditions required can damage the separated substrates, rendering them unsuitable for subsequent use. As an exemplary scenario, it is clearly desirable to remove, replace, and/or recycle components of the automotive industry, such as electric vehicle battery cells (battery cells) and housings (casque), that have been attached within the device using an adhesive. However, such adhesives are generally strong in that they are designed to remain adhered during drop or impact events as well as over a wide range of operating temperatures and other environmental conditions. If left unnoticed, the adhesively bonded equipment components may therefore be damaged or destroyed when the components are removed by mechanical means or by the application of chemicals. Some authors have attempted to develop debondable adhesive compositions in which the applied heat is used to break the bond at the interface of the adhesive and the substrate. The problem with thermal debonding is that high temperatures may damage the substrate if left unnoticed. Furthermore, the use of thermally expandable microspheres may have a negative impact on the mechanical and adhesive strength properties of the adhesive. With these problems in mind, some authors have also attempted to develop debondable adhesive compositions in which an electric current is applied through the cured composition to break the bond at the interface of the adhesive and the substrate. Accordingly, there remains a need in the art to provide means to effectively debond the bonded substrates while maintaining the optimal bonding and mechanical properties of the adhesive. Disclosure of Invention The present invention relates to a thermally debondable primer composition comprising a) a polyether urethane methacrylate resin (polyether urethane METHACRYLATE RESIN), b) two or more (meth) acrylate monomers, c) thermally expandable thermoplastic microspheres, and d) one or more photoinitiators. The invention also relates to a cured heat-debondable primer composition according to the invention, wherein the heat-debondable primer composition is cured by photo-curing. The invention also relates to the use of the heat-debondable primer composition or cured product according to the invention for bonded structures. The present invention includes an adhered structure comprising a first substrate, a second substrate, a layer of a thermally debondable primer composition or cured product according to the present invention, and an adhesive layer, wherein a thermally debondable primer is disposed on a surface of the first substrate and/or on a surface of the second substrate, and wherein the adhesive layer is disposed on top of the thermally debondable primer layer. A method of debonding a bonded structure according to the present invention, the method comprising the steps of i) applying heat, and ii) debonding a surface. Drawings FIG. 1 illustrates the tensile lap shear strength of TEROSON EP 5065 on KTL steel samples over a temperature range of-40 ℃ to 130 ℃. FIG. 2 illustrates the debonding efficiency of composition 1 as characterized by the tensile lap shear strength of TEROSON EP 5065 on an electrocoated (e-coated) steel coupon. Fig. 3 illustrates test setup to monitor the battery compartment temperature during the debonding process. Fig. 4 illustrates the change in cell temperature during the debonding stage using a structural adhesive (TEROSON EP, 5065). Fig. 5 illustrates the change in cell temperature during the debonding phase using TCA. Detailed Description The invention is described in more detail in the following paragraphs. Each aspect so described may be combined with any one or more other aspects unless clearly indicated to the contrary. In particular, any featur