Dual curable adhesive composition

Abstract

The present invention relates to a dual curable adhesive composition comprising: a) a polyurethane resin having a molecular weight of from 1000 to 1000000 Da; b) a urethane diacrylate oligomer having a molecular weight of from 1000 to 100000 Da; c) a photoinitiator; d) two or more monofunctional (meth) acrylate monomers; and e) core-shell particles. The composition has improved impact resistance at low temperatures (below 0 DEG C).

Description

Technical Field

[0001] This invention relates to a dual-curable adhesive composition that has improved impact resistance at low temperatures (below 0°C). Background Technology

[0002] There are many types of handheld electronic devices on the market that users carry around all the time, thus exposing these devices to varying environments (including harsh winter conditions).

[0003] Adhesives commonly used in electronic devices (especially handheld devices) typically exhibit glass transition temperatures (Tg) above room temperature (especially above 40°C). Furthermore, the damping factor is less than 0.5 below 0°C. Therefore, the impact resistance of adhesives decreases at low temperatures. When impacts are applied under harsh winter conditions, this low impact resistance at low temperatures causes electronic components to detach.

[0004] Attempts have been made to improve low-temperature impact resistance by increasing adhesive strength. However, as adhesive strength increases, the modulus of the adhesive also increases, so the impact resistance of the adhesive may actually decrease.

[0005] Another attempt to improve impact resistance at low temperatures has involved the use of resins and oligomers with higher molecular weights. The increased molecular weight has led to an increase in impact resistance at room temperature. However, impact resistance has not increased at low temperatures by this method because the adhesive has a high Tg above room temperature.

[0006] Therefore, adhesives with improved impact resistance at low temperatures (below 0°C) are needed. Summary of the Invention

[0007] This invention relates to a dual-curable adhesive composition comprising: a) a polyurethane resin with a molecular weight of 1,000 to 1,000,000 Da; b) a urethane diacrylate oligomer with a molecular weight of 1,000 to 100,000 Da; c) a photoinitiator; d) two or more monofunctional (meth)acrylate monomers; and e) core-shell particles, wherein the molecular weight is measured using gel permeation chromatography (GPC) with a polystyrene calibration standard, for example, according to ASTM 3536.

[0008] The present invention also relates to a cured adhesive composition according to the invention that is capable of dual curing, wherein the composition is first cured by light and then by moisture curing or heat curing.

[0009] The present invention includes the use of dual-curable adhesive compositions or cured compositions according to the present invention as adhesives for the covers of mobile phones, televisions, laptops, motor vehicles, aerospace, semiconductors, and handheld devices, or as adhesives for laminating fabrics or films. Detailed Implementation

[0010] The invention is described in more detail in the following paragraphs. Unless explicitly stated otherwise, each aspect thus described may be combined with any one or more other aspects. In particular, any feature indicated as preferred or advantageous may be combined with any one or more other features indicated as preferred or advantageous.

[0011] In the context of this invention, unless the context otherwise requires, the terminology used will be interpreted according to the following definitions.

[0012] As used herein, unless the context clearly indicates otherwise, the singular forms “a / an” and “the” include both the singular and plural referents.

[0013] As used herein, the term “comprising / comprises / comprised of” is synonymous with “including / includes” or “containing / contains”, and is inclusive or open-ended, and does not exclude additional unlisted members, elements, or method steps.

[0014] As used herein, the term “composed of” excludes any element, component, member, or method step that is not specified.

[0015] The terms “preferred / preferably,” “expected,” and “specific / particularly / especially” are generally used herein to refer to embodiments of the present disclosure that may provide particular benefits in certain circumstances. However, a description of one or more preferred, preferred, expected, or particular embodiments does not imply that other embodiments are unavailable, and is not intended to exclude those other embodiments from the scope of the present disclosure.

[0016] As used throughout this application, the word “may” is used in a permissible sense (i.e., meaning possible) rather than in a mandatory sense.

[0017] The definition of numerical endpoints includes all numbers and fractions falling into their respective ranges, as well as the listed endpoints.

[0018] Unless otherwise specified, all percentages, portions, proportions, etc. mentioned herein are based on weight.

[0019] When a quantity, concentration, or other value or parameter is expressed in the form of a range, a preferred range, or a preferred upper limit and a preferred lower limit, it should be understood that any range obtained by combining any upper limit or preferred value with any lower limit or preferred value is specifically disclosed, regardless of whether the obtained range is explicitly mentioned in the context.

[0020] All references cited in this specification are hereby incorporated in their entirety by reference.

[0021] Unless otherwise defined, all terms (including technical and scientific terms) used in this disclosure have the meanings commonly understood by one of ordinary skill in the art to which this invention pertains. Further guidance includes terminology definitions to better understand the teachings of this invention.

[0022] This invention relates to a dual-curable adhesive composition comprising: a) a polyurethane resin with a molecular weight of 1,000 to 1,000,000 Da; b) a urethane diacrylate oligomer with a molecular weight of 1,000 to 100,000 Da; c) a photoinitiator; d) two or more monofunctional (meth)acrylate monomers; and e) core-shell particles, wherein the molecular weight is measured using gel permeation chromatography (GPC) with a polystyrene calibration standard, for example, according to ASTM 3536.

[0023] The compositions according to the invention are photo-inducible curable adhesives, which are further cured by moisture curing or heat curing. When irradiated with light, the compositions according to the invention function similarly to pressure-sensitive adhesives (PSA) and can subsequently be fully cured by moisture or heat.

[0024] The compositions according to the invention exhibit improved shock resistance and excellent shock absorbing behavior at low temperatures (below 0°C).

[0025] The compositions according to the present invention comprise a polyurethane resin. The polyurethane resin is moisture-curable. In some embodiments, the polyurethane resin may be replaced by an acrylate resin or a silicone resin. The polyurethane resin affects the viscosity of the adhesive composition and also affects its impact resistance at low temperatures.

[0026] The molecular weight of the curable polyurethane resin is from 1,000 to 1,000,000 Da, where the molecular weight is measured using gel permeation chromatography (GPC) with polystyrene calibration standards, for example, according to ASTM 3536.

[0027] The above-mentioned preferred molecular weight is preferred because a molecular weight below 1000 Da will result in reduced shock absorption behavior, while a molecular weight that is too high (above 1,000,000 Da) will result in excessively high viscosity.

[0028] The polyurethane resin applicable to this invention is obtained by reacting a diol with a diisocyanate to form an isocyanate-terminated polyurethane resin containing urethane groups and reactive isocyanate groups.

[0029] The diols suitable for use in this invention are preferably selected from poly(tetramethylene ether) glycol (PTMG), polypropylene glycol (PPG), ester polyol, and caprolactone type polyol.

[0030] Commercially available diols suitable for use in this invention include, but are not limited to, PolyTHF 250 and PolyTHF 3000 from BASF.

[0031] The isocyanate suitable for use in this invention is preferably selected from methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 2,4,4-trimethylhexamethylene diisocyanate (TMDI), and H 12 Methylene diphenyl diisocyanate (MDI) and mixtures thereof.

[0032] Commercially available isocyanates suitable for use in this invention include, but are not limited to, Desmodur 44C fused from COVESTRO.

[0033] The commercially available polyurethane resin suitable for use in this invention is available from Henkel Corporation.

[0034] The polyurethane resin may be present in the dual-curable adhesive composition according to the invention at 40 to 60% by weight, preferably 45 to 55% by weight, and more preferably 47 to 58% by weight of the total weight of the composition.

[0035] These polyurethane resin contents are preferred because if the polyurethane resin content is too high, the viscosity of the composition will increase too much, while if the content is too low, the impact resistance at low temperatures (below 0°C) will decrease.

[0036] The compositions according to the present invention comprise urethane diacrylate oligomers.

[0037] The urethane diacrylate oligomers applicable to this invention have a molecular weight of 1,000 to 100,000 Da, wherein the molecular weight is measured using gel permeation chromatography (GPC) with a polystyrene calibration standard, for example, according to ASTM 3536.

[0038] The above-mentioned preferred molecular weight is preferred because a molecular weight below 1000 Da will result in reduced shock absorption behavior, while a molecular weight that is too high (above 100,000 Da) will result in excessively high viscosity.

[0039] The urethane diacrylate oligomer is preferably selected from aliphatic urethane di(meth)acrylate-terminated oligomers, aromatic urethane di(meth)acrylate oligomers, aliphatic polyester-based urethane di(meth)acrylate oligomers, aliphatic polyether-based urethane di(meth)acrylate oligomers, and mixtures thereof; preferably, the urethane diacrylate oligomer is an aliphatic urethane di(meth)acrylate-terminated oligomer.

[0040] Oligomers capped with aliphatic urethane di(meth)acrylate are preferred because they are believed to improve impact resistance at low temperatures (below 0°C).

[0041] Commercially available urethane di(meth)acrylate oligomers suitable for use in this invention include, but are not limited to, CN8891 NS and CN 8889NS from Sartamomer.

[0042] The urethane diacrylate oligomer may be present in the dual-curable adhesive composition according to the invention at 20 to 40% by weight, preferably 25 to 35% by weight, and more preferably 27 to 33% by weight of the total weight of the composition.

[0043] These urethane diacrylate oligomer contents are preferred because when the urethane diacrylate oligomer content is too high, the viscosity of the composition increases too much, while too low a content will lead to a decrease in impact resistance at low temperatures (below 0°C).

[0044] The compositions according to the present invention comprise two or more monofunctional (meth)acrylate monomers.

[0045] Two or more monofunctional (meth)acrylate monomers may be aliphatic, alicyclic, cyclic, or aromatic monofunctional (meth)acrylate monomers, or mixtures thereof.

[0046] In a highly preferred embodiment, two or more monofunctional (meth)acrylate monomers are a combination of aliphatic (meth)acrylate monomers and alicyclic (meth)acrylate monomers.

[0047] In another highly preferred embodiment, the ratio of aliphatic (meth)acrylate monomer to alicyclic (meth)acrylate monomer is 1:2.

[0048] A combination of aliphatic (meth)acrylate monomers and alicyclic (meth)acrylate monomers in a ratio of 1:2 is preferred because it enhances the adhesive properties of the composition.

[0049] Preferably, two or more monofunctional (meth)acrylate monomers are selected from tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, isobornyl acrylate, isobornyl methacrylate, alkoxylated tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl methacrylate, cyclic trimethylolpropane formal acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, ethoxylated (4)nonylphenol acrylate, alkoxylated nonylphenol acrylate, alkoxylated phenol acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, alkoxylated lauryl acrylate, stearyl acrylate, stearyl methacrylate, lauryl acrylate, lauryl methacrylate, isodecanyl ... Octyl acrylate, isooctyl methacrylate, octyl decyl acrylate, octyl decyl methacrylate, tridecyl acrylate, tridecyl methacrylate, caprolactone acrylate, caprolactone methacrylate, methoxy polyethylene glycol (350) monoacrylate and methoxy polyethylene glycol (550) monoacrylate, and mixtures thereof; preferably selected from tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, and mixtures thereof.

[0050] In a highly preferred embodiment, two or more monofunctional (meth)acrylate monomers are tetrahydrofurfuryl acrylate and 2-(2-ethoxyethoxy)ethyl acrylate.

[0051] In another highly preferred embodiment, two or more monofunctional (meth)acrylate monomers are tetrahydrofurfuryl acrylate and 2-(2-ethoxyethoxy)ethyl acrylate in a ratio of 1:2.

[0052] A combination of these specific (meth)acrylate monomers in a ratio of 1:2 is preferred because it enhances the adhesive properties of the composition.

[0053] Commercially available (meth)acrylate monomers suitable for use in this invention include, but are not limited to, SR56 and SR285 NS from Sartamomer.

[0054] Two or more monofunctional (meth)acrylate monomers may be present in the dual-curable adhesive composition according to the invention at 3 to 30% by weight, preferably 7 to 25% by weight, and more preferably 10 to 20% by weight of the total weight of the composition.

[0055] The content of these (meth)acrylate monomers is preferred because too high a content of monofunctional (meth)acrylate monomers will cause the viscosity of the composition to decrease too much, while too low a content will cause the adhesive strength to decrease.

[0056] The compositions according to the invention comprise core-shell particles. The core-shell particles are biphase materials having an internal core structure and an outer shell made of different components. Core-shell particles generally improve the shock absorption properties of the composition at low temperatures.

[0057] The polymer material of the core should have a glass transition temperature not exceeding 0°C (T0). g Preferably, the glass transition temperature (T) is -20°C or lower, more preferably -40°C or lower, or even more preferably -20 to -60°C. g ).

[0058] A low Tg value is believed to improve the impact resistance of the composition.

[0059] The polymer of the shell is the glass transition temperature (T). g The product is a non-elastic, thermoplastic, or thermosetting polymer with a temperature of 50°C or lower, preferably 30°C or lower, more preferably room temperature or lower.

[0060] The glass transition temperature (Tg) is the temperature at which a cured resin begins to change from a glassy (solid) state to a soft, rubbery state; it can be considered the point at which a measurable decrease in physical properties occurs due to exposure to elevated temperatures. The glass transition temperature is measured according to ASTM D7028-07.

[0061] Without limiting the invention, the core may consist of: diene homopolymers, such as butadiene or isoprene homopolymers; diene copolymers, such as butadiene or isoprene copolymers with one or more olefinically unsaturated monomers (such as vinyl aromatic monomers, (meth)acrylonitrile, or (meth)acrylate); polymers based on (meth)acrylate monomers, such as polybutyl acrylate; and polysiloxane elastomers, such as polydimethylsiloxane and crosslinked polydimethylsiloxane.

[0062] Similarly, without limiting the invention, the shell can be composed of a polymer or copolymer of one or more monomers selected from: (meth)acrylates, such as methyl methacrylate; vinyl aromatic monomers, such as styrene; vinyl cyanides, such as acrylonitrile; unsaturated acids and anhydrides, such as acrylic acid; and (meth)acrylamide. The polymer or copolymer used in the shell can have acid groups that are ionicly crosslinked by forming metal carboxylates, particularly by forming salts of divalent metal cations. The shell polymer or copolymer can also be covalently crosslinked by monomers having two or more double bonds per molecule.

[0063] Preferably, the core-shell particles are selected from butadiene core-shell particles, isoprene core-shell particles, nitrile butadiene core-shell particles, styrene butadiene core-shell particles, styrene-butadiene-styrene core-shell particles, styrene-ethylene-butadiene-styrene core-shell particles, styrene-isobutadiene-styrene core-shell particles, and mixtures thereof.

[0064] The particle size of the core-shell particles suitable for use in this invention is preferably 2 to 500,000 nm, more preferably 10 to 50,000 nm, more preferably 15 to 5,000 nm, and even more preferably 100 to 5,000 nm, wherein the particle size is measured according to ASTM E3340-22 Standard Guide for Development of Laser Diffraction Particle Size Analysis Methods for Powder Materials.

[0065] It is believed that the preferred core-shell particle size range maximizes the impact resistance of the core-shell particles in the composition according to the invention.

[0066] Core-shell particles may be present in the dual-curable adhesive composition according to the invention at 10 to 30% by weight, preferably 15 to 25% by weight, and more preferably 17 to 23% by weight of the total weight of the composition.

[0067] These core-shell particle contents are preferred because too high a content of core-shell particles will result in excessively high viscosity of the composition, while too low a content will result in reduced impact resistance at low temperatures (below 0°C).

[0068] The compositions according to the invention comprise a photoinitiator. The photoinitiator is used to initiate the photopolymerization of chemically unsaturated oligomers with combinations of monofunctional or polyfunctional monomers.

[0069] The photoinitiator suitable for this invention can be selected from: hydroxyhexylphenol ketone, 1-hydroxycyclohexylphenyl ketone, benzophenone, 4-chlorobenzophenone, methyl 2-benzoylbenzoate, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 4-phenylbenzophenone, 4-methylbenzophenone, 2-methyl-1-[4-ethylthio)phenyl]-2-(4-morpholino)-1-propanone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylpropanone, 2,4-diethylthioxanone, ethyl 4-(dimethylamino)benzoate, 4-(4'-methylphenylthio)-benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-benzoylbenzoate, etc. Acyl-4'-methyl diphenyl sulfide, methyl phenyl glyoxylate, methyl o-benzoyl benzoate, benzyl dimethyl ketal, 2-ethylhexyl-4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, hydroxy-2-methylphenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-isopropylthioxanthone, ethyl (2,4,6-trimethylbenzoyl)phenylphosphine, 2-benzyl-2-(dimethylamino)-1-[4-(morpholinyl)phenyl]-1-butanone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-1-butanone, and mixtures thereof; preferably, the photoinitiator is 2-isopropylthioxanthone.

[0070] Commercially available photoinitiators suitable for use in this invention include, but are not limited to, Irgacure 184 from Ciba Speciality Chemicals and ITX from Jiurichem.

[0071] The photoinitiator may be present in the composition at 1 to 10% by weight, preferably 2 to 9% by weight, and more preferably 3 to 7% by weight of the total weight of the composition.

[0072] The applicant has found these contents to be preferred because contents above 10% provide a sticky surface, while contents below 1% cause curing delay.

[0073] The dual-curable adhesive composition according to the present invention is photocurable and moisture-curable or heat-curable.

[0074] The composition according to the invention is first cured by light, preferably UV light, to obtain a PSA-type adhesive. The composition is then fully cured by moisture curing or heat curing.

[0075] Thermosetting is preferably performed at a temperature of 150°C.

[0076] The compositions or cured products according to the invention can be used as adhesives for the casings of mobile phones, televisions, laptops, motor vehicles, aerospace, semiconductors, and handheld devices, or as adhesives for laminated fabrics or films.

[0077] The adhesive composition according to the invention can be applied to assemble electronic devices to prevent damage to the devices when subjected to impact, shock, or frequent vibration at low temperatures (below 0°C).

[0078] Example

[0079] The composition according to the invention

[0080] The compositions according to the invention were prepared according to the components and contents presented in Table 1. The composition of Example 1 was prepared by placing a polyurethane resin, an aliphatic urethane diacrylate oligomer, and a monofunctional (meth)acrylate monomer into a reactor and mixing them at 40°C for 2 hours under mechanical stirring. Subsequently, core-shell particles were dispersed into the mixture over a 60-minute period while the mixture was mechanically stirred at 40°C.

[0081] Table 1

[0082] Comparative Example

[0083] Comparative compositions were prepared according to the components and contents presented in Table 2. The comparative compositions were prepared by placing polyurethane resin, aliphatic urethane diacrylate oligomer, and monofunctional (meth)acrylate monomer into a reactor and mixing them at 40°C with mechanical stirring for 2 hours.

[0084] Table 2

[0085] Shock test at break

[0086] The compositions of Example 1 and the comparative example were coated onto a SUS 304 substrate. The sample was irradiated with UV light. A glass substrate was placed on top of the adhesive on the SUS 304 substrate. Subsequently, the substrate was pressed under a pressure of 0.5 MPa for 30 seconds. Finally, the sample was exposed to moisture at 50% RH for 72 hours for curing.

[0087] In the fracture impact test, the samples were dropped from a height of 1 meter onto a metal surface at -20°C. The samples were dropped until they broke, and the number of drops was counted. The results are shown in Table 3.

[0088] Table 3

[0089] The composition according to the invention Comparative compositions Number of falls ＞100 30

[0090] The test results show that, compared with the comparative composition, the composition according to the present invention provides improved performance in the impact test.

Claims

1. A dual-curing adhesive composition, said dual-curing adhesive composition comprising: a) Polyurethane resins with a molecular weight of 1,000 to 1,000,000 Da; b) Oligomers of urethane diacrylate with a molecular weight of 1,000 to 100,000 Da; c) Photoinitiators; d) Two or more monofunctional (meth)acrylate monomers; and e) Core-shell particles, The molecular weight is measured using gel permeation chromatography (GPC) with polystyrene calibration standards, for example, according to ASTM 3536.

2. The dual-curable adhesive composition according to claim 1, wherein the polyurethane resin is obtained by reacting a diol with a diisocyanate to form an isocyanate-terminated polyurethane resin containing urethane groups and reactive isocyanate groups, wherein the suitable diol is preferably selected from poly(tetramethylene ether) glycol (PTMG), polypropylene glycol (PPG), ester polyols, and caprolactone-type polyols, and wherein the suitable isocyanate is preferably selected from methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 2,4,4-trimethylhexamethylene diisocyanate (TMDI), H 12 Methylene diphenyl diisocyanate (MDI) and mixtures thereof.

3. The dual-curable adhesive composition according to claim 1 or 2, wherein the polyurethane resin is present in 40 to 60% by weight, preferably 45 to 55% by weight, more preferably 47 to 58% by weight of the total weight of the composition.

4. The dual-curable adhesive composition according to any one of claims 1-3, wherein the urethane diacrylate oligomer is selected from aliphatic urethane di(meth)acrylate-terminated oligomers, aromatic urethane di(meth)acrylate oligomers, aliphatic polyester-based urethane di(meth)acrylate oligomers, aliphatic polyether-based urethane di(meth)acrylate oligomers, and mixtures thereof; preferably, the urethane diacrylate oligomer is an aliphatic urethane di(meth)acrylate-terminated oligomer.

5. The dual-curable adhesive composition according to any one of claims 1-4, wherein the urethane diacrylate oligomer is present in 20 to 40% by weight, preferably 25 to 35% by weight, and more preferably 27 to 33% by weight of the total weight of the composition.

6. The dual-curable adhesive composition according to any one of claims 1-5, wherein the two or more monofunctional (meth)acrylate monomers are selected from tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, isobornyl acrylate, isobornyl methacrylate, alkoxylated tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl methacrylate, cyclic trimethylolpropane acetal acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, ethoxylated (4)nonylphenol acrylate, alkoxylated nonylphenol acrylate, alkoxylated phenol acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, alkoxylated lauryl acrylate, stearyl acrylate, stearyl methacrylate, lauryl acrylate, methacrylate The monomers are lauryl acrylate, isodecyl acrylate, isodecyl methacrylate, isooctyl acrylate, isooctyl methacrylate, octyldecyl acrylate, octyldecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, caprolactone acrylate, caprolactone methacrylate, methoxy polyethylene glycol (350) monoacrylate and methoxy polyethylene glycol (550) monoacrylate, and mixtures thereof; preferably, the two or more monofunctional (meth)acrylate monomers are selected from tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, and mixtures thereof; more preferably, the two or more monofunctional (meth)acrylate monomers are tetrahydrofurfuryl acrylate and 2-(2-ethoxyethoxy)ethyl acrylate.

7. The dual-curable adhesive composition according to any one of claims 1-6, wherein the two or more monofunctional (meth)acrylate monomers are a combination of aliphatic (meth)acrylate monomers and cyclic (meth)acrylate monomers.

8. The dual-curable adhesive composition according to any one of claims 1-7, wherein the ratio of aliphatic (meth)acrylate monomer to cyclic (meth)acrylate monomer is 1:

2.

9. The dual-curable adhesive composition according to any one of claims 1-8, wherein the two or more monofunctional (meth)acrylate monomers are present in 3 to 30% by weight, preferably 7 to 25% by weight, and more preferably 10 to 20% by weight of the total weight of the composition.

10. The dual-curable adhesive composition according to any one of claims 1-9, wherein the core-shell particles have a Tg value of less than 0°C, and are preferably selected from butadiene core-shell particles, isoprene core-shell particles, nitrile butadiene core-shell particles, styrene-butadiene core-shell particles, styrene-butadiene-styrene core-shell particles, styrene-ethylene-butadiene-styrene core-shell particles, styrene-isobutadiene-styrene core-shell particles, and mixtures thereof.

11. The dual-curable adhesive composition according to any one of claims 1-10, wherein the core-shell particles have a particle size of 2 to 500,000 nm, preferably 10 to 50,000 nm, more preferably 15 to 5,000 nm, and even more preferably 100 to 5,000 nm.

12. The dual-curable adhesive composition according to any one of claims 1-11, wherein the core-shell particles are present in 10 to 30% by weight, preferably 15 to 25% by weight, and more preferably 17 to 23% by weight of the total weight of the composition.

13. The dual-curable adhesive composition according to any one of claims 1-12, wherein the composition is photocurable and moisture-curable or thermocurable.

14. A cured adhesive composition according to any one of claims 1-13 that is capable of dual curing, wherein the composition is first cured by light and then by moisture curing or heat curing.

15. The use of the dual-curable adhesive composition according to any one of claims 1-12 or the cured composition according to claim 14 as an adhesive for the casing of mobile phones, televisions, laptop computers, motor vehicles, aerospace, semiconductors, handheld devices or as an adhesive for laminating fabrics or films.

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