Dual curable adhesive composition

Abstract

The present invention relates to a dual-curable adhesive composition which can provide a cured product having a very excellent RBO prevention effect and having excellent adhesive force and reliability. With the implementation of the physical properties, the adhesive layer can be usefully applied to the adhesive layer between members such as a miniaturized and thinned camera module requiring excellent adhesive force and reliability.

Description

Technical Field

[0001] The present invention relates to a dual-curing adhesive composition that can effectively prevent the bleeding phenomenon of an adhesive and can achieve excellent adhesive force and reliability after curing. Background Art

[0002] A dual-cure adhesive of the type that performs main curing by heat after pre-curing by light irradiation is proposed for an adhesive used for assembling a camera module in order to minimize thermal damage to an image sensor or the like caused by high-temperature processing and satisfy adhesion, reliability, and production efficiency.

[0003] Furthermore, as camera modules have been recently miniaturized and thinned, components of the camera modules have also become finer, and thus the performance required of an adhesive for bonding and fixing the components has gradually become more complex.

[0004] Specifically, as the bonding area decreases, the bonding site of the adhesive is easily peeled off or damaged, and thus the adhesive is required to have an improved bonding strength per unit area and improved durability.

[0005] In addition, the material of the base material used in the camera module is mainly used after plasma treatment for adhesion improvement and cleaning. After the plasma treatment, the interface of the material shows hydrophilicity, and when a relatively high polarity adhesive is used, resin bleed out (RBO) occurs, in which the adhesive easily flows out. The resin that flows out in this way has the problem of weakening the adhesion or increasing the risk of corrosion of surrounding parts, resulting in reduced reliability, so it is necessary to be able to effectively prevent the resin bleed out phenomenon.

[0006] However, when an additive for reducing surface energy is used to prevent the resin bleeding phenomenon, there are still problems such as decreased adhesion, decreased reliability, or difficulty in adjusting viscosity.

[0007] Furthermore, there is therefore a need for an adhesive that can achieve excellent adhesion while effectively preventing the resin bleed-out phenomenon. Summary of the invention

[0008] Technical issues to be solved

[0009] One aspect of the present invention provides a dual-cure adhesive composition having excellent adhesive force while effectively preventing the resin bleed-out phenomenon.

[0010] Means of solving the problem

[0011] The present invention provides a dual-curing adhesive composition, which comprises a base epoxy resin and a multifunctional compound comprising one or more acryl terminal groups and one or more -SR1 terminal groups, wherein R1 is C 1-50 of hydrocarbon groups.

[0012] According to one embodiment of the present invention, the multifunctional compound may include three or more terminal groups.

[0013] According to an embodiment of the present invention, the percentage of the number of -SR1 terminal groups relative to the number of all terminal groups of the multifunctional compound may be 20% or more.

[0014] According to an embodiment of the present invention, the multifunctional compound may be represented by the following Chemical Formula 1.

[0015] [Chemical formula 1]

[0016]

[0017] In the chemical formula 1,

[0018] L is a (a+b)-valent linker,

[0019] R1 is C 1-50 The hydrocarbon group,

[0020] a and b are mutually independent integers of 1 or more.

[0021] According to one embodiment of the present invention, in the chemical formula 1, R1 may be C 4-15 of hydrocarbon groups.

[0022] According to one embodiment of the present invention, the linker may be selected from Any of .

[0023] According to an embodiment of the present invention, the multifunctional compound may be included in an amount of 10 to 50 parts by weight relative to 100 parts by weight of the base epoxy resin.

[0024] According to an embodiment of the present invention, a multifunctional thiol compound may be further included.

[0025] According to an embodiment of the present invention, the multifunctional thiol compound may be included in an amount of 10 to 60 parts by weight relative to 100 parts by weight of the base epoxy resin.

[0026] According to an embodiment of the present invention, the weight ratio of the multifunctional thiol compound to the multifunctional compound may be 0.5 to 2:1.

[0027] According to an embodiment of the present invention, the total weight ratio of the photocurable monomer and the multifunctional compound to the base epoxy resin may satisfy a weight ratio of 0.2 to 1:1.

[0028] According to an embodiment of the present invention, one or more additives selected from the group consisting of a thermal curing agent, a photoinitiator, a curing accelerator and an inorganic filler may be further included.

[0029] The present invention can provide a cured product prepared from the dual-cure adhesive composition.

[0030] Effects of the Invention

[0031] The dual-curing adhesive composition according to one aspect can provide a cured product having excellent RBO prevention effect and excellent adhesion and reliability. By achieving the above-mentioned physical properties, it can be usefully applied to the adhesive layer between components such as miniaturized and thinned camera modules that require excellent adhesion and reliability. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 A method for measuring the RBO prevention effect is shown.

[0033] Figure 2 A method for preparing a sample for adhesion evaluation is shown. DETAILED DESCRIPTION

[0034] Hereinafter, the present invention will be described in more detail by specific examples or embodiments including the accompanying drawings. However, the following specific examples or embodiments are only a reference for describing the present invention in detail, and the present invention is not limited thereto and can be limited to various forms.

[0035] Unless otherwise defined in this specification, all technical terms and scientific terms have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used for explanation in this specification are only used to effectively record specific examples and are not intended to limit the present invention.

[0036] Unless the context specifically indicates otherwise, the singular form used in the present specification may be intended to include the plural form as well.

[0037] In addition, units used in this specification unless otherwise specified are based on weight, and as an example, a unit of % or ratio means weight % or weight ratio, and unless otherwise defined, weight % means the weight % of any one component in the entire composition in the composition.

[0038] In addition, the resin range used in this specification includes the lower limit value and the upper limit value and all values ​​within the range, increments logically derived from the form and width of the defined range, all values ​​of the double definition, and all possible combinations of the upper and lower limits of the numerical range defined in different forms from each other. Unless otherwise specifically defined in this specification, values ​​outside the numerical range that may appear due to experimental errors or numerical rounding are also included in the defined numerical range.

[0039] The term “comprising” in this specification is an open-ended description having a meaning equivalent to expressions such as “having”, “containing”, “having” or “characterized by”, and does not exclude elements, materials or processes that are not additionally listed.

[0040] "Substituted" as described in the present invention means that the hydrogen atoms of the substituted part are replaced by a substituent. In one embodiment, each carbon atom of the substituted group is not substituted by two or more substituents. In another embodiment, each carbon atom of the substituted group is not substituted by one or more substituents. As long as it is a known substituent, the substituent can be used without restriction.

[0041] The "hydrocarbon" described in the present invention means a chemical group containing only hydrogen and carbon atoms.

[0042] The term "hydrocarbon group" in the present specification means a radical having one bond position derived from hydrocarbon by removing one hydrogen.

[0043] The term "alkyl" in this specification refers to an organic free radical derived from an aliphatic hydrocarbon by removing one hydrogen, and may include both straight-chain and branched forms. As an example, it includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, ethylhexyl, etc., but is not limited thereto.

[0044] The "alicyclic" described in the present invention as a cycloalkyl group means a non-aromatic monocyclic or multicyclic ring system having 3 to 10 carbon atoms and may have an unsaturated bond in the ring.

[0045] The term "(meth)acrylate system" in this specification includes both acrylate systems and methacrylate systems.

[0046] The "epoxy resin" described in the present invention means a cured plastic that has completed a reaction with a curing agent in an academic sense, but as generally used in the technical field, it becomes a raw material of an epoxy composition, and because it has an epoxy group, it can mean an epoxy compound that can react with a curing agent.

[0047] In addition, the "cured product" described in the present invention has a general meaning and may be a cured product generated by curing the adhesive composition. In addition, the cured product may include a semi-cured product.

[0048] The present invention adds a partially hydrophobized multifunctional compound to an adhesive composition in order to solve the conventional resin bleeding (RBO) phenomenon, thereby providing a dual-cure adhesive composition that can effectively suppress the resin bleeding (RBO) phenomenon and achieve excellent adhesion and reliability after curing.

[0049] Hereinafter, one aspect of the present invention will be described in more detail.

[0050] The present invention provides a dual-curing adhesive composition, which comprises a base epoxy resin and a polyfunctional compound comprising one or more acryl terminal groups and one or more -SR1 terminal groups, wherein R1 is C 1-50 of hydrocarbon groups.

[0051] According to one embodiment of the present invention, the multifunctional compound may include three or more or four or more terminal groups. The terminal groups may include one or more acryl terminal groups and one or more -SR1 terminal groups. In addition, the percentage of the number of -SR1 terminal groups relative to the number of all terminal groups of the multifunctional compound may be 10% or more, 15% or more, or 20% or more.

[0052] According to an embodiment of the present invention, the multifunctional compound may be an acrylic multifunctional compound, and may be represented by the following Chemical Formula 1.

[0053] [Chemical formula 1]

[0054]

[0055] In the chemical formula 1, L is a linker with a valence of (a+b), and R1 is C 1-50 wherein a and b are independently integers greater than 1. Specifically, L is a linker with a value of (a+b), wherein a+b is 3 to 6, and R1 is C 3-30 A hydrocarbon group, and a and b are integers of 1 to 5 independently of each other. In this case, the linker may be selected from Any of .

[0056] According to one embodiment of the present invention, in the chemical formula 1, R1 may be C 4-15 The hydrocarbon group, C 4-15 Alkyl, C 9-17 Alkyl or C 10-15In the case where R1 of the polyfunctional compound satisfies the carbon number, there is an advantage that a more significant resin bleeding (RBO) phenomenon suppression effect and excellent adhesive force can be achieved at the same time.

[0057] According to an embodiment of the present invention, the polyfunctional compound may be included in an amount of 5 to 80 parts by weight, 10 to 50 parts by weight, or 25 to 40 parts by weight relative to 100 parts by weight of the base epoxy resin.

[0058] According to an embodiment of the present invention, the polyfunctional compound may be included in an amount of 0.1 to 50 wt %, 0.1 to 40 wt %, 0.1 to 20 wt % or 5 to 20 wt % relative to the total weight of the composition.

[0059] The base epoxy resin may be used without limitation as long as it is commonly used in the art, and may be an aliphatic epoxy compound, an alicyclic epoxy compound, or an aromatic epoxy compound, specifically, triglycidyl ether or diglycidyl ether, but is not limited thereto.

[0060] As an example, the base epoxy resin may include any one or more bisphenol epoxy resins selected from bisphenol A series, bisphenol E series, bisphenol F series, bisphenol M series, bisphenol S series, and bisphenol H series, etc.; one or more mixtures selected from glycidyl ether epoxy resins, glycidyl amine epoxy resins, novolac epoxy resins, and cresol novolac epoxy resins, etc. As an example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, etc. may be listed, but are not limited thereto. In addition, the base epoxy resin may be liquid at room temperature, and the epoxy equivalent (EEW) may be 100 to 600 g / eq or 150 to 500 g / eq.

[0061] In addition, the base epoxy resin may be included in an amount of 5 to 80 wt %, 10 to 60 wt %, or 15 to 50 wt % relative to the entire weight of the adhesive composition.

[0062] According to one embodiment of the present invention, the composition may further include a multifunctional thiol compound. As long as it is a compound containing two or more or three or more thiol groups, the multifunctional thiol compound may be used without much restriction, and as an example, it may be selected from 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine 2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate) and tetraethylene glycol bis(3-mercaptopropionate), etc. One or a combination of more than two, but not limited thereto. In addition, the multifunctional thiol compound may be included in an amount of 1 to 80 wt%, 5 to 60 wt%, or 5 to 25 wt% relative to the overall weight of the adhesive composition.

[0063] According to an embodiment of the present invention, the multifunctional thiol compound may be included in an amount of 5 to 100 parts by weight, 10 to 60 parts by weight, or 30 to 50 parts by weight relative to 100 parts by weight of the base epoxy resin.

[0064] According to an embodiment of the present invention, the weight ratio of the multifunctional thiol compound to the multifunctional compound may be 0.1 to 5:1, 0.5 to 2:1, or 1.1 to 1.5:1.

[0065] According to an embodiment of the present invention, the total weight ratio of the photocurable monomer and the multifunctional compound to the base epoxy resin may satisfy 0.1 to 2:1, 0.2 to 1:1, or 0.5 to 0.9:1.

[0066] According to one embodiment of the present invention, the composition may further include other multifunctional acrylic compounds in addition to the multifunctional compound according to one embodiment. As long as it is a compound containing two or more or three or more acrylic groups, the multifunctional acrylic compound can be used without much restriction, and as an example, it can be selected from dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tri [2- (acryloyloxy) ethyl] isocyanurate, di-trimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and pentaerythritol tetra (meth) acrylate, etc. One or more, but not limited to this. In addition, the multifunctional acrylic compound may be included in 1 to 90 weight %, 5 to 50 weight % or 5 to 30 weight % relative to the overall weight of the adhesive composition.

[0067] According to an embodiment of the present invention, one or more additives selected from the group consisting of a thermal curing agent, a photoinitiator, a curing accelerator and an inorganic filler may be further included.

[0068] The thermosetting agent can use commonly used solid thermosetting agents and liquid thermosetting agents, and the thermosetting agent can directly participate in the crosslinking of the composition or can be used in the form of a catalyst. The thermosetting agent can be an amine curing agent, an anhydride curing agent or a phenol curing agent. These can be used alone or in combination of two or more. Preferably, an amine curing agent can be used. As an example, commercially available products such as Adeka EH-4357S, Adeka Hardener EH-4357S, Adeka Hardener EH-4357PK, Adeka Hardener EH-4380S, Fujicure FXR-1081, Fujicure FXR-1020, Sunmide LH-210, Sunmide LH-2102, Sunmide LH-2100, Ajicure PN-23, Ajicure PN-F, Ajicure PN-23J, Ajicure PN31, Ajicure PN-31J, Novacure HX-3722, Novacure HX-3742, Novacure HX-3613 and Asahi Kasei Chemicals HX3932HP can be used, but are not limited thereto.

[0069] Examples of the amine curing agent include dimethyldioxane, dicyandiamide, isophoronediamine, diethylenetriamine, triethylenetetramine, triethylenepentamine, bis(p-aminocyclohexyl)methane, methylenedianiline (e.g., 4,4'-methylenedianiline), 4,7,10-trioxotridecane-1,13-diamine, polyetheramine (e.g., Jeffamine D-230, JeffamineD-400, etc.), diaminodiphenylmethane, diaminodiphenyl sulfone, 2,4-toluenediamine, 2,6-toluenediamine, 2,4-diamino-1-methylcyclohexane, 2,6-diamino-1-methylcyclohexane, 2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene, 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, diaminodiphenyl ether, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl and 3,3'-dimethyl-4,4'-diaminobiphenyl, etc.

[0070] Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0071] Examples of the phenolic curing agent include phenolic resins such as formaldehyde condensation type resol type phenolic resins, formaldehyde-free condensation type phenolic resins, novolac type phenolic resins, novolac type phenolic resins and polyhydroxystyrene resins; resol type phenolic resins such as aniline modified novolac phenolic resins and melamine modified novolac phenolic resins; novolac type phenolic resins such as phenol novolac resins, cresol novolac resins, tert-butylphenol novolac resins, nonylphenol novolac resins and naphthol novolac resins; special phenolic resins such as dicyclopentadiene modified phenolic resins, terpene modified phenolic resins, trisphenol methane type resins, phenol aralkyl resins having a phenylene skeleton or a diphenylene skeleton, and naphthol aralkyl resins; and polyhydroxystyrene resins such as poly(p-hydroxystyrene).

[0072] In addition, the thermal curing agent may be included in an amount of 1 to 100 parts by weight, 5 to 80 parts by weight based on 100 parts by weight of the base epoxy resin included in the dual-curing adhesive composition, but is not limited thereto.

[0073] The curing accelerator is used to adjust the curing speed, and at least one selected from imidazole-based accelerators and urea-based accelerators can be used.

[0074] Examples of the imidazole accelerator include 2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2-undecylimidazole, 3-heptadecylimidazole, 2-phenylimidazole, 2-phenylimidazoline, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and 1-cyanoethyl-2-undecylimidazole, but are not limited thereto.

[0075] Examples of the urea-based accelerator include p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, and 3,4-dichlorophenyl-N,N-dimethylurea, but are not limited thereto.

[0076] In addition, the curing accelerator may be included in an amount of 0.1 to 100 parts by weight, 5 to 80 parts by weight based on 100 parts by weight of the base epoxy resin included in the adhesive composition, but is not limited thereto.

[0077] The photoinitiator may be used without limitation as long as it is common, and examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, hydroxydimethylacetophenone, dimethylaminoacetophenone, dimethoxy-2-phenylacetophenone, 3-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-chlorophenolacetophenone, 4,4-dimethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 4-hydroxycyclophenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-propane-1-one, 4-(2-hydroxyethoxy)- )phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4-diaminobenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, diphenyl ketone benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, fluorene, triphenylamine, carbazole, benzyl diphenyl sulfide and tetramethylthiuram monosulfide, and one or a mixture of two or more selected from them can be used. In addition, commercially available products such as Darocur 1173, Igacure 184, and Igacure 907 (Ciba) are exemplified.

[0078] In addition, the photoinitiator may be contained in an amount of 0.01 to 20 parts by weight, 0.1 to 10 parts by weight based on 100 parts by weight of the multifunctional monomer contained in the adhesive composition, but is not limited thereto. In this case, the multifunctional monomer is a photopolymerizable multifunctional monomer contained in the composition, and refers to the sum of the multifunctional compound according to one embodiment and the above-mentioned multifunctional thiol compound and multifunctional acrylic compound.

[0079] The inorganic filler can be used without restriction as long as it is common, and as its non-limiting examples, silicon dioxide, diatomaceous earth, aluminum oxide, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulfate, gypsum, calcium silicate, talc, glass beads, sericite, talcum clay, bentonite, aluminum nitride, silicon nitride, potassium titanate, zeolite, calcium oxide, magnesia and ferrite, etc., and can be used as a mixture of one or more selected from them. Here, the inorganic filler can be included as 5 to 60 weight %, 15 to 50 weight %, 25 to 40 weight % based on the total weight of the adhesive composition. Alternatively, the inorganic filler can be included as 10 to 200 weight parts, 50 to 180 weight parts or 80 to 150 weight parts relative to 100 weight parts of the base epoxy resin.

[0080] The dual-curing adhesive composition according to one embodiment of the present invention may include a base epoxy resin, a curing agent, a multifunctional compound according to one embodiment, a multifunctional thiol compound, a photoinitiator, and an inorganic filler. Specifically, the dual-curing adhesive composition may include 5 to 80 weight % of a base epoxy resin, 1 to 30 weight % of a curing agent, 0.1 to 50 weight % of a multifunctional compound, 1 to 80 weight % of a multifunctional thiol compound, 0.1 to 10 weight % of a photoinitiator, and 5 to 60 weight % of an inorganic filler, or 10 to 60 weight % of a base epoxy resin, 1 to 25 weight % of a curing agent, 0.1 to 20 weight % of a multifunctional compound, 5 to 60 weight % of a multifunctional thiol compound, 0.5 to 5 weight % of a photoinitiator, and 15 to 50 weight % of an inorganic filler relative to the overall weight of the adhesive composition.

[0081] In addition, any one or more other additives may be added to the dual-curing adhesive composition according to an embodiment of the present invention. For example, any additive may also include stabilizers, viscosity modifiers, surfactants, pigments or dyes, matting agents, flame retardants, curing inhibitors, defoamers, wetting agents, colorants, thermoplastic agents, processing aids, ultraviolet (UV) blockers, fluorescent compounds, UV stabilizers, antioxidants, release agents and mixtures thereof. The arbitrary additives may be used in the range of the physical properties of the adhesive composition of the present invention without interfering therewith.

[0082] According to one embodiment of the present invention, the dual-curing adhesive composition may be a one-component type or a two-component type, and may be usefully applicable as a structural adhesive. In addition, the adhesive composition may be a dual-curing adhesive composition. Specifically, the adhesive composition may form a first polymer network derived from a photopolymerizable multifunctional monomer by thermal curing and photocuring reactions, and form a second polymer network derived from a curing agent and an epoxy resin. The first polymer network and the second polymer network may densely form an interpenetrating polymer network (IPN) that is physically mixed and interpenetrated, thereby imparting high bonding strength and excellent reliability. Thus, the adhesive composition may not only be implemented by selecting photocuring, thermal curing or making it parallel dual curing according to the use environment or purpose, but may also effectively prevent resin exudation with the inclusion of the above-mentioned multifunctional compound, and may also simultaneously achieve excellent reliability under the conditions of bonding strength improved by dual curing and high temperature, humidity or thermal shock.

[0083] Although the adhesive composition according to one aspect has low viscosity before the curing reaction, after the primary curing reaction of the photocuring reaction, the viscosity increases sharply by forming the first polymer network. Thus, an adherend such as a camera module can be reliably supported on the substrate, and as the IPN is formed by the subsequent thermal curing reaction, the adherend can be firmly bonded and fixed on the substrate and can have excellent durability and reliability.

[0084] The photocuring can be performed under normal photocuring conditions and can be performed by irradiating a light source such as infrared rays, visible light, ultraviolet rays, electron rays, etc. having a wavelength of 800 nm or more, and the light source can be 100 to 3000 mW / cm 2 , 300 to 3000mW / cm 2 or 500 to 2000 mW / cm 2 The range is 1 to 20 seconds or 1 to 10 seconds. In addition, the light source irradiation means can include low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, excimer laser, chemical lamp, black light lamp, microwave excitation mercury lamp, metal halide lamp, sodium lamp, fluorescent lamp, LED SPOT type UV irradiator, xenon lamp, 365nm wavelength ultraviolet lamp or deep ultraviolet lamp, but are not limited thereto.

[0085] The thermal curing may be performed under conventional epoxy thermal curing conditions, and as an example, may be performed at a temperature of less than 150°C, less than 100°C, less than 90°C, or between 50 and 90°C for less than 6 hours, between 10 minutes and 5 hours, or between 30 minutes and 2 hours.

[0086] The present invention can provide a cured product prepared from the above-mentioned dual-curing adhesive composition. The cured product has a very outstanding RBO prevention effect, and at the same time has excellent adhesion after curing, and can also achieve excellent reliability at the same time under conditions of high temperature, high humidity or thermal shock. In this regard, the cured product according to one aspect can be usefully used as an adhesive, a sealant, a coating agent, etc. For example, it can be usefully applied as an adhesive layer between components such as camera modules that require high bonding strength and impact resistance per unit area, and it can also be used as a structural adhesive in the assembly of not only structures such as civil engineering and construction, but also in transportation means such as automobiles, airplanes, and ships. This can be used in many ways across industries by realizing excellent bonding properties between the same or different materials such as metal and metal, metal and glass, and metal and carbon fiber.

[0087] In addition, one aspect of the present invention provides a structure including the cured product. Specifically, the structure according to one aspect may include a first adherend, a second adherend, and an adhesive layer disposed between the first adherend and the second adherend, and the adhesive layer may be the cured product.

[0088] As an example, the first adherend and the second adherend may be parts of aluminum, brass or polycarbonate, etc. Specifically, the first adherend and the second adherend may be selected from lenses, lens holders and housings, etc., and part or the whole of them may be bonded with high bonding strength through the above-mentioned bonding layer to form a high-quality structure.

[0089] Specifically, the structure according to one aspect may be a camera module.

[0090] As an example, the structure may be a camera module mounted on a mobile device such as a smartphone, or a camera module for a vehicle.

[0091] The above implementation examples are described in more detail below through embodiments. However, the following embodiments are only for illustrative purposes and do not limit the scope of rights.

[0092] [Preparation Examples 1 to 11] Preparation of polyfunctional compounds

[0093] After dissolving 1 mol of pentaerythritol tetraacrylate (PETTA, Meiyuan) and 1 mol of alkyl mercaptan in 1 L of methyl ethyl ketone (MEK) solvent, 0.01 mol of triethylamine (TEA) was added and the mixture was reacted for 1 hour and 30 minutes. After the reaction was completed, the mixture was cooled, the salt was removed by filtration, the solvent was evaporated under reduced pressure, and the product was separated, thereby finally preparing a multifunctional compound.

[0094] At this time, the alkyl mercaptan used was the one listed in the following Table 1.

[0095]

Table 1

[0096] Multifunctional compounds Alkyl mercaptan / carbon number Preparation Example 1 1-Butanethiol / 4 Preparation Example 2 1-Pentanethiol / 5 Preparation Example 3 1-Hexanethiol / 6 Preparation Example 4 1-Octylthiol / 8 Preparation Example 5 1-Nonanethiol / 9 Preparation Example 6 1-Decanethiol / 10 Preparation Example 7 1-Undecanethiol / 11 Preparation Example 8 1-Dodecanethiol / 12 Preparation Example 9 1-Tetradecanethiol / 14 Preparation Example 10 1-Hexadecanethiol / 16 Preparation Example 11 1-Octadecanethiol / 18

[0097] [Examples 1 to 11] Preparation of dual-cure adhesive composition

[0098] 30 wt % of a base epoxy resin (YD-128K; bisphenol A type epoxy resin, Kukto Chemical Co., Ltd.), 14 wt % of an amine curing agent (PN-23J, Ajinomoto Fine Chemicals), 13 wt % of a multifunctional thiol compound (KarenzMT PE1; a mixture of pentaerythritol tetrakis (3-mercaptobutyrate) and pentaerythritol tris (3-mercaptobutyrate), Showa Denko), 1 wt % of a photoinitiator (Irgacure 184, Ciba), 2 wt % of fumed silica (Fumedsilica, TS-720, Cabot Corporation), 30 wt % of fused silica (Fused silica, FB-3SDC, Nippon Electric Chemical Co., Ltd.) and 10 wt % of the multifunctional compound prepared in any one of the preparation examples 1 to 11 were mixed at room temperature to prepare a dual-cure adhesive composition (total 100 wt %).

[0099] [Comparative Example 1]

[0100] The preparation was carried out in the same manner as in Example 1 except that 10 wt % of pentaerythritol tetraacrylate (PETTA, Meiyuan) was added instead of the multifunctional compound in the preparation example of Example 1.

[0101] [Comparative Example 2]

[0102] The same method as in Example 1 was used except that 5 wt % of pentaerythritol tetraacrylate (PETTA, Meiyuan) and 5 wt % of 1-tetradecanethiol (1-tetradecanethiol) were added instead of the multifunctional compound in the preparation example of Example 1.

[0103] [Evaluation Example 1] Evaluation of bleeding phenomenon (RBO)

[0104] After plasma treatment of a substrate made of polyimide (200W, N2, 5min), the dual-curing adhesive composition prepared in the embodiment and the comparative example was horizontally coated with a radius of 0.5mm, and after being placed at 25°C for 1 hour, it was moved to a hot plate set at 80°C and cured for 150 seconds. Figure 1 The difference between the radius (R0) of the first applied adhesive and the radius (R1) of the adhesive flowing out after final curing was calculated and the RBO value (R1-R0) was recorded in Table 2 below.

[0105] [Evaluation Example 2] Storage stability evaluation

[0106] The dual-cure adhesive compositions of the examples and comparative examples were stored in a plastic sealed container at 25° C. for 72 hours, and the viscosities before and after storage were measured. The storage stability was evaluated based on the following criteria, and the results are recorded in the following Table 2. At this time, the viscosity was measured using a Brookfield corn plate viscosity analyzer under the measurement conditions of 25° C., spindle 51z, and Rpm 5.0.

[0107] X: Increased by more than 20% compared to the initial viscosity

[0108] O: Less than 20% increase compared to initial viscosity

[0109] [Evaluation Example 3] Adhesion Evaluation

[0110] As in Figure 2 As observed in the embodiment, the dual-curing adhesive composition (discharge: 50 mg) prepared in the embodiment and the comparative example is distributed in a form of an inner diameter of 13.5 mm and an outer diameter of 15.5 mm under the conditions of nozzle spacing: 1.0 mm (19G) and speed 6.0 mm / sec at the aluminum first adherend (Holder) interface. Subsequently, the unit is prepared by bonding with the aluminum second adherend (Lens). At this time, the spacing between the first adherend and the second adherend is called 0.3 mm. The prepared unit uses four light sources for the first curing (1000 mW / cm2) while keeping the distance between the ultraviolet light of LED 365 nm and the adhesive composition and the light source at 25 mm in the horizontal direction of the unit. 2 , 7s), and then heated in a convection oven at 80°C for 1 hour and subjected to a second curing.

[0111] Subsequently, the adhesive force of the cured unit was measured using UTM (AMETEK LD50), and the tensile speed was set to 30 mm / min. The results are shown in Table 2 below.

[0112] [Evaluation Example 4] Reliability Evaluation

[0113] The same unit as in the adhesion evaluation was exposed for 500 hours in an environment maintained at 85°C, 85%RH using a temperature / humidity resister, and the adhesion was measured. The reliability for temperature / humidity resistance was evaluated according to the following criteria, and the results are recorded in Table 2 below.

[0114] In addition, the cured unit was placed at -40°C for 30 minutes and at 85°C for 30 minutes as one cycle, and the adhesive strength was measured after repeating 500 cycles. The reliability against thermal shock was evaluated according to the following criteria, and the results are recorded in the following Table 2.

[0115] X: Adhesion strength is reduced by 20% or more compared to the unit before reliability evaluation

[0116] O: Adhesion strength decreased by less than 20% compared to the unit before reliability evaluation

[0117] The physical properties of the dual-cure adhesive compositions prepared in Examples 1 to 11 and Comparative Examples 1 and 2 were evaluated and shown in Table 2 below.

[0118]

Table 2

[0119]

[0120] As shown in Table 2, it was confirmed that the dual-cure adhesive composition according to the embodiment of the present invention exhibited a very excellent RBO prevention effect while maintaining both excellent adhesion and reliability. On the contrary, in the case of Comparative Examples 1 and 2 not including the multifunctional compound according to one aspect, it was confirmed that the RBO prevention effect and stability were very poor.

[0121] In addition, the best RBO prevention effect, adhesiveness and reliability were confirmed in the case of Example 9. Thus, in the case of containing a partially hydrophobized multifunctional acrylate monomer (especially a multifunctional acrylate monomer whose terminal is hydrophobized with an alkyl group having 10 to 15 carbon atoms), it was confirmed that a more significant RBO prevention effect and excellent adhesiveness were simultaneously exhibited.

[0122] The effect of the present invention is analyzed. By using a dual-curing adhesive composition containing a multifunctional compound in which an alkyl group as a hydrophobic group is introduced into a hydrophilic substrate by plasma treatment, the hydrophilic functional group is converted into partial hydrophobicity, thereby reducing the affinity between the interface and the adhesive, thereby partially blocking the resin exudation, and through the embodiment, the degree of hydrophobization according to the carbon number of the alkyl group and the RBO prevention effect according to this are experimented. It is analyzed that when the carbon number is large, the bonding area between the interface of the alkyl group and the substrate increases, thereby relatively suppressing the resin exudation, but in the case where the carbon number is too large, the bonding force of the adhesive composition is reduced due to the steric hindrance of the alkyl group.

[0123] In other words, the dual-curing adhesive composition according to one aspect can have an excellent RBO prevention effect and can achieve a further improved adhesive force through dual curing. By achieving the above-mentioned physical properties, it is expected that it can be usefully applied as an adhesive layer between components such as camera modules that require high adhesive strength and water resistance per unit area and are miniaturized and thinned.

[0124] Although the embodiments of the present invention are described in more detail above with reference to the accompanying drawings, the present invention is not necessarily limited to such embodiments, and various modifications can be implemented without departing from the technical concept of the present invention. Therefore, the embodiments disclosed in the present invention are not used to limit the technical concept of the present invention, but are used for illustration, and the scope of the technical concept of the present invention is not limited by such embodiments. The protection scope of the present invention should be interpreted by the attached claims, and all technical concepts falling within the scope equivalent thereto should be interpreted as being included in the scope of the rights of the present invention.

Claims

1. A dual-curing adhesive composition comprising: Base epoxy resin; as well as A polyfunctional compound comprising one or more acryloyl terminal groups and one or more -SR1 terminal groups, The R1 is C 1-50 of hydrocarbon groups.

2. The dual-curing adhesive composition according to claim 1, wherein The polyfunctional compound includes three or more terminal groups.

3. The dual-curing adhesive composition according to claim 1, wherein The percentage of the number of -SR1 terminal groups relative to the number of all terminal groups of the polyfunctional compound is 20% or more.

4. The dual-curing adhesive composition according to claim 1, wherein The multifunctional compound is represented by the following chemical formula 1: [Chemical formula 1] In the chemical formula 1, L is a (a+b)-valent linker, R1 is C 1-50 The hydrocarbon group, a and b are mutually independent integers of 1 or more.

5. The dual-curing adhesive composition according to claim 4, wherein: In the chemical formula 1, R1 is C 4-15 of hydrocarbon groups.

6. The dual-curing adhesive composition according to claim 4, wherein: The linker is selected from Any of .

7. The dual-curing adhesive composition according to claim 1, wherein: The multifunctional compound may be included in an amount of 10 to 50 parts by weight relative to 100 parts by weight of the base epoxy resin.

8. The dual-curing adhesive composition according to claim 1, wherein The dual-cure adhesive composition further includes a multifunctional thiol compound.

9. The dual-curing adhesive composition according to claim 8, wherein: The polyfunctional thiol compound is contained in an amount of 10 to 60 parts by weight relative to 100 parts by weight of the base epoxy resin.

10. The dual-curing adhesive composition according to claim 8, wherein: The weight ratio of the multifunctional thiol compound to the multifunctional compound is 0.5 to 2:

1.

11. The dual-curing adhesive composition according to claim 8, wherein: The total of the photocurable monomer and the multifunctional compound satisfies a weight ratio of 0.2 to 1:1 with respect to the base epoxy resin.

12. The dual-cure adhesive composition according to claim 1, wherein: The dual-curing adhesive composition further includes one or more additives selected from a thermal curing agent, a photoinitiator, a curing accelerator and an inorganic filler.

13. A solidified product, wherein The cured product is prepared from the dual-cure adhesive composition according to any one of claims 1 to 12.

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