Radiation-curable (meth)acrylic adhesive composition

Abstract

Disclosed is a radiation curable (meth)acrylic adhesive composition consisting essentially of: i) a (meth)acrylated polydiene resin; ii) a multifunctional (meth)acrylic monomer component; iii) a monofunctional (meth)acrylic monomer component; and iv) a photoinitiator component.

Description

Technical Field

[0001] Technical Field The present invention relates to a radiation-curable (meth)acrylic adhesive composition that has both good chemical resistance and good mechanical properties at high temperatures when cured.

Background Art

[0002] Background of the Invention Adhesive compositions are widely used in many applications. Depending on the application, it is necessary for the adhesive to be tough in the case of an impact such as when the adhered device falls, and for the adhesive line to have chemical resistance when exposed to chemical attacks such as ethanol in a finger disinfectant or an oil-containing composition (such as those present on an individual's skin).

[0003] Radiation-curable adhesives with excellent chemical resistance, such as radiation-curable epoxy adhesives, have also been developed. However, such radiation-curable epoxy adhesives are brittle and have extremely insufficient elongation.

[0004] Also, among radiation-curable (meth)acrylic adhesives, some are strong and tough against impacts, but generally have poor chemical resistance, especially chemical resistance at high temperatures.

[0005] Regarding mechanical properties, as shown in FIG. 1, the greater the area under the curve, the higher the toughness. Therefore, it is difficult to obtain a material that simultaneously has a high Young's modulus, high tensile strength, and high elongation. For example, a material with a high elastic modulus and high tensile strength but low elongation (for example, a comparative example of the present invention) does not have a large area under the curve and thus cannot be said to be tough.

[0006] There is a need to develop a radiation-curable adhesive that has excellent chemical resistance at high temperatures and excellent mechanical properties such as tensile strength, elongation, and Young's modulus.

Summary of the Invention

Problems to be Solved by the Invention

[0007] Summary of the Invention As a result of diligent research, the inventors have found that by using a (meth)acrylic polydiene resin and polyfunctional and monofunctional (meth)acrylic monomers in combination in an adhesive composition, a radiation-curable (meth)acrylic adhesive can be obtained that possesses both good chemical resistance at high temperatures and good mechanical properties such as tensile strength, elongation, and Young's modulus. [Means for solving the problem]

[0008] In one aspect, the present invention is i) (Meth)acrylic polydiene resin; ii) Polyfunctional (meth)acrylic monomer components; iii) Monofunctional (meth)acrylic monomer components; and iv) Photoinitiator components The present invention provides a radiation-curable (meth)acrylic adhesive composition containing, or essentially composed of, the above.

[0009] In another aspect, the present invention provides a method for bonding substrates using the radiation-curable (meth)acrylic adhesive composition of the present invention.

[0010] In another aspect, the present invention provides articles bonded with cured products of the radiation-curable (meth)acrylic adhesive composition of the present invention. [Brief explanation of the drawing]

[0011] [Figure 1] Regarding mechanical properties, as shown in Figure 1, the larger the area under the curve, the higher the toughness. [Figure 2] The graphs showing the results for Examples 1 to 3 are shown in Figures 2 to 4, respectively. [Figure 3] The graphs showing the results for Examples 1 to 3 are shown in Figures 2 to 4, respectively. [Figure 4] The graphs showing the results for Examples 1 to 3 are shown in Figures 2 to 4, respectively. [Modes for carrying out the invention]

[0012] Detailed description of the invention Those skilled in the art should understand that this discussion describes only exemplary embodiments and does not limit the broader aspects of the invention. Each of the embodiments described herein can be combined with any other embodiments unless otherwise explicitly stated. In particular, any feature indicated as preferred or advantageous can be combined with any other feature indicated as preferred or advantageous.

[0013] Unless otherwise specified, terms used in the context of this invention should be interpreted according to the following definitions.

[0014] Unless otherwise specified, all wt.% or weight % values ​​cited herein are weight percentages.

[0015] Unless otherwise specified, the terms “a,” “an,” and “the” as used herein include both singular and plural referents.

[0016] As used herein, the terms “comprising” and “comprises” are synonymous with “including,” “includes,” or “contains,” and are inclusive or unrestricted, not excluding any additional members, elements, or process steps not listed.

[0017] As used herein, the term "consisting essentially of" means that the listed components constitute the main part of the composition, for example, at least 80% by weight of the composition, at least 85% by weight of the composition, or at least 90% by weight of the composition.

[0018] As used herein, the term "consisting of" is limiting and excludes additional members, elements, or process steps not listed.

[0019] As used herein, the term "(meth)acrylic" means both "acrylic" and "methacrylic" and refers to a compound having one or more (meth)acryloyl groups.

[0020] As used herein, the term "(meth)acrylate" means both "acrylate" and "methacrylate" and refers to a compound having one or more (meth)acryloyloxy groups.

[0021] As used herein, the term "at least one" or "one or more" used to define a component refers to the type of component, not the absolute numerical value of the molecule. For example, "one or more monomers" means one type of monomer or a mixture of multiple different monomers.

[0022] As used herein, terms such as "about" and "around" with respect to numerical values refer to the numerical value ±10%, preferably ±5%. All numerical values in this specification should be interpreted as being modified by the term "about".

[0023] Unless otherwise specified, the description of numerical endpoints includes not only the recited endpoints but also all numerical values and fractions included within the range of the numerical values.

[0024] All references cited herein are hereby incorporated by reference in their entirety.

[0025] Unless otherwise defined, all terms used in the present invention, including technical and scientific terms, have the meaning commonly understood by those skilled in the art to which the present invention pertains.

[0026] The radiation-curable (meth)acrylic adhesive compositions will be described in detail below. The radiation-curable (meth)acrylic adhesive composition of the present invention, i) (Meth)acrylic polydiene resin; ii) Polyfunctional (meth)acrylic monomer components; iii) Monofunctional (meth)acrylic monomer components; and iv) Photoinitiator components It includes, or is essentially composed of, these.

[0027] Component i) The adhesive composition of the present invention may contain one or more (meth)acrylic polydiene resins as a first essential component. Here, (meth)acrylic polydiene resin means a resin having a polydiene as the main chain and one or more (meth)acryloyloxy groups grafted onto it.

[0028] Preferred polydiene skeletons are poly(C4-C8)dienes, such as polybutadiene, polypentadiene, polyisoprene, polyhexadiene, polyheptadiene, polyoctadiene, and their isomers. More preferably, the polydiene backbone does not originate from an accumulated diene. More preferably, the polydiene backbone originates from a diene having a double bond at its terminal. Furthermore, the polydiene backbone can be derived from one or more dienes. The polydiene backbone is preferably derived from one type of diene, and more preferably from polybutadiene.

[0029] The (meth)acrylic polydiene resin used herein can be selected from (meth)acrylic polybutadiene resin, (meth)acrylic polypentadiene resin, (meth)acrylic polyisoprene resin, (meth)acrylic polyhexadiene resin, (meth)acrylic polyheptadiene resin, (meth)acrylic polyoctadiene resin, and mixtures thereof. In a preferred embodiment, the (meth)acrylic polydiene resin used herein is a (meth)acrylic polybutadiene resin.

[0030] The bond between the polydiene skeleton and the (meth)acryloyloxy group is not particularly limited. In preferred embodiments, the bond is a urethane bond. That is, the (meth)acryloyloxy group is connected to the polydiene main chain via a urethane bond. Graft It is being done.

[0031] In a preferred embodiment, the (meth)acrylic polydiene resin useful in the present invention has at least two (meth)acryloyloxy groups, for example, 2 to 4 (meth)acryloyloxy groups on the polydiene main chain. Graft This is a resin. In a more preferred embodiment, the (meth)acrylic polydiene resin useful in the present invention has two (meth)acryloyloxy groups on the main chain of the polydiene. Graft This is a resin in which two (meth)acryloyloxy groups are attached to the two ends of the polydiene main chain. Graft can.

[0032] In a more preferred embodiment, the (meth)acrylic polydiene resin useful in the present invention is arranged in a lattice pattern on the polybutadiene main chain via urethane groups. Graft This is a (meth)acrylic polybutadiene resin having two (meth)acryloyloxy groups. For example, the two (meth)acryloyloxy groups can be grafted to the two ends of the polybutadiene main chain, respectively.

[0033] In preferred embodiments, the (meth)acrylic polydiene resin useful in the present invention has a viscosity of less than 24,000 cP at 60°C, preferably 10,000 to 23,000 cP at 60°C. The viscosity values ​​herein can be determined using any suitable viscosity measurement method conventionally used in the art.

[0034] Examples of commercially available (meth)acrylic polydiene resins that can be used in the present invention include Bomar 641D from Dymax, which has two acryloyloxy groups on the polybutadiene main chain via urethane groups. Graft It is a difunctional acylated polybutadiene.

[0035] In preferred embodiments, the adhesive composition does not contain (meth)acrylicated polyether resin and / or (meth)acrylicated urethane resin. In other words, the adhesive composition does not contain a resin having a polyether and / or polyurethane main chain on which (meth)acryloyloxy groups are grafted.

[0036] In the present invention, the (meth)acrylic polydiene resin can be contained in the adhesive composition in an amount of 10 to 65% by weight, preferably 30 to 55% by weight, and more preferably 40 to 50% by weight, based on the total weight of the adhesive composition.

[0037] Component ii) The adhesive composition of the present invention may contain one or more polyfunctional (meth)acrylic monomers as a second essential component.

[0038] A polyfunctional (meth)acrylic monomer refers to a monomer having more than one (meth)acryloyl group, for example, a monomer having two to six (meth)acryloyl groups. In other words, 2 to 6 functional (meth)acrylic monomers can preferably be used as polyfunctional (meth)acrylic monomers.

[0039] Conventionally, it was believed that adding a polyfunctional (meth)acrylic monomer component to a (meth)acrylic adhesive composition increased the degree of crosslinking, improving the chemical resistance of the adhesive, but also making the adhesive brittle. However, in the present invention, it was unexpectedly discovered that by combining a (meth)acrylicated polydiene resin with a polyfunctional (meth)acrylic monomer, it is possible to achieve both good chemical resistance at high temperatures and good mechanical properties, including Young's modulus, elongation, and tensile strength.

[0040] In the present invention, the type of polyfunctional (meth)acrylic monomer is not particularly limited, and conventionally used polyfunctional (meth)acrylic monomers can be used in the adhesive composition.

[0041] Examples of polyfunctional (meth)acrylic monomers include, but are not limited to, the following: difunctional (meth)acrylic monomers, e.g., 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, bisphenol A-ethylene glycol Gol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, di(a Cryloxyethyl isocyanurate, allylated cyclohexyl di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, adamantine di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, etc.; trifunctional monomers, e.g., trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate Examples include propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloyloxyethyl) isocyanurate, etc.; tetrafunctional monomers, such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, tetramethylolpropane tetra(meth)acrylate, etc.; pentahythritol penta(meth)acrylate, etc.; hexahythritol hexa(meth)acrylate, etc.

[0042] The polyfunctional (meth)acrylic monomer component may be included in the adhesive composition in an amount of 0.1 to 25% by weight, preferably 5 to 15% by weight, based on the total weight of the adhesive composition. If the content of the polyfunctional (meth)acrylic monomer component is less than 0.1 wt%, the desired chemical resistance may not be obtained, and if the content of the polyfunctional (meth)acrylic monomer component exceeds 25 wt%, the desired mechanical properties such as elongation may not be obtained.

[0043] ingredient iii) The adhesive composition of the present invention may contain one or more monofunctional (meth)acrylic monomers as a third essential component.

[0044] In this invention, a monofunctional (meth)acrylic monomer is used as a diluent monomer having a functional group that can be crosslinked with a (meth)acrylic polydiene resin, while simultaneously controlling the viscosity of the adhesive composition.

[0045] In the present invention, the type of monofunctional (meth)acrylic monomer is not particularly limited, and conventionally used monofunctional (meth)acrylic monomers can be used in adhesive compositions. Examples include monofunctional (meth)acrylic monomers without hydroxyl groups, monofunctional (meth)acrylic monomers having hydroxyl groups, or mixtures thereof.

[0046] Examples of monofunctional (meth)acrylic monomers that do not have a hydroxyl group include, but are not limited to, the following: acrylic acid, n-butyl (meth)acrylate, 2-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, pentyl (meth)acrylate, n-octyl (meth)acrylate Acrylate, isooctyl (meth)acrylate, 2-methylbutyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, isoamyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, 4-methyl-2-pentyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, allyl (meth)acrylate.

[0047] Examples of monofunctional (meth)acrylic monomers having a hydroxyl group include, but are not limited to, the following: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and hydroxyalkylene (having 2 to 4 carbon atoms) glycol (meth)acrylates such as 2-hydroxyethylene glycol (meth)acrylate and 2-hydroxypropylene glycol (meth)acrylate.

[0048] The amount of monofunctional (meth)acrylic monomer component may be adjusted according to practical requirements for the viscosity of the adhesive. In a preferred embodiment, the monofunctional (meth)acrylic monomer component may be contained in the adhesive composition in an amount of 1 to 40% by weight, preferably 7 to 39% by weight, and more preferably 15 to 38% by weight, based on the total weight of the adhesive composition.

[0049] Component iv) The photopolymerization initiator is a component for sufficiently curing the adhesive composition, and its type and species are not particularly limited. In this invention, generally known photopolymerization initiators can be used.

[0050] Examples of photoinitiators include, but are not limited to, 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-diethoxy-2-phenylacetophenone, 4-chloro Acetophenone, 4,4-dimethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-hydroxycyclophenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxyl-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4-diaminobenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, anthraquinone, 2-methyl Anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, diphenyl ketone benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, fluorene, Riphenylamine, carbazole, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, or ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, 1-hydroxycyclohexyl phenyl ketone, oxy-phenyl-acetate 2-[2-oxo-2-phenylacetoxy-ethoxy]-ethyl ester, oxy-phenyl-acetate 2-[2-hydroxy-ethoxy]-ethyl ester, 2-hydroxy-2-methyl-1-phenyl-1-propanone, phosphine oxide phenylbis(2,4,Examples include 6-trimethylbenzoyl, iodonium (4-methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate(1-), etc. The aforementioned photopolymerization initiators can be used alone or in combination.

[0051] In the present invention, the photoinitiator component may be contained in the adhesive composition in an amount of 0.1 to 10% by weight, preferably 0.3 to 5% by weight, and more preferably 0.5 to 4.5% by weight, based on the total weight of the adhesive composition. If the photoinitiator content is less than 0.1 wt%, the curing rate may become too slow. On the other hand, if the photoinitiator content exceeds 10 wt%, yellowing may occur or durability may decrease.

[0052] Other ingredients In addition to the above components i) to iv), the adhesive composition of the present invention may optionally contain other additives conventionally used in the art, such as organosilanes, antioxidants, corrosion inhibitors, leveling agents, surface lubricants, dyes, pigments, defoamers, fillers, and light stabilizers.

[0053] The adhesive composition of the present invention may optionally contain organosilanes to improve adhesive strength. Examples of organosilanes include, but are not limited to, the following: vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(amino Examples include ethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatetopropyltriethoxysilane, etc., which may be used individually or in any combination.

[0054] In a preferred embodiment, the organosilane may be included in an amount of 0 to 10% by weight, for example, 0.005 to 5% by weight, based on the total weight of the adhesive composition. If the coupling agent content exceeds 10 wt%, durability may decrease.

[0055] Examples of useful antioxidants include hindered phenol antioxidants, phosphite ester antioxidants, and thioether antioxidants.

[0056] Fillers can take various forms, including, for example, particles (spherical particles, beads, elongated particles), fibers, and combinations thereof. Examples of fillers include, but are not limited to, talc, clay, silica and its processed products, carbon black, and mica.

[0057] Useful pigments include inorganic pigments, organic pigments, reactive pigments, non-reactive pigments, and combinations thereof.

[0058] The (meth)acrylic adhesive composition of the present invention can be cured by light irradiation, for example, by an LED light source, electron beam, mercury arc light source, ultraviolet light, visible light, etc. In a preferred embodiment, the (meth)acrylic adhesive composition of the present invention does not contain an isocyano-containing compound.

[0059] Method for joining substrates The present invention provides a method for bonding substrates using the radiation-curable (meth)acrylic adhesive composition of the present invention. This method comprises applying the adhesive composition of the present invention to at least one of the substrates, then interlocking the substrates, and then exposing them to active radiation until the adhesive composition is cured. In one embodiment, at least one substrate may include a light-transmitting portion, or at least one substrate may be light-transmitting. In a further embodiment, at least one substrate may include a plastic or glass material that is transparent to ultraviolet or visible light.

[0060] The adhesive composition can be applied to the substrate using any suitable application method, including, for example, automatic fine-line dispensing, jet dispensing, slot die dispensing, roll dispensing, pattern dispensing, screen printing, spray dispensing, filament dispensing, air knife, trailing blade, brush application, dipping, doctor blade, and combinations thereof. The adhesive composition can be applied as a continuous or discontinuous coating, in single layers, multiple layers, or combinations thereof.

[0061] glued articles The present invention provides articles bonded with a cured product of the radiation-curable (meth)acrylic adhesive composition of the present invention.

[0062] The adhesive composition of the present invention is useful for a variety of electronic devices, including, for example, wearable electronic devices (e.g., watches, eyeglasses), handheld electronic devices (e.g., telephones (mobile phones and smartphones, etc.), cameras, tablets, e-readers, monitors (e.g., monitors used in hospitals, by medical professionals, athletes, and by individuals, etc.), clocks, calculators, mice, touchpads, and joysticks), computers (e.g., desktop computers and laptop computers), computer monitors, televisions, media players, electrical appliances (e.g., refrigerators, washing machines, dryers, ovens, microwave ovens), light bulbs (e.g., incandescent lamps, light-emitting diodes, fluorescent lamps, etc.), and protective transparent coatings for visible transparent or transparent components, glass housing structures, displays, or other optical components. [Examples]

[0063] Examples Next, the present invention will be described by the following examples. The following examples are intended to help those skilled in the art to better understand and implement the present invention. The scope of the present invention is not limited by the examples but is defined by the appended claims. Unless otherwise specified, all parts and percentages are based on weight.

[0064] Radiation-curable (meth)acrylic adhesive compositions (Examples 1-3 and Comparative Example 1) The adhesive composition was prepared by mixing the components listed in Table 1.

[0065] Chemical resistance test Bonds were created on soda glass with a 3mm x 25mm overlap using 125μm spacer beads. All of these were illuminated with a 375nm LED at 100mW / cm². 2 It was cured for 20 seconds, and then at 160°C for 90 minutes. Twenty bonds were created in each composition, five of which were tested for initial wrap shear strength. Each of these five bonds was then placed in an aqueous solution of isopropanol (IPA), an aqueous solution of ethanol, and oleic acid, respectively, at 65°C for 72 hours.

[0066] The lap shear strength was tested using a tensile testing machine at a tensile speed of 10 mm / min. The recorded average strengths are shown in Table 1.

[0067] Mechanical properties test Mechanical properties were tested using a 1 mm thick ASTM D638 Type IV dogbone cured in the same manner as the adhesive used for the chemical resistance test described above. Tensile strength, elongation, and Young's modulus were measured at a tensile speed of 100 mm / min. Average values ​​are shown in Table 1. Graphs showing the results for Examples 1-3 are shown in Figures 2-4, respectively.

[0068] [Table 1]

[0069] As can be seen from Table 1, the adhesive composition according to the present invention achieved both good chemical resistance at high temperatures and good mechanical properties including tensile strength, elongation, and Young's modulus. However, the adhesive composition of Comparative Example 1 (CE1), which contains urethane dimethacrylate instead of methacrylated polybutadiene resin, exhibited extremely low elongation and brittleness of the cured product.

[0070] Comparative Example 2 (CE2) The CE2 adhesive composition was prepared by mixing the components shown in Table 2.

[0071] Bonds were created on soda glass with a 3mm x 25mm overlap using 125μm spacer beads. All of these were cured with a 375nm LED at 100mW / cm2 for 20 seconds, followed by 90 minutes at 160°C.

[0072] Thirty-five bonds were formed using this composition, and five of them were tested for their initial lap shear strength. Each of the five bonds was immersed in IPA:aqueous solution, ethanol:aqueous solution, and oleic acid at room temperature (RT) for 72 hours, and each of the five bonds was immersed in IPA:aqueous solution, ethanol:aqueous solution, and oleic acid at 65°C for 90 hours. The lap shear strength was tested using a tensile testing machine at a tensile speed of 10 mm / min. The recorded average strengths are shown in Table 2.

[0073] Mechanical properties were tested according to ASTM D882-09 using a film thickness of 500 μm and a width of 6 mm. The film was cured in the same manner as the bonds described above, and tensile strength, elongation, and Young's modulus were measured using a tensile speed of 10 mm / min. The average values ​​are shown in Table 2.

[0074] [Table 2]

[0075] The cured product of adhesive composition CE2, which contains methacrylated polyether resin (methacrylated polytetrahydrofuran resin) instead of methacrylated polybutadiene resin, exhibits extremely low chemical resistance at high temperatures and relatively low tensile strength.

[0076] While several preferred embodiments have been described, many modifications and variations can be made to them in light of the above teachings. Therefore, it should be understood that the present invention can be carried out in ways other than those specifically described without departing from the scope of the appended claims. Preferred embodiments of the present invention include the following: [1] i) (meth)acrylicated polydiene resin; ii) Polyfunctional (meth)acrylic monomer components; iii) Monofunctional (meth)acrylic monomer components; and iv) Photoinitiator components A radiation-curable (meth)acrylic adhesive composition comprising, or essentially consisting of, the above. [2] (meth)acrylic polydiene resin is (meth)acrylic poly(C 4 ~C 8 The composition according to [1], wherein the composition is one or more resins selected from diene resins. [3] The composition according to [1] or [2], wherein the (meth)acrylic polydiene resin is selected from (meth)acrylic polybutadiene resin, (meth)acrylic polypentadiene resin, (meth)acrylic polyisoprene resin, (meth)acrylic polyhexadiene resin, (meth)acrylic polyheptadiene resin, (meth)acrylic polyoctadiene resin, and mixtures thereof, preferably (meth)acrylic polybutadiene resin. [4] The composition according to any one of [1] to [3], wherein the (meth)acrylic polydiene resin is a (meth)acrylic polydiene resin in which at least two (meth)acryloyloxy groups, for example, 2 to 4 (meth)acryloyloxy groups are arranged in a lattice. [5] The composition according to any one of [1] to [4], wherein the (meth)acrylic polydiene resin has a viscosity of less than 24,000 cP at 60°C, preferably 10,000 to 23,000 cP at 60°C. [6] The adhesive composition is the composition according to any one of [1] to [5], which does not contain (meth)acrylic polyether resin and / or (meth)acrylic urethane resin. [7] The composition according to any one of [1] to [6], wherein the (meth)acrylic polydiene resin is contained in the adhesive composition in an amount of 10 to 65% by weight, preferably 30 to 55% by weight, more preferably 40 to 50% by weight, based on the total weight of the adhesive composition. [8] The composition according to any one of [1] to [7], wherein the polyfunctional (meth)acrylic monomer is a 2- to 6-functional (meth)acrylic monomer. [9] Polyfunctional (meth)acrylic monomers are difunctional (meth)acrylic monomers, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, bisphenol A-ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate Acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, di(acrylooxyethyl) isocyanurate, allylated cyclohexyl Sil di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, adamantine di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate; trifunctional monomers, e.g., trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate A composition according to any one of [1] to [8], selected from (t) acrylates, tris(acryloxyethyl) isocyanurate; tetrafunctional monomers, e.g., pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, tetramethylolpropane tetra(meth)acrylate; pentahyfunctional monomers, e.g., dipentaerythritol penta(meth)acrylate; hexahyfunctional monomers, e.g., dipentaerythritol hexa(meth)acrylate; and mixtures thereof.

[10] The composition according to any one of [1] to [9], wherein the polyfunctional (meth)acrylic monomer component is contained in the adhesive composition in an amount of 0.1 to 25% by weight, preferably 5 to 15% by weight, based on the total weight of the adhesive composition.

[11] Monofunctional (meth)acrylic monomers include acrylic acid, n-butyl (meth)acrylate, 2-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, pentyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-methylbutyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, isoamyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, 4 A composition according to any one of [1] to [9], selected from hydroxyalkylene (having 2 to 4 carbon atoms) glycol (meth)acrylates such as -methyl-2-pentyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, allyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, and 2-hydroxypropylene glycol (meth)acrylate, and mixtures thereof.

[12] The composition according to any one of [1] to

[11] , wherein the monofunctional (meth)acrylic monomer component is contained in the adhesive composition in an amount of 1 to 40% by weight, preferably 7 to 39% by weight, more preferably 15 to 38% by weight, based on the total weight of the adhesive composition.

[13] The composition according to any one of [1] to

[12] , wherein the photoinitiator component is contained in the adhesive composition in an amount of 0.1 to 10% by weight, preferably 0.3 to 5% by weight, and more preferably 0.5 to 4.5% by weight, based on the total weight of the adhesive composition.

[14] A composition according to any one of [1] to

[13] , further comprising organosilane, antioxidant, corrosion inhibitor, leveling agent, surface lubricant, dye, pigment, defoamer, filler, light stabilizer, and combinations thereof.

[15] The adhesive composition is the composition described in any of [1] to

[14] , which does not contain an isocyano-containing compound.

[16] First substrate, A second substrate, and Cured adhesive between the first substrate and the second substrate Articles containing, Here, the cured adhesive includes or consists of a cured product obtained from any of the adhesive compositions described in [1] to

[15] . An article in which at least one substrate includes a light-transmitting portion, or at least one substrate is light-transmitting.

[17] The articles described in

[16] include wearable electronic devices, handheld electronic devices, eyeglasses, telephones, tablets, sound players, remote control devices, mice, watch bands, drug delivery pumps, or combinations thereof.

[18] A method for bonding two substrates, the method comprising: applying a substrate adhesive composition according to any one of [1] to

[15] to at least one of the substrates; laminating the two substrates; and then irradiating the adhesive composition with radiation, for example, an LED source, an electron beam, a mercury arc light source, UV light, or visible light, wherein at least one of the substrates includes a light-transmitting portion or at least one of the substrates is light-transmitting.

Claims

1. i) A (meth)acrylicated polydiene resin in which two (meth)acryloyloxy groups are grafted onto a polybutadiene main chain via urethane groups; ii) Polyfunctional (meth)acrylic monomer component: The polyfunctional (meth)acrylic monomer component is present in the adhesive composition in an amount of 0.1 to 25% by weight based on the total weight of the adhesive composition; iii) Monofunctional (meth)acrylic monomer components; and iv) Photoinitiator components A radiation-curable (meth)acrylic adhesive composition comprising or comprising the above.

2. (Meth)acrylicated polydiene resin is (meth)acrylicated poly(C ４ ~C ８ The composition according to claim 1, wherein the composition is one or more resins selected from diene resins.

3. The composition according to claim 1 or 2, wherein the (meth)acrylicated polydiene resin is selected from (meth)acrylicated polybutadiene resin, (meth)acrylicated polypentadiene resin, (meth)acrylicated polyisoprene resin, (meth)acrylicated polyhexadiene resin, (meth)acrylicated polyheptadiene resin, (meth)acrylicated polyoctadiene resin, and mixtures thereof.

4. The adhesive composition is the composition according to any one of claims 1 to 3, wherein the adhesive composition does not contain a (meth)acrylic polyether resin and / or a (meth)acrylic urethane resin.

5. The composition according to any one of claims 1 to 4, wherein the (meth)acrylic polydiene resin is contained in the adhesive composition in an amount of 10 to 65% by weight based on the total weight of the adhesive composition.

6. The composition according to any one of claims 1 to 5, wherein the polyfunctional (meth)acrylic monomer is a 2- to 6-functional (meth)acrylic monomer.

7. The composition according to any one of claims 1 to 6, wherein the polyfunctional (meth)acrylic monomer is selected from a difunctional (meth)acrylic monomer, a trifunctional monomer, a tetrafunctional monomer, a pentafunctional monomer, a hexafunctional monomer, and mixtures thereof.

8. The composition according to any one of claims 1 to 7, wherein the polyfunctional (meth)acrylic monomer component is contained in the adhesive composition in an amount of 5 to 15% by weight based on the total weight of the adhesive composition.

9. Monofunctional (meth)acrylic monomers include acrylic acid, n-butyl (meth)acrylate, 2-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, pentyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-methylbutyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, isoamyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, and 4 A composition according to any one of claims 1 to 7, selected from hydroxyalkylene (having 2 to 4 carbon atoms) glycol (meth)acrylates such as methyl-2-pentyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, allyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, and 2-hydroxypropylene glycol (meth)acrylate, and mixtures thereof.

10. The composition according to any one of claims 1 to 9, wherein the monofunctional (meth)acrylic monomer component is contained in the adhesive composition in an amount of 1 to 40% by weight based on the total weight of the adhesive composition.

11. The composition according to any one of claims 1 to 10, wherein the photoinitiator component is contained in the adhesive composition in an amount of 0.1 to 10% by weight based on the total weight of the adhesive composition.

12. A composition according to any one of claims 1 to 11, further comprising organosilane, antioxidant, corrosion inhibitor, leveling agent, surface lubricant, dye, pigment, defoamer, filler, light stabilizer, and combinations thereof.

13. The adhesive composition is the composition according to any one of claims 1 to 12, wherein the adhesive composition does not contain an isocyano-containing compound.

14. First substrate, A second substrate, and Cured adhesive between the first substrate and the second substrate Articles containing, Here, the cured adhesive consists of a cured product obtained from the adhesive composition described in any of claims 1 to 13. An article in which at least one substrate includes a light-transmitting portion, or at least one substrate is light-transmitting.

15. The article according to claim 14, wherein the article includes wearable electronic devices, handheld electronic devices, eyeglasses, telephones, tablets, sound players, remote control devices, mice, watch bands, drug delivery pumps, or combinations thereof.

16. A method for bonding two substrates, comprising: applying a substrate adhesive composition according to any one of claims 1 to 13 to at least one of the substrates; laminating the two substrates; and then irradiating the adhesive composition with radiation, wherein at least one of the substrates includes a light-transmitting portion or at least one of the substrates is light-transmitting.

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