Composition for bonding dissimilar materials and method for producing same

Abstract

The present invention relates to a composition for bonding dissimilar materials and a manufacturing method thereof, and more particularly to a composition for bonding dissimilar materials which contains a (meth)acrylic-modified polyurethane component including a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane, a (meth)acrylic monomer, an epoxy resin, an epoxy curing accelerator, a thermal polymerization initiator and a polymerization inhibitor in a specific weight ratio, and which can achieve high adhesive strength between dissimilar materials at room temperature and high temperatures and has excellent oil resistance, and a manufacturing method thereof.

Description

[Technical Field]

[0001] The present invention relates to a composition for bonding dissimilar materials and a method for producing the same. More specifically, the present invention relates to a composition for bonding dissimilar materials, which comprises a (meth)acrylic-modified polyurethane component including a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane, a (meth)acrylic monomer, an epoxy resin, an epoxy curing accelerator, a thermal polymerization initiator, and a polymerization inhibitor in a specific weight ratio, and which is capable of achieving high adhesive strength between dissimilar materials at room temperature and at high temperatures and has excellent oil resistance, and a method for producing the same. [Background technology]

[0002] Polyols and isocyanates, which are essential components of polyurethanes, are typically produced from petroleum-derived raw materials. However, due to various reasons in the polyurethane field, such as the accelerating depletion of petroleum resources, demands to reduce greenhouse gas emissions due to climate change, rising raw material prices, and the growing need for renewable raw materials, there is a demand for methods to replace some or all of the polyols and isocyanates produced from petroleum-based raw materials with environmentally friendly components.

[0003] Polyols can be produced from renewable biomass, such as natural vegetable oils, cellulose, and lignin, and bio-polyols derived from natural vegetable oils are already being produced on a commercial scale. The properties of the bio-polyols produced vary depending on the type of biomass used in their production. Generally, castor oil and palm oil are used to produce flexible and rigid polyurethanes and synthetic polyols, while soybean oil is used to produce polyols for flexible polyurethanes. However, bio-polyols currently produced from biomass have the disadvantage of high viscosity.

[0004] Isocyanates derived from natural vegetable oils are essentially aliphatic compounds, which have the disadvantage of being less reactive than petroleum-derived aromatic diisocyanates, so there has been little research into the production of diisocyanates from biomass.

[0005] Hydrogenated sugars (also called "sugar alcohols") are compounds obtained by adding hydrogen to the reducing end group of sugars. Generally, HOCH2(CHOH) n They have the formula CH2OH (where n is an integer between 2 and 5) and are classified according to the number of carbon atoms into tetritols, pentitols, hexitols, and heptitols (4, 5, 6, and 7 carbon atoms, respectively). Among them, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, and galactitol, with sorbitol and mannitol being particularly useful substances.

[0006] Anhydroalcohols are substances formed by removing one or more water molecules from hydrogenated sugars. Removal of one water molecule results in a tetraol, which has four hydroxyl groups per molecule, and removal of two water molecules results in a diol, which has two hydroxyl groups per molecule. Anhydroalcohols can be produced using starch-derived hexitol (see, for example, Patent Documents 1 and 2). Anhydroalcohols are environmentally friendly substances derived from renewable natural resources, and have long been of interest, leading to extensive research into production methods. Among these anhydroalcohols, isosorbide produced from sorbitol currently has the widest range of industrial applications.

[0007] Anhydroalcohols are used in a variety of fields, including the treatment of heart and vascular diseases, adhesives for patches, pharmaceuticals such as oral cleansers, solvents for cosmetic compositions, and emulsifiers in the food industry. They also increase the glass transition temperature of polymeric materials such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, improving the strength of such materials. Being environmentally friendly materials derived from natural products, they are extremely useful in the plastics industry, including bioplastics. Furthermore, anhydroalcohols are known to be useful as adhesives, environmentally friendly plasticizers, biodegradable polymers, and environmentally friendly solvents for water-soluble lacquers.

[0008] Thus, anhydroalcohols have attracted considerable interest due to their wide range of applications, and their level of industrial practical application is increasing.

[0009] Patent Document 3 discloses the production of a conductive adhesive for metal-metal interfaces from an acrylic-modified polyurethane and other acrylic monomers in the presence of a thermal polymerization initiator. However, the adhesive composition produced in this manner had insufficient oil resistance, and its adhesive properties needed to be further improved. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Korean Patent No. 10-1079518 [Patent Document 2] Korean Patent No. 10-2012-0066904 [Patent Document 3] Korea Patent No. 10-2017-0125328 Summary of the Invention [Problem to be solved by the invention]

[0011] The object of the present invention is to provide a composition for bonding dissimilar materials that can achieve high adhesive strength between dissimilar materials not only at room temperature but also at high temperatures by utilizing a derivative of an anhydrosugar alcohol, and that has excellent oil resistance, and a method for producing the same. [Means for solving the problem]

[0012] In order to achieve the above object, the present invention provides a composition for bonding dissimilar materials, comprising, relative to 100 parts by weight of the total amount of the composition, 25.5 to 84.5 parts by weight of a (meth)acrylic-modified polyurethane component containing a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane; 9.5 to 63.5 parts by weight of a (meth)acrylic monomer; 2.5 to 34.5 parts by weight of an epoxy resin; 0.06 to 2.95 parts by weight of an epoxy curing accelerator; 0.0006 to 2.95 parts by weight of a thermal polymerization initiator; and 0.006 to 0.65 parts by weight of a polymerization inhibitor.

[0013] In another aspect of the present invention, there is provided a method for producing a composition for bonding dissimilar materials, comprising the step of mixing, relative to 100 parts by weight of the total amount of the composition, 25.5 to 84.5 parts by weight of a (meth)acrylic-modified polyurethane component containing a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane; 9.5 to 63.5 parts by weight of a (meth)acrylic monomer; 2.5 to 34.5 parts by weight of an epoxy resin; 0.06 to 2.95 parts by weight of an epoxy curing accelerator; 0.0006 to 2.95 parts by weight of a thermal polymerization initiator; and 0.006 to 0.65 parts by weight of a polymerization inhibitor.

[0014] In yet another aspect, the present invention provides an article to which the above-mentioned composition for bonding dissimilar materials of the present invention is applied. [Effects of the Invention]

[0015] The composition for bonding dissimilar materials according to the present invention has the advantage that it achieves high adhesive strength between dissimilar materials and at the same time does not lose adhesive strength at high temperatures after curing. In addition, because it has excellent oil resistance, the adhesive material can exhibit excellent performance retention characteristics even in environments where it is exposed to oil. BEST MODE FOR CARRYING OUT THE INVENTION

[0016] The present invention will now be described in more detail.

[0017] As used herein, the term "(meth)acrylic" includes acrylic, methacrylic, or a combination thereof, and the term "(meth)acrylate" includes acrylate, methacrylate, or a combination thereof.

[0018] The composition for bonding dissimilar materials of the present invention contains, relative to 100 parts by weight of the total amount of the composition, 25.5 to 84.5 parts by weight of a (meth)acrylic-modified polyurethane component containing a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane; 9.5 to 63.5 parts by weight of a (meth)acrylic monomer; 2.5 to 34.5 parts by weight of an epoxy resin; 0.06 to 2.95 parts by weight of an epoxy curing accelerator; 0.0006 to 2.95 parts by weight of a thermal polymerization initiator; and 0.006 to 0.65 parts by weight of a polymerization inhibitor.

[0019] When the content of the (meth)acrylic-modified polyurethane component containing the hydrophilic (meth)acrylic-modified polyurethane and the lipophilic (meth)acrylic-modified polyurethane is less than 25.5 parts by weight, adhesion at room temperature and high temperature and oil resistance are both reduced. Conversely, when the content exceeds 84.5 parts by weight, high-temperature adhesion is reduced. In one embodiment, the content of the (meth)acrylic-modified polyurethane component containing the hydrophilic (meth)acrylic-modified polyurethane and the lipophilic (meth)acrylic-modified polyurethane may be 25.5 parts by weight or more, 26 parts by weight or more, 27 parts by weight or more, 28 parts by weight or more, 29 parts by weight or more, or 30 parts by weight or more, or may be 84.5 parts by weight or less, 84 parts by weight or less, 83 parts by weight or less, 82 parts by weight or less, 81 parts by weight or less, or 80 parts by weight or less, but is not limited thereto.

[0020] If the content of the (meth)acrylic monomer is less than 9.5 parts by weight, the adhesiveness and oil resistance at high temperatures will decrease, whereas if the content exceeds 63.5 parts by weight, the adhesiveness at room temperature and high temperatures will decrease. In one embodiment, the content of the (meth)acrylic monomer per 100 parts by weight of the composition may be 9.5 parts by weight or more, 10 parts by weight or more, 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, or 14 parts by weight or more, or may be 63.5 parts by weight or less, 63 parts by weight or less, 60 parts by weight or less, 58 parts by weight or less, 55 parts by weight or less, 53 parts by weight or less, or 50 parts by weight or less, but is not limited thereto.

[0021] If the content of the epoxy resin is less than 2.5 parts by weight, the high-temperature adhesiveness will decrease, whereas if the content exceeds 34.5 parts by weight, the adhesiveness at room temperature and high temperature and the oil resistance will all decrease. In one embodiment, the content of the epoxy resin in 100 parts by weight of the composition may be 2.5 parts by weight or more, 3 parts by weight or more, 3.5 parts by weight or more, 4 parts by weight or more, 4.5 parts by weight or more, or 5 parts by weight or more, or may be 34.5 parts by weight or less, 34 parts by weight or less, 33 parts by weight or less, 32 parts by weight or less, 31 parts by weight or less, 30 parts by weight or less, or 29 parts by weight or less, but is not limited thereto.

[0022] If the content of the epoxy curing accelerator is less than 0.06 parts by weight, the adhesion and oil resistance at room temperature and high temperature will decrease, whereas if the content exceeds 2.95 parts by weight, the adhesion at room temperature and high temperature will decrease. In one embodiment, the content of the epoxy curing accelerator may be at least 0.06 parts by weight, at least 0.1 parts by weight, at least 0.2 parts by weight, at least 0.3 parts by weight, at least 0.4 parts by weight, or at least 0.5 parts by weight, or may be at most 2.95 parts by weight, at most 2.5 parts by weight, at most 2 parts by weight, at most 1.5 parts by weight, or at most 1 part by weight, but is not limited thereto.

[0023] If the content of the thermal polymerization initiator is less than 0.0006 parts by weight per 100 parts by weight of the composition for bonding dissimilar materials of the present invention, curing does not occur even when heated, and initial peeling makes it difficult to bond dissimilar materials. Conversely, if the content exceeds 2.95 parts by weight, adhesion at room temperature and high temperatures is reduced. In one embodiment, the content of the thermal polymerization initiator per 100 parts by weight of the composition may be 0.0006 parts by weight or more, 0.001 parts by weight or more, 0.005 parts by weight or more, 0.01 parts by weight or more, 0.02 parts by weight or more, 0.03 parts by weight or more, or 0.04 parts by weight or more, or may be 2.95 parts by weight or less, 2.8 parts by weight or less, 2.5 parts by weight or less, 2.3 parts by weight or less, or 2 parts by weight or less, but is not limited thereto.

[0024] If the content of the polymerization inhibitor is less than 0.006 parts by weight per 100 parts by weight of the dissimilar material bonding composition of the present invention, the storage stability will be poor and hardening may occur within the composition even when stored at room temperature, while if the content exceeds 0.65 parts by weight, the adhesion and oil resistance at room temperature and high temperatures will all be reduced. In one embodiment, the content of the polymerization inhibitor per 100 parts by weight of the total composition may be 0.006 parts by weight or more, 0.007 parts by weight or more, 0.008 parts by weight or more, 0.009 parts by weight or more, or 0.01 parts by weight or more, or may be 0.65 parts by weight or less, 0.6 parts by weight or less, 0.55 parts by weight or less, or 0.5 parts by weight or less, but is not limited thereto.

[0025] Hereinafter, embodiments of the components contained in the composition for bonding dissimilar materials of the present invention will be described.

[0026] [(Meth)acrylic-modified polyurethane component] The (meth)acrylic-modified polyurethane component contained in the composition for bonding dissimilar materials of the present invention includes a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane.

[0027] In one embodiment, the hydrophilic (meth)acrylic-modified polyurethane can include polymerized units derived from an anhydrosugar alcohol-alkylene oxide adduct; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate.

[0028] In one embodiment, the lipophilic (meth)acrylic-modified polyurethane can include polymerized units derived from a lipophilic polyol; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate.

[0029] In one embodiment, the (meth)acrylic-modified polyurethane component can comprise 16 to 84 parts by weight of the hydrophilic (meth)acrylic-modified polyurethane and 16 to 84 parts by weight of the lipophilic (meth)acrylic-modified polyurethane, relative to 100 parts by weight of the total amount of the (meth)acrylic-modified polyurethane component. If the content of the hydrophilic (meth)acrylic-modified polyurethane in the (meth)acrylic-modified polyurethane component is too low (i.e., if the content of the lipophilic (meth)acrylic-modified polyurethane is too high), the composition for bonding dissimilar materials produced therefrom may exhibit low adhesive strength to metals. Conversely, if the content of the hydrophilic (meth)acrylic-modified polyurethane is too high (i.e., if the content of the lipophilic (meth)acrylic-modified polyurethane is too low), the composition for bonding dissimilar materials produced therefrom may exhibit low adhesive strength to organic materials.

[0030] More specifically, relative to 100 parts by weight of the total amount of the (meth)acrylic-modified polyurethane components, each of the hydrophilic and lipophilic (meth)acrylic-modified polyurethanes may be contained in an amount of 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, or 20 parts by weight or more, and each of the hydrophilic and lipophilic (meth)acrylic-modified polyurethanes may be contained in an amount of 84 parts by weight or less, 83 parts by weight or less, 82 parts by weight or less, 81 parts by weight or less, or 80 parts by weight or less, but is not limited thereto.

[0031] Anhydrosugar alcohol-alkylene oxide adduct In one embodiment, the anhydrosugar alcohol-alkylene oxide adduct (also referred to as "anhydrosugar alcohol-alkylene glycol") contained as a polymerization unit in the hydrophilic (meth)acrylic-modified polyurethane is an adduct obtained by reacting hydroxy groups at both ends or one end (preferably both ends) of an anhydrosugar alcohol with an alkylene oxide, and refers to a compound in which the hydrogen atoms of the hydroxy groups at both ends or one end (preferably both ends) of the anhydrosugar alcohol are substituted with hydroxyalkyl groups in a ring-opened form of the alkylene oxide.

[0032] In one embodiment, the alkylene oxide may be a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, and more specifically, may be ethylene oxide, propylene oxide, or a combination thereof.

[0033] The anhydrosugar alcohols can be produced by dehydration of hydrogenated sugars derived from natural products. Hydrogenated sugars (also called "sugar alcohols") are compounds obtained by adding hydrogen to the reducing end groups of sugars. Generally, HOCH2(CHOH) n They have the formula CH2OH (where n is an integer between 2 and 5) and are classified according to the number of carbon atoms into tetritols, pentitols, hexitols, and heptitols (4, 5, 6, and 7 carbon atoms, respectively). Among them, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, and galactitol, with sorbitol and mannitol being particularly useful substances.

[0034] The anhydrosugar alcohol may be a monoanhydrosugar alcohol, a dianhydrosugar alcohol or a mixture thereof, and although there is no particular limitation, a dianhydrosugar alcohol can be used.

[0035] Monoanhydrosugar alcohols are anhydrosugar alcohols produced by removing one water molecule from the interior of a hydrogenated sugar, and have a tetraol form with four hydroxy groups in the molecule. In the present invention, the type of monoanhydrosugar alcohol is not particularly limited, but may be preferably monoanhydrosugar hexitol, more specifically 1,4-anhydrohexitol, 3,6-anhydrohexitol, 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more thereof.

[0036] Dianhydrosugar alcohols are anhydrosugar alcohols produced by removing two water molecules from hydrogenated sugars. They are diols with two hydroxyl groups per molecule and can be produced using starch-derived hexitols. Dianhydrosugar alcohols have long attracted attention as environmentally friendly substances obtained from renewable natural resources, and research into their production methods is ongoing. Among these dianhydrosugar alcohols, isosorbide produced from sorbitol currently has the widest range of industrial applications.

[0037] In the present invention, the type of the dianhydrosugar alcohol is not particularly limited, but is preferably a dianhydrohexitol, more specifically, a 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

[0038] In one embodiment, the anhydrosugar alcohol-alkylene oxide adduct may be a compound represented by the following formula (1) or a mixture thereof.

[0039] [ka] (In the formula, R 1 and R 2each independently represents a linear alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms, m and n each independently represent an integer of 0 to 15; m+n represents an integer of 1 to 30. More preferably, in the above formula 1, R 1 and R 2 each independently represents an ethylene group, a propylene group, or an isopropylene group, and preferably R 1 and R 2 are identical, m and n each independently represent an integer of 0 to 14, Here, m+n is an integer of 1 or more, 2 or more, or 3 or more, and is an integer of 25 or less, 20 or less, 15 or less, or 12 or less, for example, an integer of 1 to 25, preferably an integer of 2 to 20, more preferably an integer of 3 to 15.

[0040] In one embodiment, the anhydrosugar alcohol-alkylene oxide adduct may be an anhydrosugar alcohol-propylene oxide adduct represented by the following formula (1-1), an anhydrosugar alcohol-ethylene oxide adduct represented by the following formula (1-2), or a mixture thereof.

[0041] [ka] (In the formula, a and b each independently represent an integer of 0 to 15, a+b represent integers between 1 and 30, More preferably, a and b each independently represent an integer of 0 to 14, Here, a+b is an integer of 1 or more, 2 or more, or 3 or more, and is an integer of 25 or less, 20 or less, 15 or less, or 12 or less, for example, an integer of 1 to 25, preferably an integer of 2 to 20, more preferably an integer of 3 to 15.

[0042] [ka] (In the formula, c and d each independently represent an integer of 0 to 15, c+d represent an integer from 1 to 30, More preferably, c and d each independently represent an integer of 0 to 14, Here, c+d is an integer of 1 or more, 2 or more, or 3 or more, and is an integer of 25 or less, 20 or less, 15 or less, or 12 or less, for example, an integer of 1 to 25, preferably an integer of 2 to 20, more preferably an integer of 3 to 15.

[0043] In one embodiment, the anhydrosugar alcohol-alkylene oxide adduct may be produced by a production method including: (1) a step of treating an anhydrosugar alcohol with an acid component; and (2) a step of performing an addition reaction between the anhydrosugar alcohol treated with the acid component obtained in step (1) and an alkylene oxide.

[0044] More specifically, the anhydrosugar alcohol-alkylene oxide adduct may be produced by a production method including: (1) a step of treating an anhydrosugar alcohol with an acid component; (2) a step of performing an addition reaction between the anhydrosugar alcohol treated with the acid component obtained in step (1) and an alkylene oxide; and (3) a step of performing an addition reaction between the product obtained in step (2) and an alkylene oxide in the presence of a base catalyst.

[0045] The acid component is not particularly limited and may be selected from the group consisting of phosphoric acid, sulfuric acid, acetic acid, formic acid, heteropolyacids, and mixtures thereof. In one embodiment, the heteropolyacid may be phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, or the like. Other useful acid components include commercially available acid components such as Amberlyst 15 (manufactured by Dow Chemical Company).

[0046] In one embodiment, the acid treatment can be carried out by using 0.1 to 10 moles, preferably 0.1 to 8 moles, and more preferably 0.1 to 5 moles of an acid component per mole of anhydrosugar alcohol, raising the temperature (for example, 80°C to 200°C or 90°C to 180°C) under a nitrogen atmosphere, and then reducing the pressure under vacuum to remove moisture from the reactor, but the method is not limited to this.

[0047] The acid component used in the acid treatment is used to promote ring-opening of alkylene oxide in the alkylene oxide addition reaction described below.

[0048] Generally, the addition reaction of alkylene oxide to alcohol proceeds under base catalysis. However, in the case of anhydrosugar alcohols, due to their structural characteristics, the rate of alkylene oxide addition competes with the rate of base-catalyzed ring-opening and decomposition of the anhydrosugar alcohol ring structure. Therefore, not only the anhydrosugar alcohol itself but also its decomposition products react with alkylene oxide, and the reaction products of the base-catalyzed anhydrosugar alcohol decomposition products and alkylene oxide may act as a factor in reducing product quality and storage stability. In contrast, if anhydrosugar alcohols are treated with an acid component and then subjected to an addition reaction with alkylene oxide, the acid component promotes ring-opening of the alkylene oxide, thereby easily producing an anhydrosugar alcohol-alkylene oxide adduct by the addition reaction of anhydrosugar alcohols with alkylene oxide without producing base-catalyzed decomposition products of the anhydrosugar alcohol. Therefore, the conventional problems can be solved by the addition reaction of acid-treated anhydrosugar alcohols with alkylene oxide.

[0049] In one embodiment, the addition reaction between the anhydrosugar alcohol treated with the acid component and the alkylene oxide can be carried out by slowly supplying the alkylene oxide to the anhydrosugar alcohol treated with the acid component at a high temperature (e.g., 100°C to 180°C or 120°C to 160°C) over a period of, for example, 1 to 8 hours or 2 to 4 hours, but is not limited thereto. The reaction molar ratio of alkylene oxide to 1 mole of anhydrosugar alcohol is, for example, 1 mole or more or 2 moles or more, and 30 moles or less, 20 moles or less, 15 moles or less, or 12 moles or less, and may be, for example, 1 mole to 30 moles, preferably 2 to 20 moles, but is not limited thereto.

[0050] In one embodiment, the further addition reaction of the product obtained by the alkylene oxide addition reaction with additional alkylene oxide can be carried out, for example, in a high-pressure reactor capable of being pressurized (e.g., pressurized to 3 MPa or more) in the presence of a base catalyst (e.g., an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an alkaline earth metal hydroxide such as calcium hydroxide) at a high temperature (e.g., 100°C to 180°C or 120°C to 160°C) for, for example, 1 hour to 8 hours or 2 hours to 4 hours, but is not limited thereto. The reaction molar ratio of alkylene oxide to 1 mole of anhydrosugar alcohol is, for example, 1 mole or more, 2 moles or more, or 3 moles or more, and 30 moles or less, 20 moles or less, 15 moles or less, or 12 moles or less, and may be, for example, 1 mole to 30 moles, preferably 2 to 20 moles, and more preferably 3 to 15 moles, but is not limited thereto. Before adding the base catalyst, the acid component used in the treatment can be removed by filtration.

[0051] The product obtained by the addition reaction of an acid-treated anhydrosugar alcohol with an alkylene oxide (i.e., a compound in which an alkylene oxide is added to an anhydrosugar alcohol) has a very stable structure, so the ring structure of the anhydrosugar alcohol does not easily open or decompose at high temperatures, even in the presence of a base catalyst. This is therefore very advantageous for the further addition reaction of the alkylene oxide. If an acid catalyst is continued to be used during the further addition reaction of the alkylene oxide, the acid catalyst helps to promote the ring opening of the alkylene oxide, but the reaction rate decreases as the number of moles of alkylene oxide added increases. In other words, the addition rate of the alkylene oxide competes with the ring opening rate of the alkylene oxide itself, and at this time, the addition rate of the alkylene oxide slows, leading to self-condensation reactions between the ring-opened alkylene oxides and the formation of by-products, resulting in quality deterioration. Therefore, the further addition reaction of the alkylene oxide is carried out under a base catalyst.

[0052] An additional step may then be carried out to remove the metal ions released from the spent base catalyst, for which a metal ion adsorbent such as Ambosol MP20 (magnesium silicate component) can be used.

[0053] Lipophilic polyols In one embodiment, the lipophilic polyol contained as a polymerized unit in the lipophilic (meth)acrylic-modified polyurethane is a polyol having low surface energy characteristics, and specifically may be selected from, but is not limited to, polytetrahydrofuran, polypropylene glycol, polydimethylsiloxane (PDMS) polyol, or a combination thereof.

[0054] In one embodiment, the number average molecular weight (Mn) of the lipophilic polyol is not particularly limited, but may be specifically 200 to 3,000 g / mol, more specifically 500 to 2,500 g / mol, even more specifically 700 to 2,300 g / mol, and even more specifically 1,000 to 2,000 g / mol. If the number average molecular weight of the lipophilic polyol is too low, the shear strength of a dissimilar material bonded specimen to which a dissimilar material bonding composition containing a (meth)acrylic-modified polyurethane component produced therefrom is applied may be low, resulting in poor adhesion. Conversely, if the number average molecular weight of the lipophilic polyol is too high, the oil resistance of a dissimilar material bonded specimen to which a dissimilar material bonding composition containing a (meth)acrylic-modified polyurethane component produced therefrom is applied may be low.

[0055] Polyisocyanate In one embodiment, the polyisocyanate contained as a polymerized unit in the hydrophilic and lipophilic (meth)acrylic-modified polyurethane is, for example, an aromatic polyisocyanate such as methylene diphenyl diisocyanate (MDI) (e.g., 2,4- or 4,4′-methylene diphenyl diisocyanate), xylene diisocyanate (XDI), m- or p-tetramethyl xylene diisocyanate (TMXDI), toluene diisocyanate (TDI), di- or tetra-alkyldiphenylmethane diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate (TODI), phenylene diisocyanate (e.g., 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate), naphthalene diisocyanate (NDI), or 4,4′-dibenzyl diisocyanate. aliphatic polyisocyanates such as hydrogenated MDI (H12MDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,12-diisocyanatododecane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, isophorone diisocyanate (IPDI), tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate (HDI) (e.g., 1,6-hexamethylene diisocyanate), dimer fatty acid diisocyanates, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate (e.g., cyclohexane-1,4-diisocyanate), or ethylene diisocyanate; or combinations thereof.

[0056] In another embodiment, the polyisocyanate is selected from the group consisting of methylene diphenyl diisocyanate (MDI), ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate (HMDI). ), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, toluene diisocyanate, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (2,4- / 2,6-isomer ratio = 80 / 20), diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polydiphenylmethane diisocyanate (PMDI), naphthalene-1,5-diisocyanate, or a combination thereof, but are not limited thereto.

[0057] More specifically, the polyisocyanate may be methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.

[0058] Hydroxyalkyl (meth)acrylate In one embodiment, the hydroxyalkyl (meth)acrylate contained as a polymerized unit in the hydrophilic and lipophilic (meth)acrylic-modified polyurethane may be, for example, a linear or branched alkyl acrylate having a hydroxy group, a linear or branched alkyl methacrylate having a hydroxy group, or a combination thereof, and more specifically, a hydroxy-C 1-8 Alkyl (meth)acrylate, i.e., linear C having a hydroxy group 1-8Alkyl acrylate, branched C with hydroxyl group 3-8 Alkyl acrylate, linear C with hydroxyl group 1-8 Alkyl methacrylate, branched C with hydroxyl groups 3-8 The alkyl methacrylate may be an alkyl methacrylate or a combination thereof, and more specifically, the alkyl methacrylate may be, but is not limited to, methyl hydroxyacrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypentyl acrylate, hydroxypentyl methacrylate, 2-hydroxyethylhexyl acrylate, 2-hydroxyethylhexyl methacrylate, 2-hydroxyethylbutyl acrylate, 2-hydroxyethylbutyl methacrylate, hydroxyoctyl acrylate, hydroxyoctyl methacrylate, or a combination thereof.

[0059] More specifically, the hydroxyalkyl (meth)acrylate may be 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, or a combination thereof.

[0060] Hydrophilic (meth)acrylic modified polyurethane In one embodiment, the hydrophilic (meth)acrylic-modified polyurethane can be represented by the following formula (2):

[0061] [ka] [wherein each R1 is independently an alkylene group, specifically a C2-C8 linear or C3-C8 branched alkylene group, more specifically a C2-C6 linear or C3-C6 branched alkylene group; R2 each independently represents an alkylene group, a cycloalkylene group, or an arylene group, specifically a C2-C20 linear or C3-C20 branched alkylene group, a C3-C20 cycloalkylene group, or a C6-C20 arylene group; R3 is independently an alkylene group, specifically a C1-C8 linear or C3-C8 branched alkylene group, more specifically a C2-C6 linear or C3-C6 branched alkylene group; R4 is independently a hydrogen atom or an alkyl group, specifically a hydrogen atom or a C1-C4 linear or C3-C4 branched alkyl group; M is a divalent organic group derived from an anhydrosugar alcohol, more specifically a divalent organic group derived from isosorbide, isomannide, or isoidide, more specifically selected from the following formulae:

[0062] [ka] m and n each independently represent an integer of 0 to 15; m+n represents an integer of 1 to 30, specifically an integer of 1 to 25, more specifically an integer of 1 to 20, even more specifically an integer of 3 to 15, and even more specifically an integer of 5 to 15.]

[0063] More specifically, the hydrophilic (meth)acrylic-modified polyurethane can be represented by any of the following formulas, but is not limited thereto:

[0064] [ka] (In the formula, m, n, and m+n are each independently defined as in formula (2) above.)

[0065] The hydrophilic (meth)acrylic-modified polyurethane can be obtained by reacting an anhydrosugar alcohol-alkylene oxide adduct with polyisocyanate, and then reacting the adduct with a hydroxyalkyl (meth)acrylate.

[0066] In one embodiment, the hydrophilic (meth)acrylic-modified polyurethane can be produced by a method comprising: (a) reacting an anhydrosugar alcohol-alkylene oxide adduct with a polyisocyanate to produce an intermediate having a terminal isocyanate group; and (b) reacting the intermediate obtained in step (a) with a hydroxyalkyl (meth)acrylate.

[0067] According to one embodiment, a hydrophilic (meth)acrylic-modified polyurethane can be prepared by reacting two equivalents of a diisocyanate with one equivalent of an anhydrosugar alcohol (e.g., isosorbide (ISB))-alkylene oxide adduct to produce an intermediate having a terminal isocyanate group, and then reacting the terminal isocyanate group of the intermediate with two equivalents of a hydroxyalkyl (meth)acrylate (e.g., 2-hydroxyethyl methacrylate).

[0068] According to one embodiment, the reaction of the anhydrosugar alcohol-alkylene oxide adduct with the polyisocyanate can be carried out, optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)), at room temperature or at an elevated temperature (e.g., 50 to 100°C, preferably 50 to 70°C) for an appropriate time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours).

[0069] According to one embodiment, the reaction of the reaction product of the anhydrosugar alcohol-alkylene oxide adduct and polyisocyanate (i.e., the intermediate obtained in the above step (a)) with the hydroxyalkyl (meth)acrylate can be carried out, optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)), at a high temperature (e.g., 50 to 100°C, preferably 50 to 70°C) for an appropriate time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours).

[0070] Lipophilic (meth)acrylic modified polyurethane In one embodiment, the lipophilic (meth)acrylic-modified polyurethane may be represented by the following formula (3): [ka] [In the formula, each R1 independently represents an alkylene group, a cycloalkylene group, or an arylene group, Each R2 is independently an alkylene group; Each R3 is independently a hydrogen atom or an alkyl group, L is a divalent organic group derived from a lipophilic polyol, The lipophilic polyol has a number average molecular weight of 200 to 3,000 g / mol, More specifically, R1 is independently a C2-C20 linear or C3-C20 branched alkylene group, a C3-C20 cycloalkylene group, or a C6-C20 arylene group; R2 is independently a C1-C8 linear or C3-C8 branched alkylene group; R3 is independently a hydrogen atom or a C1-C4 linear or C3-C4 branched alkyl group; L is a divalent organic group derived from a lipophilic polyol selected from polytetrahydrofuran, polypropylene glycol, polydimethylsiloxane (PDMS) polyol, or a combination thereof; The number average molecular weight of the lipophilic polyol is 500 to 2,500 g / mol.]

[0071] The lipophilic (meth)acrylic-modified polyurethane can be obtained by reacting a lipophilic polyol with a polyisocyanate and then with a hydroxyalkyl (meth)acrylate.

[0072] More specifically, the lipophilic (meth)acrylic-modified polyurethane can be produced by a method comprising: (c) a step of reacting a lipophilic polyol with a polyisocyanate to produce an intermediate having a terminal isocyanate group; and (d) a step of reacting the intermediate obtained in the step (c) with a hydroxyalkyl (meth)acrylate.

[0073] According to one embodiment, the lipophilic (meth)acrylic-modified polyurethane can be prepared by reacting two equivalents of a diisocyanate with one equivalent of a lipophilic polyol (e.g., polytetrahydrofuran, polypropylene glycol, or polydimethylsiloxane diol having a number average molecular weight of 200 to 3,000 g / mol) to produce an intermediate having terminal isocyanate groups, and then reacting the terminal isocyanate groups of the intermediate with two equivalents of a hydroxyalkyl (meth)acrylate (e.g., 2-hydroxyethyl methacrylate).

[0074] According to one embodiment, the reaction between the lipophilic polyol and the polyisocyanate can be carried out, optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)), at room temperature or at an elevated temperature (e.g., 50 to 100°C, preferably 50 to 70°C) for an appropriate time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours).

[0075] According to one embodiment, the reaction of the reaction product of the lipophilic polyol and polyisocyanate (i.e., the intermediate obtained in step (c)) with the hydroxyalkyl (meth)acrylate can be carried out, optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)), at an elevated temperature (e.g., 50 to 100°C, preferably 50 to 70°C) for an appropriate time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours).

[0076] (Meth)acrylic modified polyurethane component manufacturing method In one embodiment, the (meth)acrylic-modified polyurethane component can be produced by a method (first production method) comprising: (1) a step of reacting a polyol component containing an anhydrosugar alcohol-alkylene oxide adduct and a lipophilic polyol with a polyisocyanate to produce an intermediate having a terminal isocyanate group; and (2) a step of reacting the intermediate obtained in the step (1) with a hydroxyalkyl (meth)acrylate.

[0077] In another embodiment, the (meth)acrylic-modified polyurethane component can be produced by a method (second production method) comprising the step of mixing a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane. More specifically, the (meth)acrylic-modified polyurethane component can be produced by a method comprising the step of mixing (i) a hydrophilic (meth)acrylic-modified polyurethane comprising polymerization units derived from an anhydrosugar alcohol-alkylene oxide adduct; polymerization units derived from a polyisocyanate; and polymerization units derived from a hydroxyalkyl (meth)acrylate; and (ii) a lipophilic (meth)acrylic-modified polyurethane comprising polymerization units derived from a lipophilic polyol; polymerization units derived from a polyisocyanate; and polymerization units derived from a hydroxyalkyl (meth)acrylate.

[0078] In the first and second production methods of the (meth)acrylic-modified polyurethane component, the anhydrosugar alcohol-alkylene oxide adduct, lipophilic polyol, polyisocyanate, and hydroxyalkyl (meth)acrylate are the same as those described above.

[0079] According to one embodiment, in the first production method of the (meth)acrylic-modified polyurethane component, the polyol component may contain 16 to 84 parts by weight of an anhydrosugar alcohol-alkylene oxide adduct and 16 to 84 parts by weight of a lipophilic polyol, relative to 100 parts by weight of the total amount of the polyol component. More specifically, relative to 100 parts by weight of the total amount of the polyol component, the anhydrosugar alcohol-alkylene oxide adduct and the lipophilic polyol may each be contained in an amount of 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, or 20 parts by weight or more. Furthermore, the anhydrosugar alcohol-alkylene oxide adduct and the lipophilic polyol may each be contained in an amount of 84 parts by weight or less, 83 parts by weight or less, 82 parts by weight or less, 81 parts by weight or less, or 80 parts by weight or less, but are not limited thereto.

[0080] According to one embodiment, in the first production method of the (meth)acrylic-modified polyurethane component, the reaction of the polyol component with the polyisocyanate in step (1) can be carried out optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)) at room temperature or at an elevated temperature (e.g., 50 to 100°C, preferably 50 to 70°C) for an appropriate time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours). The reaction of the reaction product of the polyol component with the polyisocyanate (i.e., the intermediate obtained in step (1)) with the hydroxyalkyl (meth)acrylate in step (2) can be carried out optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)) at an elevated temperature (e.g., 50 to 100°C, preferably 50 to 70°C) for an appropriate time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours).

[0081] According to one embodiment, in the second production method of the (meth)acrylic-modified polyurethane component, 16 to 84 parts by weight of (i) hydrophilic (meth)acrylic-modified polyurethane and 16 to 84 parts by weight of (ii) lipophilic (meth)acrylic-modified polyurethane may be mixed with respect to 100 parts by weight of the total amount of the (meth)acrylic-modified polyurethane component to be produced. More specifically, each of the (i) hydrophilic and (ii) lipophilic (meth)acrylic-modified polyurethanes may be mixed in an amount of 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, or 20 parts by weight or more. Each of the hydrophilic and lipophilic (meth)acrylic-modified polyurethanes may be mixed in an amount of 84 parts by weight or less, 83 parts by weight or less, 82 parts by weight or less, 81 parts by weight or less, or 80 parts by weight or less, but is not limited thereto.

[0082] In the second method for producing the (meth)acrylic-modified polyurethane component, the methods for producing the (i) hydrophilic and (ii) lipophilic (meth)acrylic-modified polyurethanes to be mixed are the same as those explained above.

[0083] [(Meth)acrylic monomer] The (meth)acrylic monomer contained in the composition for bonding dissimilar materials of the present invention adjusts the viscosity of the composition for bonding dissimilar materials, improves workability such as the ease of application to a bonding substrate, increases the thermal curing rate of the composition for bonding dissimilar materials, and improves the strength of the cured product, thereby improving adhesion.

[0084] In one embodiment, the (meth)acrylic monomer contained in the composition for bonding dissimilar materials of the present invention may be one or more monomers having 1 to 4 (meth)acrylic groups in the molecule.

[0085] The (meth)acrylic monomer may be a monomer having one (meth)acrylic group, such as (meth)acrylic acid, lauryl (meth)acrylate, stearyl (meth)acrylate, ethyl carbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, methyl ... Acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethyl glycol (meth)acrylate, nonylphenoxyethyl (meth)acrylate, nonylphenoxytetraethyl glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, butoxyethyl (meth)acrylate, butoxytriethylene glycol (meth)acrylate, 2-ethylhexyl polyethylene glycol (meth)acrylate, nonylphenyl polypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycerol (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, epichlorohydrin (hereinafter abbreviated as ECH)-modified butyl (meth)acrylate, E Examples of the methacrylate include, but are not limited to, CH-modified phenoxy (meth)acrylate, ethylene oxide (hereinafter abbreviated as EO)-modified phthalic acid (meth)acrylate, EO-modified succinic acid (meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, and combinations thereof.

[0086] Furthermore, the (meth)acrylic monomer may be a monomer having two or more (for example, 2 to 4) (meth)acrylic groups in the molecule, such as 1,6-hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), tripropylene glycol diacrylate (TPGDA), bisphenol A [EO] 4-30 diacrylate (BPA [EO] 4-30DA, EO is an ethylene oxide unit), trimethylolpropane triacrylate (TMPTA), trimethylol Examples of suitable acrylates include, but are not limited to, propane[EO]3-15 triacrylate (TMP[EO]3-15TA, where EO is an ethylene oxide unit), pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PETTA), ditrimethylolpropane tetraacrylate (DTMPTTA), dipentaerythritol pentaacrylate (DPPA), dipentaerythritol hexaacrylate (DPHA), or combinations thereof.

[0087] [Epoxy resin] The epoxy resin contained in the dissimilar material bonding composition of the present invention is used to increase the strength of the cured product of the dissimilar material bonding composition and improve the adhesiveness.

[0088] In one embodiment, the epoxy resin contained in the dissimilar material bonding composition of the present invention may be an epoxy resin having two or more epoxy groups in the molecule. The epoxy resin may be used alone or in combination of two or more.

[0089] Examples of the epoxy resin having two or more epoxy groups include, but are not limited to, bisphenol-based epoxy resins, phenol novolac-based epoxy resins, o-cresol novolac-based epoxy resins, multifunctional epoxy resins, amine-based epoxy resins, heterocycle-containing epoxy resins, substituted epoxy resins, naphthol-based epoxy resins, and combinations thereof.

[0090] [Epoxy curing accelerator] The epoxy curing accelerator contained in the dissimilar material bonding composition of the present invention is used to increase the curing rate of the epoxy resin.

[0091] In one embodiment, the epoxy curing accelerator contained in the composition for bonding dissimilar materials of the present invention is, for example, a substituted imidazole such as 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethylimidazole, imidazoline such as 2-phenylimidazoline, tertiary amine such as N,N-dimethylbenzylamine, 2,4,6-tris(dimethylaminomethyl)phenol (DMP30), bisphenol A, bisphenol F, nonylphenol, p-tert-butylphenol, novolac-type phenolic resin, salicylic acid, p-toluenesulfonic acid, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]Undec-7-ene (DBU), S-triazine (LUPRAGEN N600), bis(2-dimethylaminoethyl) ether (LUPRAGEN N206), pentamethyldiethylenetriamine (LUPRAGEN N301), trimethylaminoethylethanolamine (LUPRAGEN N400), tetramethyl-1,6-hexanediamine (LUPRAGEN N500), aminoethyl morpholine, aminopropyl morpholine, aminoethyl ethylene urea, ketimines such as Epi-Kure 3502 (reaction product of ethylenediamine and methyl isobutyl ketone), urons such as 3-(4-chlorophenyl)-1,1-dimethylurea (monuron), 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron), 3-phenyl-1,1-dimethylurea (phenuron) and 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea (chlorotoluron), tolyl-2,4-bis-N,N-dimethylcarbamide (AMICURE UR2T), dicyandiamide (DICY), Mannich bases or secondary amines, such as dialkylamines, e.g., di(2-ethylhexyl)amine, dibutylamine, dipropylamine, ditridecylamine, N,N'-diisopropylisophoronediamine (JEFFLINK® XTJ-584), N,N'-diisobutyl-4,4'-diaminodicyclohexylmethane (CLEARLINK 1000), N-(hydroxyethyl)aniline, and di(2-methoxyethyl)amine, or combinations thereof.

[0092] [Thermal polymerization initiator] The thermal polymerization initiator contained in the composition for bonding dissimilar materials of the present invention is used to initiate polymerization of the (meth)acrylic monomer and the (meth)acrylic-modified polyurethane component and to promote curing.

[0093] In one embodiment, the thermal polymerization initiator contained in the composition for bonding dissimilar materials of the present invention may be, for example, a compound represented by the following formula (4-1), a compound represented by the following formula (4-2), or a mixture thereof, but is not limited thereto.

[0094] [ka] wherein R and R' are each independently a C2-C8 linear or C3-C8 branched alkyl group; a C3-C20 cycloalkyl group; a C6-C20 aryl group; or a C2-C8 linear or C3-C8 branched methoxy-alkyl group; X is -CN or -CO2R'' (wherein R'' is a C2-C8 linear or C3-C8 branched alkyl group; a C3-C20 cycloalkyl group; or a C6-C20 aryl group).

[0095] [ka] (In the formula, each R is independently a C2-C8 linear or C3-C8 branched alkyl group; a C3-C20 cycloalkyl group; or a C6-C20 aryl group.)

[0096] [Polymerization inhibitor] The polymerization inhibitor contained in the composition for bonding dissimilar materials of the present invention is used to suppress the curing reaction that occurs naturally within the composition at room temperature while the composition for bonding dissimilar materials is stored and not in use, thereby improving the storage stability of the composition before use.

[0097] In one embodiment, the polymerization inhibitor contained in the dissimilar material bonding composition of the present invention includes, but is not limited to, those selected from hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), hydroquinone monoethyl ether (EEHQ), or mixtures thereof.

[0098] In addition to the components described above, the dissimilar material bonding composition of the present invention may further contain one or more additive components that may be included in conventional bonding compositions.

[0099] [Method for producing a composition for bonding dissimilar materials and an article to which the composition is applied] In another aspect, the present invention provides a method for producing a composition for bonding dissimilar materials, the method comprising the step of mixing, relative to 100 parts by weight of the total amount of the composition, 25.5 to 84.5 parts by weight of a (meth)acrylic-modified polyurethane component containing a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane; 9.5 to 63.5 parts by weight of a (meth)acrylic monomer; 2.5 to 34.5 parts by weight of an epoxy resin; 0.06 to 2.95 parts by weight of an epoxy curing accelerator; 0.0006 to 2.95 parts by weight of a thermal polymerization initiator; and 0.006 to 0.65 parts by weight of a polymerization inhibitor.

[0100] In the method for producing the dissimilar materials bonding composition, the (meth)acrylic-modified polyurethane component, the (meth)acrylic monomer, the epoxy resin, the epoxy curing accelerator, the thermal polymerization initiator, and the polymerization inhibitor are the same as those described above.

[0101] In one embodiment, the mixing of the above components (i.e., the (meth)acrylic-modified polyurethane component, the (meth)acrylic monomer, the epoxy resin, the epoxy curing accelerator, the thermal polymerization initiator and polymerization inhibitor, and any further additives) can be carried out in a controlled environment of 60°C or less (e.g., 10 to 60°C).

[0102] According to yet another aspect of the present invention, there is provided an article to which the above-mentioned composition for bonding dissimilar materials of the present invention is applied.

[0103] In one embodiment, the different materials may be a metal material and a non-metal material (for example, an organic material such as a plastic material).

[0104] In one embodiment, the article includes a metal material; a non-metallic material; and an adhesive layer therebetween, and the adhesive layer can include the dissimilar material bonding composition of the present invention.

[0105] The present invention will be described in more detail below with reference to examples and comparative examples, but the scope of the present invention is not limited thereto.

[0106] Example <Production of anhydrosugar alcohol-alkylene oxide adduct> Production Example 1: Production of isosorbide-ethylene oxide 5 mole adduct In a pressurizable reactor, 146 g of isosorbide and 0.15 g of phosphoric acid (85%) were added as an acid component. The reactor was then purged with nitrogen, heated to 100°C, and depressurized under vacuum to remove moisture from the reactor. Next, 88 g of ethylene oxide was slowly added to the reactor, and the reaction was carried out at 100°C to 140°C for 2 to 3 hours. The reaction temperature was controlled so as not to exceed 140°C. The internal temperature of the reactor was then cooled to 50°C, 0.3 g of potassium hydroxide was added to the reactor, the reactor was purged with nitrogen, heated to 100°C, and depressurized under vacuum to remove moisture from the reactor. Next, 132 g of ethylene oxide was slowly added, and the reaction was carried out at 100°C to 140°C for 2 to 3 hours. After the reaction was completed, the internal temperature of the reactor was cooled to 50°C, 4.0 g of Ambosol MP20 was added as an adsorbent, and the reactor was reheated and stirred at 100-120°C for 1-5 hours to remove metal ions. At this time, the reactor was purged with nitrogen and / or evacuated. After confirming that no metal ions were detected, the internal temperature of the reactor was cooled to 60-90°C, and residual by-products were removed, yielding 362 g of a transparent liquid isosorbide-ethylene oxide 5-mol adduct.

[0107] Production Example 2: Production of isosorbide-ethylene oxide 10 mole adduct In the same manner as in Production Example 1, except that the amount of ethylene oxide added in the second run was changed from 132 g to 352 g, 551 g of a transparent liquid isosorbide-ethylene oxide 10 mol adduct was obtained.

[0108] Production Example 3: Production of isosorbide-propylene oxide 5 mole adduct Propylene oxide was used instead of ethylene oxide as an addition reaction raw material. Specifically, 116 g of propylene oxide was added instead of 88 g of ethylene oxide, and then 174 g of propylene oxide was added instead of 132 g of ethylene oxide in the same manner as in Production Example 1, except that 423 g of a transparent liquid isosorbide-propylene oxide 5-mol adduct was obtained.

[0109] Production Example 4: Production of isosorbide-propylene oxide 10 mole adduct Propylene oxide was used instead of ethylene oxide as an addition reaction raw material. Specifically, 116 g of propylene oxide was added instead of 88 g of ethylene oxide, and then 465 g of propylene oxide was added instead of 132 g of ethylene oxide in the same manner as in Production Example 1, except that 698 g of a transparent liquid isosorbide-propylene oxide 10 mol adduct was obtained.

[0110] <Production of (meth)acrylic-modified polyurethane component> Production Example A1: Production of a (meth)acrylic-modified polyurethane component using polypropylene glycol (80 parts by weight based on 100 parts by weight of all polyols) and isosorbide-ethylene oxide 5-mol adduct (20 parts by weight based on 100 parts by weight of all polyols) as polyols, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate A three-necked glass reactor equipped with a stirrer was charged with 600 g of isophorone diisocyanate (IPDI) and 0.6 g of dibutyltin dilaurate (DBTDL) as a reaction catalyst. While stirring this mixture at room temperature, 800 g of polypropylene glycol (number average molecular weight: 1,000 g / mol, manufactured by Kumho Petrochemical Co., Ltd.) as a polyol component and 200 g of the isosorbide-ethylene oxide 5-mol adduct obtained in Production Example 1 were slowly added to carry out a crosslinking reaction. After the addition of the polyol component was completed, the mixture was stirred at 50°C for 1 hour and then 350 g of 2-hydroxyethyl methacrylate was slowly added to carry out an acrylic modification reaction. After the addition of 2-hydroxyethyl methacrylate was completed, the mixture was stirred at 50°C for 1 hour and then cooled to room temperature to obtain 1,950 g of a (meth)acrylic-modified polyurethane component containing 390 g of the (meth)acrylic-modified polyurethane of the following formula (A-1) and 1,560 g of the (meth)acrylic-modified polyurethane of the following formula (A-2).

[0111] [ka] [ka]

[0112] Production Example A2: Production of a (meth)acrylic-modified polyurethane component using polytetrahydrofuran (50 parts by weight based on 100 parts by weight of all polyols) and isosorbide-ethylene oxide 10-mol adduct (50 parts by weight based on 100 parts by weight of all polyols) as polyols, hexamethylene diisocyanate (HDI) as polyisocyanate, and 2-hydroxyethyl acrylate as hydroxyalkyl (meth)acrylate. The same method as in Production Example A1 was repeated, except that 270 g of hexamethylene diisocyanate (HDI) was used instead of isophorone diisocyanate (IPDI) as the polyisocyanate, 365 g of polytetrahydrofuran (number average molecular weight: 2,000 g / mol, manufactured by Sigma-Aldrich Corporation) and 365 g of the isosorbide-ethylene oxide 10 mol adduct obtained in Production Example 2 were used instead of polypropylene glycol (number average molecular weight: 1,000 g / mol, manufactured by Kumho Petrochemical Corporation) and the isosorbide-ethylene oxide 5 mol adduct obtained in Production Example 1, and 186 g of 2-hydroxyethyl acrylate were used instead of 2-hydroxyethyl methacrylate as the hydroxyalkyl (meth)acrylate, to obtain 1,185 g of a (meth)acrylic-modified polyurethane component containing 593 g of a (meth)acrylic-modified polyurethane of the following formula (B-1) and 592 g of a (meth)acrylic-modified polyurethane of the following formula (B-2).

[0113] [ka] [ka]

[0114] Production Example A3: Production of a (meth)acrylic-modified polyurethane component using polydimethylsiloxane diol (20 parts by weight based on 100 parts by weight of all polyols) and isosorbide-propylene oxide 5-mol adduct (80 parts by weight based on 100 parts by weight of all polyols) as polyols, methylene diphenyl diisocyanate (MDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate

[0111] In the same manner as in Production Example A1, except that 700 g of methylene diphenyl diisocyanate (MDI) was used instead of isophorone diisocyanate (IPDI) as the polyisocyanate, 140 g of polydimethylsiloxane diol (number average molecular weight: 1,000 g / mol, manufactured by Sigma-Aldrich Corporation) and 560 g of the isosorbide-propylene oxide 5-mol adduct obtained in Production Example 3 were used instead of polypropylene glycol (number average molecular weight: 1,000 g / mol, manufactured by Kumho Petrochemical Co., Ltd.) and the isosorbide-ethylene oxide 5-mol adduct obtained in Production Example 1, and the 2-hydroxyethyl methacrylate content was changed from 350 g to 364 g, 1,763 g of a (meth)acrylic-modified polyurethane component containing 1,410 g of a (meth)acrylic-modified polyurethane of the following formula (C-1) and 353 g of a (meth)acrylic-modified polyurethane of the following formula (C-2) was obtained.

[0115] [ka] [ka]

[0116] Production Example A4: Production of a (meth)acrylic-modified polyurethane component using polytetrahydrofuran (30 parts by weight based on 100 parts by weight of all polyols) and isosorbide-propylene oxide 10-mol adduct (70 parts by weight based on 100 parts by weight of all polyols) as polyols, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate In the same manner as in Production Example A1, except that 324 g of polytetrahydrofuran (number average molecular weight: 1,000 g / mol, manufactured by Sigma-Aldrich Corporation) and 746 g of the isosorbide-propylene oxide 10 mol adduct obtained in Production Example 4 were used instead of polypropylene glycol (number average molecular weight: 1,000 g / mol, manufactured by Kumho Petrochemical Corporation) as the polyol and the isosorbide-ethylene oxide 5 mol adduct obtained in Production Example 1, 2,020 g of a (meth)acrylic-modified polyurethane component containing 1,414 g of a (meth)acrylic-modified polyurethane of the following formula (D-1) and 606 g of a (meth)acrylic-modified polyurethane of the following formula (D-2) was obtained.

[0117] [ka] [ka]

[0118] Production Example A5: Preparation of a (meth)acrylic-modified polyurethane component by separately preparing a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane and mixing them. 1,930 g of a (meth)acrylic-modified polyurethane of the following formula (A-1) was obtained in the same manner as in Production Example A1, except that polypropylene glycol (number average molecular weight: 1,000 g / mol, manufactured by Kumho Petrochemical Corporation) was not used as the polyol component, and only 981 g of the isosorbide-ethylene oxide 5-mol adduct obtained in Production Example 1 was used.

[0119] [ka]

[0120] In addition, 2,250 g of a (meth)acrylic-modified polyurethane of the following formula (A-2) was obtained in the same manner as in Production Example A1, except that the isosorbide-ethylene oxide 5-mol adduct obtained in Production Example 1 was not used as the polyol component, and only 1,349 g of polypropylene glycol (number average molecular weight: 1,000 g / mol, manufactured by Kumho Petrochemical Corporation) was used.

[0121] [ka]

[0122] 200 g of the (meth)acrylic-modified polyurethane of formula (A-1) obtained above and 800 g of the (meth)acrylic-modified polyurethane of formula (A-2) obtained above were simply mixed to obtain 1,000 g of a (meth)acrylic-modified polyurethane component.

[0123] Production Example A6: Preparation of a (meth)acrylic-modified polyurethane component by separately preparing a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane and mixing them. The (meth)acrylic-modified polyurethane of formula (A-1) and the (meth)acrylic-modified polyurethane of formula (A-2) were simply mixed in the same manner as in Production Example A5, except that the content of the (meth)acrylic-modified polyurethane of formula (A-1) obtained above was changed from 200 g to 500 g, and the content of the (meth)acrylic-modified polyurethane of formula (A-2) obtained above was changed from 800 g to 500 g, to obtain 1,000 g of a (meth)acrylic-modified polyurethane component.

[0124] Production Example A7: Preparation of a (meth)acrylic-modified polyurethane component by separately preparing a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane and mixing them. The (meth)acrylic-modified polyurethane of formula (A-1) and the (meth)acrylic-modified polyurethane of formula (A-2) were simply mixed in the same manner as in Production Example A5, except that the content of the (meth)acrylic-modified polyurethane of formula (A-1) obtained above was changed from 200 g to 800 g, and the content of the (meth)acrylic-modified polyurethane of formula (A-2) obtained above was changed from 800 g to 200 g, to obtain 1,000 g of a (meth)acrylic-modified polyurethane component.

[0125] Comparative Production Example A1: Production of (meth)acrylic-modified polyurethane using isosorbide-ethylene oxide 5-mol adduct as polyol, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate 1,930 g of a (meth)acrylic-modified polyurethane of the following formula (A-1) was obtained in the same manner as in Production Example A1, except that polypropylene glycol (number average molecular weight: 1,000 g / mol, manufactured by Kumho Petrochemical Corporation) was not used as the polyol, and only 981 g of the isosorbide-ethylene oxide 5-mol adduct obtained in Production Example 1 was used.

[0126] [ka]

[0127] Comparative Preparation Example A2: Preparation of (meth)acrylic-modified polyurethane by using polypropylene glycol as polyol, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate 2,250 g of a (meth)acrylic-modified polyurethane of the following formula (A-2) was obtained in the same manner as in Production Example A1, except that the isosorbide-ethylene oxide 5-mol adduct obtained in Production Example 1 was not used as the polyol, and only 1,349 g of polypropylene glycol (number average molecular weight: 1,000 g / mol, manufactured by Kumho Petrochemical Corporation) was used.

[0128] [ka]

[0129] <Production of Composition for Adhesion of Dissimilar Materials> Examples A1 to A7 and Comparative Examples A1 to A14: Standard Production Method A (meth)acrylic-modified polyurethane component, a (meth)acrylic monomer, an epoxy resin, an epoxy curing accelerator, a thermal polymerization initiator, and a polymerization inhibitor were charged in the weight ratios shown in Table 1 below in a mixing reactor controlled at 60°C or below, and these were stirred and mixed at 60°C or below to produce a liquid composition for bonding dissimilar materials.

[0130] At this time, the total amount of the (meth)acrylic-modified polyurethane component, (meth)acrylic monomer, epoxy resin, epoxy curing accelerator, thermal polymerization initiator, and polymerization inhibitor was 100 parts by weight.

[0131] <Ingredients> (1) (Meth)acrylic-modified polyurethane component ((meth)acrylic-modified PU component) Production Example A1: (meth)acrylic-modified polyurethane component obtained in Production Example A1 Production Example A2: (meth)acrylic-modified polyurethane component obtained in Production Example A2 Production Example A3: (meth)acrylic-modified polyurethane component obtained in Production Example A3 Production Example A4: (Meth)acrylic-modified polyurethane component obtained in Production Example A4 Production Example A5: (meth)acrylic-modified polyurethane component obtained in Production Example A5 Production Example A6: (meth)acrylic-modified polyurethane component obtained in Production Example A6 Production Example A7: (meth)acrylic-modified polyurethane component obtained in Production Example A7 Comparative Production Example A1: (meth)acrylic-modified polyurethane of formula (A-1) obtained in Comparative Production Example A1 Comparative Production Example A2: (meth)acrylic-modified polyurethane of formula (A-2) obtained in Comparative Production Example A2 (2) (Meth)acrylic monomer 2-HEMA: 2-hydroxyethyl methacrylate (manufactured by Samchun Pure Chemical Co., Ltd.) 4-HBA: 4-hydroxybutyl acrylate (manufactured by Samchun Pure Chemical Co., Ltd.) BA: Butyl acrylate (manufactured by Samchun Pure Chemical Co., Ltd.) PETTA: Pentaerythritol tetraacrylate (Miwon Commercial) P-2M: 2-methacryloyloxyethyl acid phosphate (Kyoei Chemical Co., Ltd.) BDDA: 1,4-butanediol diacrylate (Sigma-Aldrich) (3) Epoxy resin DGEBA: Bisphenol A epoxy resin (manufactured by KUKDO CHEMICAL) YDF-170: Bisphenol F epoxy resin (manufactured by KUKDO CHEMICAL) 1,4-BDGE: 1,4-butanediol diglycidyl ether (KUKDO CHEMICAL) (4) Epoxy curing accelerator DICY: Dicyandiamide (manufactured by Evonik) UR2T: 1,1'-(4-methyl-m-phenylene)bis(3,3-dimethylurea) (manufactured by Evonik) (5) Thermal polymerization initiator V-65: 2,2'-azobis(2,4-dimethylvaleronitrile) (Fujifilm) V-40: 1,1'-azobis(cyclohexane-1-carbonitrile) (Fujifilm) Peroyl TCP: Bis(4-t-butylcyclohexyl) peroxydicarbonate (NOF Corporation) (6) Polymerization inhibitor MEHQ: Hydroquinone monomethyl ether (Sigma-Aldrich)

[0132] [Table 1-1]

[0133] [Table 1-2]

[0134] [Table 1-3]

[0135] <Evaluation of physical properties of adhesive compositions for bonding dissimilar materials> The dissimilar material bonding compositions prepared in each of Examples A1 to A7 and Comparative Examples A1 to A14 were applied to the surface of a rolled steel plate cut to a size of 2.5 cm x 12 cm and a carbon fiber reinforced plastic (CFRP) cut to a size of 2.5 cm x 12 cm in an area of ​​2.5 cm x 1.25 cm, and the thickness was adjusted using 0.2 mm glass beads. The coated areas were overlapped and fixed, and then heated and cured at 100°C for 2 minutes to prepare dissimilar material bonding specimens. The adhesion, oil resistance, and storage stability of each specimen were evaluated using the methods described below, and the results are shown in Table 2 below.

[0136] <Method for evaluating physical properties> (1) Adhesiveness To evaluate the adhesiveness of the composition to dissimilar materials, the shear strength (unit: MPa) of each bonded specimen of dissimilar materials was measured at room temperature (23°C) using a UTM (Instron 5967 product, manufactured by Instron Corporation), and also after heating each bonded specimen of dissimilar materials to 100°C in a hot air dryer. Specifically, the shear strength of each bonded specimen of dissimilar materials was measured a total of five times, and the average value was calculated. The higher the shear strength, the better the adhesiveness.

[0137] (2) Oil resistance The dissimilar material bonded specimens were immersed in mineral oil (manufactured by Daejung Chemical Co.) and heated at 90°C for 50 hours. The shear strength of each immersed dissimilar material bonded specimen was measured five times using the adhesion measurement method described in (1) above, and the average value was calculated. The reduction rate (%) of shear strength after immersion relative to the shear strength before immersion for each dissimilar material bonded specimen was then calculated. A lower reduction rate of shear strength indicates better oil resistance. Shear strength reduction rate (%) = (shear strength before immersion - shear strength after immersion) x 100 / shear strength before immersion

[0138] (3) Storage stability Each of the compositions for bonding dissimilar materials prepared in Examples A1 to A7 and Comparative Examples A1 to A14 was placed in a transparent glass vial, sealed, and left at room temperature (23°C) for 3 days, after which the presence or absence of hardening was confirmed with the naked eye.

[0139] [Table 2]

[0140] As shown in Table 2 above, in the case of the dissimilar material bonding compositions of Examples A1 to A7 produced using the (meth)acrylic-modified polyurethane component according to the present invention, the adhesiveness between dissimilar materials was good, with a shear strength of 23 MPa or more at room temperature (23°C), and the adhesiveness was maintained well, with a shear strength of 17 MPa or more even at high temperatures (100°C). Furthermore, even after immersion in mineral oil at 90°C for 50 hours, the reduction in shear strength was less than 20%, maintaining good adhesiveness and excellent oil resistance.

[0141] However, in the case of the dissimilar material bonding composition of Comparative Example A1, which used a (meth)acrylic-modified polyurethane component produced without using a lipophilic polyol, the adhesive strength with carbon fiber reinforced plastic (CFRP) decreased, resulting in low shear strength at both room temperature and high temperatures. Furthermore, in the case of the dissimilar material bonding composition of Comparative Example A2, which used a (meth)acrylic-modified polyurethane component produced without using an anhydrosugar alcohol-alkylene oxide adduct, the adhesive strength with metal (rolled steel plate) decreased, resulting in low shear strength at both room temperature and high temperatures, and poor oil resistance. When the dissimilar material bonding specimens were immersed in oil and heated, spontaneous peeling of the dissimilar material bonding specimens was observed.

[0142] Furthermore, the composition for bonding dissimilar materials of Comparative Example A3 had poor adhesion and oil resistance both at room temperature and at high temperatures, and the composition for bonding dissimilar materials of Comparative Example A4 had poor adhesion at high temperatures.

[0143] In the case of the composition for bonding dissimilar materials of Comparative Example A5, spontaneous peeling of the bonded specimens of dissimilar materials was observed after heating was completed, and the adhesive strength and oil resistance at high temperatures were poor. In the case of the composition for bonding dissimilar materials of Comparative Example A6, the adhesive strength decreased and the shear strength was low both at room temperature and at high temperatures.

[0144] Furthermore, the composition for bonding dissimilar materials of Comparative Example A7 had poor adhesion at high temperatures, and the composition for bonding dissimilar materials of Comparative Example A8 had poor adhesion and oil resistance both at room temperature and at high temperatures.

[0145] In addition, in the case of the composition for bonding dissimilar materials of Comparative Example A9, the adhesiveness at room temperature decreased, and spontaneous peeling of the bonded specimens of dissimilar materials was observed after heating was completed, resulting in poor adhesiveness and oil resistance at high temperatures. In the case of the composition for bonding dissimilar materials of Comparative Example A10, the adhesiveness decreased both at room temperature and at high temperatures.

[0146] Furthermore, in the case of the composition for bonding dissimilar materials of Comparative Example A11, when preparing a bonded specimen of dissimilar materials, the composition did not harden even after heating at 100°C for 2 minutes, and initial peeling was observed, making it impossible to prepare a bonded specimen of dissimilar materials. In the case of the composition for bonding dissimilar materials of Comparative Example A12, the adhesiveness decreased both at room temperature and at high temperatures.

[0147] Furthermore, in the case of the composition for bonding dissimilar materials of Comparative Example A13, the composition hardened when stored at room temperature for more than 3 days, resulting in poor storage stability. In the case of the composition for bonding dissimilar materials of Comparative Example A14, when preparing a bonded specimen of dissimilar materials, the composition did not completely harden even after heating at 100°C for 2 minutes, resulting in reduced adhesiveness at room temperature. After heating of the bonded specimen of dissimilar materials was completed, spontaneous peeling of the bonded specimen of dissimilar materials was observed, and the adhesiveness and oil resistance at high temperatures were poor.

[0148] As explained above, when the composition for bonding dissimilar materials according to the present invention is used in an amount within a specific range, it has been confirmed that the composition has excellent adhesion between dissimilar materials at room temperature, and that the adhesion is well maintained even when heated to high temperatures or stored in mineral oil at high temperatures, and therefore has excellent adhesion and oil resistance at high temperatures.

Claims

1. Based on 100 parts by weight of the total amount of the composition, 25.5 to 84.5 parts by weight of a (meth)acrylic-modified polyurethane component containing a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane; 9.5 to 63.5 parts by weight of (meth)acrylic monomer; 2.5 to 34.5 parts by weight of epoxy resin; 0.06 to 2.95 parts by weight of an epoxy curing accelerator; 0.0006 to 2.95 parts by weight of a thermal polymerization initiator; and 0.006 to 0.65 parts by weight of a polymerization inhibitor; Including, the hydrophilic (meth)acrylic-modified polyurethane comprises polymerized units derived from an anhydrosugar alcohol-alkylene oxide adduct; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate; The lipophilic (meth)acrylic-modified polyurethane contains polymerized units derived from a lipophilic polyol; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate; the lipophilic polyol is selected from polytetrahydrofuran, polypropylene glycol, polydimethylsiloxane (PDMS) polyol, or a combination thereof; The (meth)acrylic-modified polyurethane component contains 16 to 84 parts by weight of the hydrophilic (meth)acrylic-modified polyurethane and 16 to 84 parts by weight of the lipophilic (meth)acrylic-modified polyurethane relative to 100 parts by weight of the total amount of the (meth)acrylic-modified polyurethane component. Composition for bonding dissimilar materials.

2. The composition for bonding dissimilar materials according to claim 1, wherein the anhydrosugar alcohol-alkylene oxide adduct is obtained by reacting hydroxy groups at both ends or one end of the anhydrosugar alcohol with an alkylene oxide, and the alkylene oxide is a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms.

3. The composition for bonding dissimilar materials according to claim 2, wherein the anhydrosugar alcohol is isosorbide, isomannide, isoidide, or a combination thereof.

4. 2. The composition for bonding dissimilar materials according to claim 1, wherein the polyisocyanate is methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.

5. The hydroxyalkyl (meth)acrylate is hydroxy-C 1-8 2. The composition for bonding dissimilar materials according to claim 1, wherein the adhesive is an alkyl (meth)acrylate.

6. The composition for bonding dissimilar materials according to claim 1 , wherein the hydrophilic (meth)acrylic-modified polyurethane is represented by the following formula (2): 【Chemical 1】 (wherein each R is independently an alkylene group, Each R is independently an alkylene group, a cycloalkylene group, or an arylene group; Each R is independently an alkylene group; Each R is independently a hydrogen atom or an alkyl group, M is a divalent organic group derived from an anhydrosugar alcohol; m and n each independently represent an integer of 0 to 15; m+n represents an integer of 1 to 30.

7. In the formula (2), Each R1 is independently a C2-C8 linear or C3-C8 branched alkylene group; R2's are each independently a C2-C20 linear or C3-C20 branched alkylene group, a C3-C20 cycloalkylene group, or a C6-C20 arylene group; R3 is independently a C1-C8 linear or C3-C8 branched alkylene group; R4's are each independently a hydrogen atom or a C1-C4 linear or C3-C4 branched alkyl group; M is a divalent organic group derived from isosorbide, isomannide, or isoidide; m and n each independently represent an integer of 0 to 15; 7. The composition for bonding dissimilar materials according to claim 6, wherein m+n represents an integer of 1 to 25.

8. 2. The composition for bonding dissimilar materials according to claim 1, wherein the lipophilic (meth)acrylic-modified polyurethane is represented by the following formula (3): 【Chemistry 2】 (wherein each R is independently an alkylene group, a cycloalkylene group, or an arylene group, Each R is independently an alkylene group; Each R is independently a hydrogen atom or an alkyl group, L is a divalent organic group derived from a lipophilic polyol, wherein the number average molecular weight of the lipophilic polyol is 200 to 3,000 g / mol.

9. In the formula (3), R1's are each independently a C2-C20 linear or C3-C20 branched alkylene group, a C3-C20 cycloalkylene group, or a C6-C20 arylene group; R2 is independently a C1-C8 linear or C3-C8 branched alkylene group; R3 is independently a hydrogen atom or a C1-C4 linear or C3-C4 branched alkyl group; L is a divalent organic group derived from a lipophilic polyol selected from polytetrahydrofuran, polypropylene glycol, polydimethylsiloxane (PDMS) polyol, or a combination thereof, wherein the lipophilic polyol has a number average molecular weight of 500 to 2,500 g / mol. The dissimilar material bonding composition according to claim 8.

10. 2. The composition for bonding dissimilar materials according to claim 1, wherein the (meth)acrylic monomer is a monomer having 1 to 4 (meth)acrylic groups in the molecule.

11. 2. The composition for bonding dissimilar materials according to claim 1, wherein the epoxy resin is a resin having two or more epoxy groups in the molecule.

12. 2. The composition for bonding dissimilar materials according to claim 1, wherein the thermal polymerization initiator is selected from the group consisting of a compound represented by the following formula (4-1), a compound represented by the following formula (4-2), and a mixture thereof: 【Chemistry 3】 wherein R and R' are each independently a C2-C8 linear or C3-C8 branched alkyl group; a C3-C20 cycloalkyl group; a C6-C20 aryl group; or a C2-C8 linear or C3-C8 branched methoxy-alkyl group; and X is -CN or -CO 2 R″ (wherein R″ is a C2-C8 linear or C3-C8 branched alkyl group; a C3-C20 cycloalkyl group; or a C6-C20 aryl group). 【Chemistry 4】 (In the formula, each R is independently a C2-C8 linear or C3-C8 branched alkyl group; a C3-C20 cycloalkyl group; or a C6-C20 aryl group.)

13. Based on 100 parts by weight of the total amount of the composition, 25.5 to 84.5 parts by weight of a (meth)acrylic-modified polyurethane component containing a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane; 9.5 to 63.5 parts by weight of (meth)acrylic monomer; 2.5 to 34.5 parts by weight of epoxy resin; 0.06 to 2.95 parts by weight of an epoxy curing accelerator; 0.0006 to 2.95 parts by weight of a thermal polymerization initiator; and 0.006 to 0.65 parts by weight of a polymerization inhibitor; mixing the the hydrophilic (meth)acrylic-modified polyurethane comprises polymerized units derived from an anhydrosugar alcohol-alkylene oxide adduct; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate; The lipophilic (meth)acrylic-modified polyurethane contains polymerized units derived from a lipophilic polyol; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate; the lipophilic polyol is selected from polytetrahydrofuran, polypropylene glycol, polydimethylsiloxane (PDMS) polyol, or a combination thereof; The (meth)acrylic-modified polyurethane component contains 16 to 84 parts by weight of the hydrophilic (meth)acrylic-modified polyurethane and 16 to 84 parts by weight of the lipophilic (meth)acrylic-modified polyurethane relative to 100 parts by weight of the total amount of the (meth)acrylic-modified polyurethane component. A method for producing a composition for bonding dissimilar materials.

14. An article to which the composition for bonding dissimilar materials according to any one of claims 1 to 12 is applied.

15. a metallic material; a non-metallic material; and an adhesive layer therebetween; The article according to claim 14, wherein the adhesive layer comprises the composition for bonding dissimilar materials according to any one of claims 1 to 12.

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