(Meth)acrylic-modified polyurethane composition and method for producing the same

Abstract

The present invention relates to a (meth)acrylic-modified polyurethane composition and a method for producing the same. More specifically, the present invention relates to a (meth)acrylic-modified polyurethane composition and a method for producing the same, which comprises a hydrophilic (meth)acrylic-modified polyurethane containing polymerization units derived from an anhydrosugar alcohol-alkylene oxide adduct and a lipophilic (meth)acrylic-modified polyurethane containing polymerization units derived from a lipophilic polyol, and which can provide an adhesive composition having excellent environmental friendliness, adhesive strength (particularly, adhesive strength between different materials) and oil resistance, as well as a hygroscopic coating composition having excellent hygroscopicity and suitable for anti-fogging applications, and a method for producing the same.

Description

[Technical Field]

[0001] The present invention relates to a (meth)acrylic-modified polyurethane composition and a method for producing the same. More specifically, the present invention relates to a (meth)acrylic-modified polyurethane composition and a method for producing the same, which comprises a hydrophilic (meth)acrylic-modified polyurethane containing polymerization units derived from an anhydrosugar alcohol-alkylene oxide adduct and a lipophilic (meth)acrylic-modified polyurethane containing polymerization units derived from a lipophilic polyol, and which can provide an adhesive composition that is excellent in all of environmental friendliness, adhesive strength (particularly adhesive strength between different materials), and oil resistance, as well as a moisture-absorbing coating composition that has excellent moisture absorption properties and is suitable for anti-fogging applications, 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 attracted much attention, leading to extensive research into their 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. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Korean Patent No. 10-1079518 [Patent Document 2] Korean Patent No. 10-2012-0066904 Summary of the Invention [Problem to be solved by the invention]

[0010] An object of the present invention is to provide a (meth)acrylic-modified polyurethane composition and a method for producing the same, which can provide an adhesive composition that is excellent in all of environmental friendliness, adhesive strength (particularly adhesive strength between different materials) and oil resistance by utilizing an anhydrosugar alcohol derivative, as well as a moisture-absorbing coating composition that is excellent in moisture absorption and suitable for anti-fogging applications. [Means for solving the problem]

[0011] In order to achieve the above object, the present invention provides a (meth)acrylic-modified polyurethane composition comprising: (1) a hydrophilic (meth)acrylic-modified polyurethane containing 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; and (2) a lipophilic (meth)acrylic-modified polyurethane containing polymerized units derived from a lipophilic polyol; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate.

[0012] According to another aspect of the present invention, there is provided a method for producing a (meth)acrylic-modified polyurethane composition, 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.

[0013] According to yet another aspect of the present invention, there is provided a hydrophilic (meth)acrylic-modified polyurethane comprising: (i) 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; (ii) a lipophilic (meth)acrylic-modified polyurethane containing polymerized units derived from a lipophilic polyol; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate; The present invention provides a method for producing a (meth)acrylic-modified polyurethane composition, comprising the step of mixing:

[0014] According to yet another aspect of the present invention, there is provided an adhesive composition comprising the (meth)acrylic-modified polyurethane composition of the present invention.

[0015] According to yet another aspect of the present invention, there is provided an article to which the above-mentioned adhesive composition of the present invention is applied.

[0016] According to yet another aspect of the present invention, there is provided a moisture-absorbing coating composition comprising the (meth)acrylic-modified polyurethane composition of the present invention. [Effects of the Invention]

[0017] The (meth)acrylic-modified polyurethane composition according to the present invention has excellent environmental friendliness, and when used as an adhesive composition, it can improve both the adhesive strength (especially the adhesive strength between different materials) and oil resistance. When used as a moisture-absorbing coating composition, it can provide a coating that has excellent adhesive strength to glass plates even after absorbing moisture and has excellent anti-fogging properties. BEST MODE FOR CARRYING OUT THE INVENTION

[0018] The present invention will now be described in more detail.

[0019] 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.

[0020] The (meth)acrylic-modified polyurethane composition of the present invention comprises: (1) a hydrophilic (meth)acrylic-modified polyurethane containing 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; and (2) a lipophilic (meth)acrylic-modified polyurethane containing polymerized units derived from a lipophilic polyol; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate.

[0021] In one embodiment, the (meth)acrylic-modified polyurethane composition can contain 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, based on 100 parts by weight of the total amount of the (meth)acrylic-modified polyurethane composition. If the hydrophilic (meth)acrylic-modified polyurethane content in the (meth)acrylic-modified polyurethane composition is too low (i.e., if the lipophilic (meth)acrylic-modified polyurethane content is too high), a composition produced therefrom may exhibit low adhesion to metals. Conversely, if the hydrophilic (meth)acrylic-modified polyurethane content is too high (i.e., if the lipophilic (meth)acrylic-modified polyurethane content is too low), a composition produced therefrom may exhibit low adhesion to organic materials.

[0022] More specifically, the hydrophilic and lipophilic (meth)acrylic-modified polyurethanes 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 relative to 100 parts by weight of the total amount of the (meth)acrylic-modified polyurethane composition, and the hydrophilic and lipophilic (meth)acrylic-modified polyurethanes 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.

[0023] Anhydrosugar alcohol-alkylene oxide adduct The anhydrosugar alcohol-alkylene oxide adduct (also referred to as "anhydrosugar alcohol-alkylene glycol") contained as a polymerization unit in the above-mentioned 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 the ring-opened form of the alkylene oxide.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] In one embodiment, the anhydrosugar alcohol-alkylene oxide adduct may be a compound represented by the following formula (1) or a mixture thereof.

[0031] [ka] (In the formula, R 1 and R 2 each 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.

[0032] 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.

[0033] 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.

[0034] [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.

[0035] [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.

[0036] 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.

[0037] 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.

[0038] 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).

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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 per mole of anhydrosugar alcohol is, for example, 1 mole or more or 2 moles or more, and may be 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.

[0043] 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 pressurizable high-pressure reactor (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 per 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. Prior to adding the base catalyst, the acid component used in the treatment can be removed by filtration.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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 bonded specimen of dissimilar materials to which a bonding composition containing a (meth)acrylic-modified polyurethane composition 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 bonded specimen of dissimilar materials to which a bonding composition containing a (meth)acrylic-modified polyurethane composition produced therefrom is applied may be low.

[0048] 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; The isocyanate may be, but is not limited to, an aliphatic polyisocyanate 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), dimeric fatty acid diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate (e.g., cyclohexane-1,4-diisocyanate), or ethylene diisocyanate; or a combination thereof.

[0049] 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.

[0050] More specifically, the polyisocyanate may be methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.

[0051] 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.

[0052] 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.

[0053] Hydrophilic (meth)acrylic modified polyurethane In one embodiment, the hydrophilic (meth)acrylic-modified polyurethane can be represented by the following formula (2):

[0054] [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:

[0055] [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.

[0056] More specifically, the hydrophilic (meth)acrylic-modified polyurethane can be represented by any of the following formulas, but is not limited thereto:

[0057] [ka] (In the formula, m, n, and m+n are each independently defined as in formula (2) above.) 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.

[0058] 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.

[0059] 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).

[0060] 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).

[0061] 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).

[0062] Lipophilic (meth)acrylic modified polyurethane In one embodiment, the lipophilic (meth)acrylic-modified polyurethane may be represented by the following formula (3):

[0063] [ka] (In the formula, each R1 is independently 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.

[0064] The lipophilic (meth)acrylic-modified polyurethane can be obtained by reacting a lipophilic polyol with a polyisocyanate and then with a hydroxyalkyl (meth)acrylate.

[0065] 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.

[0066] 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).

[0067] 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).

[0068] 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).

[0069] Method for producing a (meth)acrylic-modified polyurethane composition In one embodiment, the (meth)acrylic-modified polyurethane composition 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.

[0070] In another embodiment, the (meth)acrylic-modified polyurethane composition 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 composition 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.

[0071] In the first and second production methods of the (meth)acrylic-modified polyurethane composition, the anhydrosugar alcohol-alkylene oxide adduct, lipophilic polyol, polyisocyanate, and hydroxyalkyl (meth)acrylate are the same as those described above.

[0072] According to one embodiment, in the first production method for the (meth)acrylic-modified polyurethane composition, 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.

[0073] According to one embodiment, in the first production method for the (meth)acrylic-modified polyurethane composition, the reaction between the polyol component and 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 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 between the reaction product of the polyol component and the polyisocyanate (i.e., the intermediate obtained in step (1)) and 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).

[0074] According to one embodiment, in the second production method of the (meth)acrylic-modified polyurethane composition, 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 each other relative to 100 parts by weight of the total amount of the (meth)acrylic-modified polyurethane composition 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.

[0075] In the second method for producing the (meth)acrylic-modified polyurethane composition, the methods for producing the (i) hydrophilic and (ii) lipophilic (meth)acrylic-modified polyurethanes to be mixed are the same as those explained above.

[0076] The (meth)acrylic-modified polyurethane composition according to the present invention is environmentally friendly, and when used in an adhesive composition, can satisfactorily improve both adhesive strength (particularly adhesive strength between different materials) and oil resistance.

[0077] Therefore, in another aspect, the present invention provides an adhesive composition containing the (meth)acrylic-modified polyurethane composition of the present invention, and an article to which the adhesive composition is applied.

[0078] In one embodiment, the adhesive composition can be used for bonding between dissimilar materials, for example, between a metal material and a material other than a metal (for example, an organic material such as a plastic material), and the article can also include such dissimilar materials bonded by the adhesive composition.

[0079] In one embodiment, the adhesive composition may further include a (meth)acrylic monomer and / or an epoxy resin.

[0080] In one embodiment, the adhesive composition may further include one or more additives that may be included in conventional adhesive compositions, such as a curing accelerator, a polymerization initiator, and / or a polymerization inhibitor.

[0081] According to yet another aspect of the present invention, there is provided a moisture-absorbing coating composition comprising the (meth)acrylic-modified polyurethane composition of the present invention.

[0082] In one embodiment, the moisture-absorbing coating composition can be particularly suitable for use in anti-fogging applications.

[0083] In one embodiment, the moisture-absorbing coating composition can further include a (meth)acrylic monomer.

[0084] In one embodiment, the moisture-absorbing coating composition may further include additives that may be conventionally used in moisture-absorbing coating agents (e.g., anti-fogging agents, etc.), such as a polymerization initiator (e.g., a thermal polymerization initiator, a photopolymerization initiator, etc.) and / or a polymerization inhibitor.

[0085] The present invention will be described in detail below with reference to examples and comparative examples, but the scope of the present invention is not limited thereto in any way.

[0086] Example <Production of anhydrosugar alcohol-alkylene oxide adduct> Production Example A1: 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.

[0087] Production Example A2: Production of isosorbide-ethylene oxide 10 mole adduct In the same manner as in Production Example A1, 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.

[0088] Production Example A3: 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, and the same procedure as in Production Example A1 was repeated to obtain 423 g of a transparent liquid isosorbide-propylene oxide 5-mol adduct.

[0089] Production Example A4: 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 A1, except for this, 698 g of a transparent liquid isosorbide-propylene oxide 10 mol adduct was obtained.

[0090] <Production of (meth)acrylic-modified polyurethane composition> Example A1: Preparation of a (meth)acrylic-modified polyurethane composition using polypropylene glycol (80 parts by weight based on 100 parts by weight of the total polyols) and an isosorbide-ethylene oxide 5-mol adduct (20 parts by weight based on 100 parts by weight of the total 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 A1 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 composition 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).

[0091] [ka] [ka]

[0092] Example A2: Preparation of a (meth)acrylic-modified polyurethane composition using polytetrahydrofuran (50 parts by weight based on 100 parts by weight of the total polyols) and an isosorbide-ethylene oxide 10-mol adduct (50 parts by weight based on 100 parts by weight of the total polyols) as polyols, hexamethylene diisocyanate (HDI) as polyisocyanate, and 2-hydroxyethyl acrylate as hydroxyalkyl (meth)acrylate

[0111] In the same manner as in Production Example A1, 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 A2 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 A1, and 186 g of 2-hydroxyethyl acrylate was used instead of 2-hydroxyethyl methacrylate as the hydroxyalkyl (meth)acrylate, 1,185 g of a (meth)acrylic-modified polyurethane composition 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) was obtained.

[0093] [ka] [ka]

[0094] Example A3: Preparation of a (meth)acrylic-modified polyurethane composition using polydimethylsiloxane diol (20 parts by weight based on 100 parts by weight of the total polyols) and isosorbide-propylene oxide 5-mol adduct (80 parts by weight based on 100 parts by weight of the total polyols) as polyols, methylene diphenyl diisocyanate (MDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate The same method as in Example A1 was repeated, 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 A3 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 A1, and the 2-hydroxyethyl methacrylate content was changed from 350 g to 364 g, to obtain 1,763 g of a (meth)acrylic-modified polyurethane composition 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).

[0095] [ka] [ka]

[0096] Example A4: Preparation of a (meth)acrylic-modified polyurethane composition using polytetrahydrofuran (30 parts by weight based on 100 parts by weight of the total polyol) and isosorbide-propylene oxide 10-mol adduct (70 parts by weight based on 100 parts by weight of the total polyol) as polyols, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate In the same manner as in 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 A4 were used instead of polypropylene glycol (number average molecular weight: 1,000 g / mol, manufactured by Kumho Petrochemical Corporation) as the polyol component and the isosorbide-ethylene oxide 5 mol adduct obtained in Production Example A1, 2,020 g of a (meth)acrylic-modified polyurethane composition containing 1,414 g of the (meth)acrylic-modified polyurethane of the following formula (D-1) and 606 g of the (meth)acrylic-modified polyurethane of the following formula (D-2) was obtained.

[0097] [ka] [ka]

[0098] Example A5: Preparation of a (meth)acrylic-modified polyurethane composition by preparing a hydrophilic (meth)acrylic-modified polyurethane and a lipophilic (meth)acrylic-modified polyurethane and mixing them. In the same manner as in 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 A1 was used, 1,930 g of a (meth)acrylic-modified polyurethane of the following formula (A-1) was obtained.

[0099] [ka]

[0100] 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 Example A1, except that the isosorbide-ethylene oxide 5-mol adduct obtained in Production Example A1 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.

[0101] [ka]

[0102] 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 composition.

[0103] Example A6: Preparation of a (meth)acrylic-modified polyurethane composition by 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 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 composition.

[0104] Production Example A7: Preparation of a (meth)acrylic-modified polyurethane composition 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 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 composition.

[0105] Comparative Example A1: Preparation of (meth)acrylic-modified polyurethane by using isosorbide-ethylene oxide 5-mol adduct as polyol, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate In the same manner as in 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 A1 was used, 1,930 g of a (meth)acrylic-modified polyurethane of the following formula (A-1) was obtained.

[0106] [ka]

[0107] Comparative 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 Example A1, except that the isosorbide-ethylene oxide 5-mol adduct obtained in Production Example A1 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.

[0108] [ka]

[0109] <Production of Composition for Adhesion of Dissimilar Materials> Examples B1 to B7 and Comparative Examples B1 to B2: Standard Production Method A (meth)acrylic-modified polyurethane composition, 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.

[0110] At this time, the total amount of the (meth)acrylic-modified polyurethane composition, (meth)acrylic monomer, epoxy resin, epoxy curing accelerator, thermal polymerization initiator, and polymerization inhibitor was 100 parts by weight. <Ingredients> (1) (Meth)acrylic-modified polyurethane component ((meth)acrylic-modified PU component) Example A1: (Meth)acrylic-modified polyurethane composition obtained in Example A1 Example A2: (Meth)acrylic-modified polyurethane composition obtained in Example A2 Example A3: (Meth)acrylic-modified polyurethane composition obtained in Example A3 Example A4: (Meth)acrylic-modified polyurethane composition obtained in Example A4 Example A5: (Meth)acrylic-modified polyurethane composition obtained in Example A5 Example A6: (Meth)acrylic-modified polyurethane composition obtained in Example A6 Example A7: (Meth)acrylic-modified polyurethane composition obtained in Example A7 Comparative Example A1: (meth)acrylic-modified polyurethane of formula (A-1) obtained in Comparative Example A1 Comparative Example A2: (meth)acrylic-modified polyurethane of formula (A-2) obtained in Comparative 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)

[0111] [Table 1-1] [Table 1-2]

[0112] <Evaluation of physical properties of adhesive compositions for bonding dissimilar materials> The dissimilar material bonding compositions prepared in each of Examples B1 to B7 and Comparative Examples B1 and B2 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 adhesive test specimens for dissimilar materials. The adhesion, oil resistance, and storage stability of each test specimen were evaluated using the following methods, and the results are shown in Table 2 below.

[0113] <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.

[0114] (2) Oil resistance The above 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. Then, the reduction rate (%) of shear strength after immersion relative to the shear strength before immersion for each dissimilar material bonded specimen was 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

[0115] (3) Storage stability Each of the compositions for bonding dissimilar materials prepared in Examples B1 to B7 and Comparative Examples B1 to B2 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.

[0116] [Table 2]

[0117] As shown in Table 2 above, in the case of the adhesive compositions of Examples B1 to B7 produced using the (meth)acrylic-modified polyurethane composition of the present invention, the adhesion between dissimilar materials was good, with a shear strength of 23 MPa or more at room temperature (23°C), and the adhesion was well maintained, 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 adhesion and excellent oil resistance.

[0118] However, in the case of the adhesive composition of Comparative Example B1, in which a (meth)acrylic-modified polyurethane composition produced without using a lipophilic polyol was used, the adhesive strength with carbon fiber reinforced plastic (CFRP) was reduced, resulting in low shear strength at both room temperature and high temperatures. Furthermore, in the case of the adhesive composition of Comparative Example B2, in which a (meth)acrylic-modified polyurethane composition produced without using an anhydrosugar alcohol-alkylene oxide adduct was used, the adhesive strength with metal (rolled steel plate) was reduced, resulting in low shear strength at both room temperature and high temperatures, and poor oil resistance. When a bonded specimen of a different material was immersed in oil and heated, spontaneous peeling of the bonded specimen of the different material was observed.

[0119] <Production of Hygroscopic Coating Composition> Examples C1 to C7 and Comparative Examples C1 to C2: Standard Production Method A (meth)acrylic-modified polyurethane composition, a (meth)acrylic monomer, a thermal polymerization initiator, and a polymerization inhibitor were charged into a mixing reactor controlled at 60°C or below in the weight ratios shown in Table 3 below, and mixed with stirring at a temperature of 60°C or below to produce a liquid moisture-absorbing coating composition.

[0120] At this time, the total content of the (meth)acrylic-modified polyurethane composition, the (meth)acrylic monomer, the thermal polymerization initiator, and the polymerization inhibitor was 100 parts by weight.

[0121] <Ingredients> (1) (Meth)acrylic-modified polyurethane component ((meth)acrylic-modified PU component) Example A1: (Meth)acrylic-modified polyurethane composition obtained in Example A1 Example A2: (Meth)acrylic-modified polyurethane composition obtained in Example A2 Example A3: (Meth)acrylic-modified polyurethane composition obtained in Example A3 Example A4: (Meth)acrylic-modified polyurethane composition obtained in Example A4 Example A5: (Meth)acrylic-modified polyurethane composition obtained in Example A5 Example A6: (Meth)acrylic-modified polyurethane composition obtained in Example A6 Example A7: (Meth)acrylic-modified polyurethane composition obtained in Example A7 Comparative Example A1: (meth)acrylic-modified polyurethane of formula (A-1) obtained in Comparative Example A1 Comparative Example A2: (meth)acrylic-modified polyurethane of formula (A-2) obtained in Comparative 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 Chemical Co., Ltd.) P-2M: 2-methacryloyloxyethyl acid phosphate (Kyoeisha Chemical Co., Ltd.) (3) Thermal polymerization initiator V-40: 1,1'-azobis(cyclohexane-1-carbonitrile) (Fujifilm) Peroyl TCP: Bis(4-t-butylcyclohexyl) peroxydicarbonate (manufactured by Nichiyu Corporation) (4) Polymerization inhibitor MEHQ: Hydroquinone monomethyl ether (Aldrich)

[0122] [Table 3-1] [Table 3-2]

[0123] <Evaluation of physical properties of moisture-absorbing coating composition> (1) Hygroscopicity To evaluate the moisture absorption of the moisture-absorbing coating compositions, the moisture-absorbing coating compositions prepared in Examples C1 to C7 and Comparative Examples C1 to C2 were filled into a Teflon frame measuring 5 cm x 5 cm x 2 cm (width x length x height), and then heat-treated at 100°C for 20 minutes to cure, thereby preparing test specimens for evaluating moisture absorption. The moisture absorption evaluation specimen was weighed and immersed in water at room temperature (15 to 25°C) for 10 hours to absorb moisture. Next, the moisture absorption evaluation specimen was removed from the water, and the entire surface of the moisture absorption evaluation specimen was wiped with a dry microfiber cloth. The specimen was then weighed and the moisture absorption rate was calculated using the following formula. Moisture absorption rate (%) = [(weight of specimen after immersion - weight of specimen before immersion) / weight of specimen before immersion] x 100

[0124] (2) Adhesion to glass The moisture-absorbing coating compositions prepared in Examples C1 to C7 and Comparative Examples C1 to C2 were coated onto transparent glass at a coating speed of 35 mm / s using a No. 10 bar by bar coating method, and then heat-treated at 100°C for 20 minutes to prepare moisture-absorbing coating specimens.

[0125] To evaluate the adhesion of moisture-absorbing coating specimens, specimens were immersed in water at room temperature (15–25°C) for 10 hours to absorb moisture. Then, a crosshatch cutter was used to create 100 grids measuring 10 mm x 10 mm (horizontal x vertical). Tape was then applied to the grids and rubbed evenly to remove them. The number of grids that peeled from the coating and remained attached to the tape was counted. The adhesion was graded from 0B to 5B based on the number of grids that peeled from the coating. The fewer grids that peeled from the coating, the stronger the adhesion of the coating to the glass (a grade of 3B or higher was required).

[0126] [Table 4]

[0127] (3) Anti-fogging properties The moisture-absorbing coating compositions prepared in Examples C1 to C7 and Comparative Examples C1 to C2 were coated onto transparent glass at a coating speed of 35 mm / s using a No. 10 bar by bar coating method, and then heated at 100°C for 20 minutes to prepare moisture-absorbing coating specimens.

[0128] To evaluate the anti-fogging properties of the moisture-absorbing coated specimens, the coated surface of the moisture-absorbing coated specimen was placed at the outlet of a beaker filled with water at 50°C, and the fogging phenomenon was confirmed. The anti-fogging test was evaluated as "pass" if there was no fogging during 1 minute of exposure, and as "fail" if there was at least slight fogging.

[0129] [Table 5]

[0130] As shown in Table 4 above, the moisture-absorbing coating compositions of Examples C1 to C7, which were produced using the (meth)acrylic-modified polyurethane composition of the present invention, exhibited excellent moisture absorption, with moisture absorption rates of 10% to 40% after immersion in water at room temperature (15°C to 25°C) for 10 hours. The adhesion to glass was also excellent, exhibiting an adhesive strength of 3B or higher even after moisture absorption, and excellent anti-fogging properties were also achieved.

[0131] However, in the case of the moisture-absorbing coating composition of Comparative Example C1, which was applied with a (meth)acrylic-modified polyurethane composition prepared without using a lipophilic polyol, the moisture absorption rate was high at 40% or more, causing excessive expansion, and the adhesion strength to the glass plate was very poor, at grade 1B.

[0132] In the case of the moisture-absorbing coating composition of Comparative Example C2, which used a (meth)acrylic-modified polyurethane composition prepared without using an anhydrosugar alcohol-alkylene oxide adduct, the moisture absorption rate was too low, resulting in poor adhesion to the glass plate (grade 2B) and poor anti-fogging properties.

[0133] As described above, the moisture-absorbing coating composition containing the (meth)acrylic-modified polyurethane composition according to the present invention has excellent adhesion to glass plates even after absorbing moisture, and also has excellent anti-fogging properties.

Claims

1. (1) A hydrophilic (meth)acrylic-modified polyurethane containing 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; and (2) A lipophilic (meth)acrylic-modified polyurethane containing polymerized units derived from a lipophilic polyol having a number average molecular weight of 200 to 3,000 g / mol; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate; Including, the anhydrosugar alcohol-alkylene oxide adduct is obtained by reacting hydroxy groups at both ends or one end of an anhydrosugar alcohol with an alkylene oxide; The (meth)acrylic-modified polyurethane composition, wherein the alkylene oxide is a linear alkylene oxide having 2 to 3 carbon atoms or a branched alkylene oxide having 3 carbon atoms.

2. The (meth)acrylic-modified polyurethane composition according to claim 1, wherein the (meth)acrylic-modified polyurethane composition 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 composition.

3. 2. The (meth)acrylic-modified polyurethane composition according to claim 1, wherein the anhydrosugar alcohol is isosorbide, isomannide, isoidide, or a combination thereof.

4. 2. The (meth)acrylic-modified polyurethane composition 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 The (meth)acrylic-modified polyurethane composition according to claim 1, wherein the (meth)acrylic-modified polyurethane composition is an alkyl (meth)acrylate.

6. The (meth)acrylic-modified polyurethane composition according to claim 1, wherein the hydrophilic (meth)acrylic-modified polyurethane is represented by the following formula (2): 【Chemistry 1】 (In the formula (2), Each R1 is independently a C2-C3 linear or C3 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; m+n represents an integer of 1 to 25.

7. 2. The (meth)acrylic-modified polyurethane composition according to claim 1, wherein the lipophilic polyol is selected from polytetrahydrofuran, polypropylene glycol, polydimethylsiloxane (PDMS) polyol, or a combination thereof.

8. The (meth)acrylic-modified polyurethane composition 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.

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; The (meth)acrylic-modified polyurethane composition according to claim 8, wherein L is a divalent organic group derived from a lipophilic polyol selected from polytetrahydrofuran, polypropylene glycol, polydimethylsiloxane (PDMS) polyol, or a combination thereof, and wherein the lipophilic polyol has a number average molecular weight of 500 to 2,500 g / mol.

10. (1) a step of reacting a polyol component containing an anhydrosugar alcohol-alkylene oxide adduct and a lipophilic polyol having a number average molecular weight of 200 to 3,000 g / mol 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; Including, the anhydrosugar alcohol-alkylene oxide adduct is obtained by reacting hydroxy groups at both ends or one end of an anhydrosugar alcohol with an alkylene oxide; The method for producing a (meth)acrylic-modified polyurethane composition, wherein the alkylene oxide is a linear alkylene oxide having 2 to 3 carbon atoms or a branched alkylene oxide having 3 carbon atoms.

11. The method for producing a (meth)acrylic-modified polyurethane composition according to claim 10, wherein the polyol component contains 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.

12. (i) a hydrophilic (meth)acrylic-modified polyurethane containing 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; (ii) a lipophilic (meth)acrylic-modified polyurethane containing polymerized units derived from a lipophilic polyol having a number average molecular weight of 200 to 3,000 g / mol; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate; mixing the the anhydrosugar alcohol-alkylene oxide adduct is obtained by reacting hydroxy groups at both ends or one end of an anhydrosugar alcohol with an alkylene oxide; The method for producing a (meth)acrylic-modified polyurethane composition, wherein the alkylene oxide is a linear alkylene oxide having 2 to 3 carbon atoms or a branched alkylene oxide having 3 carbon atoms.

13. (i) the hydrophilic (meth)acrylic-modified polyurethane is produced by a method comprising: (a) a step of reacting an anhydrosugar alcohol-alkylene oxide adduct with a polyisocyanate to produce an intermediate having a terminal isocyanate group; and (b) a step of reacting the intermediate obtained in the step (a) with a hydroxyalkyl (meth)acrylate; (ii) The method for producing the (meth)acrylic-modified polyurethane composition according to claim 12, wherein the lipophilic (meth)acrylic-modified polyurethane is 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.

14. The method for producing a (meth)acrylic-modified polyurethane composition according to claim 12, wherein 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 are mixed with respect to 100 parts by weight of the total amount of the (meth)acrylic-modified polyurethane composition.

15. An adhesive composition comprising the (meth)acrylic-modified polyurethane composition according to any one of claims 1 to 9.

16. An article to which the adhesive composition according to claim 15 is applied.

17. A moisture-absorbing coating composition comprising the (meth)acrylic-modified polyurethane composition according to any one of claims 1 to 9.

18. 18. The moisture-absorbing coating composition of claim 17 for use in anti-fog applications.

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