(METH)acryl-modified polyurethane composition and preparation method therefor, impact reinforcer comprising the (METH)acryl-modified polyurethane composition, epoxy resin composition comprising the impact reinforcer, and adhesive composition comprising the epoxy resin composition

Abstract

The present invention relates to a (meth)acryl-modified polyurethane composition and use thereof. More particularly, the present invention relates to a (meth)acryl-modified polyurethane composition and a preparation method therefor, an impact reinforcer comprising the (meth)acryl-modified polyurethane composition, an epoxy resin composition comprising the impact reinforcer, and an adhesive composition comprising the epoxy resin composition. The (meth)acryl-modified polyurethane composition is prepared by reacting, with hydroxyalkyl(meth)acrylate, an isocyanate prepolymer composition which is a urethane reaction product of polyisocyanate and a polyol composition comprising a specific anhydrosugar alcohol-alkylene glycol composition, is environmentally friendly by respectively delimiting, to specific ranges, the OH equivalent ratio of the anhydrosugar alcohol-alkylene glycol composition to the total OH equivalent of the polyol composition and the total NCO equivalent ratio of polyisocyanate to the total OH equivalent of the polyol composition, and in particular, when used as an impact reinforcer for an epoxy resin, is capable of improving the shear strength and room-temperature impact strength of an adhesive epoxy resin composition comprising same.

Description

(Meth)acrylic-modified polyurethane composition and method for producing the same, impact modifier comprising the (meth)acrylic-modified polyurethane composition, epoxy resin composition comprising the impact modifier, and adhesive composition comprising the epoxy resin composition

[0001] The present invention relates to a (meth)acryl-modified polyurethane composition and its use, and more particularly, to a (meth)acryl-modified polyurethane composition and a method for producing the same, which is produced by reacting a polyol composition comprising a specific anhydrous alcohol-alkylene glycol composition with an isocyanate prepolymer composition, which is a result of a urethane reaction of a polyisocyanate, and a hydroxyalkyl (meth)acrylate, and wherein the OH equivalent ratio of the anhydrous alcohol-alkylene glycol composition to the total OH equivalents of the polyol composition and the total NCO equivalent ratio of the polyisocyanate to the total OH equivalents of the polyol composition are each limited to a specific range, thereby being environmentally friendly and, in particular, when used as an impact modifier for an epoxy resin, improving the shear strength and room temperature impact strength of an adhesive epoxy resin composition comprising the same, an impact modifier comprising the (meth)acryl-modified polyurethane composition, an epoxy resin composition comprising the impact modifier, and an adhesive composition comprising the epoxy resin composition.

[0002] Epoxy resins possess excellent heat resistance, mechanical properties, electrical properties, and adhesiveness. These properties are utilized to create encapsulating materials for wiring boards, circuit boards, and multilayer circuit boards, semiconductor chips, coils, and electrical circuits. Epoxy resins are also used as adhesives, paints, and fiber-reinforced resins.

[0003] Epoxy resins find widespread use as thermosetting resins in numerous applications. They are used as the thermosetting matrix in prepregs, which consist of fibers embedded in a thermosetting matrix. Their toughness, flexibility, adhesion, and chemical resistance also make them suitable for surface coatings, bonding, molding, and laminating. All of these properties find diverse applications in a wide range of industries, including aerospace, automotive, electronics, construction, furniture, green energy, and sporting goods.

[0004] A wide range of epoxy resins are readily available and can be selected based on their reactivity requirements for specific applications. For example, resins can be solid, liquid, or semi-solid, and can have varying reactivity depending on their intended use. The reactivity of epoxy resins is often measured in terms of their epoxy equivalent weight, which is the molecular weight of the resin containing a single reactive epoxy group. The lower the epoxy equivalent weight, the higher the reactivity of the epoxy resin. Different epoxy resin applications require different reactivity requirements, but this varies depending on whether the resin is used as a matrix in fiber-reinforced prepregs, adhesive coatings, or structural adhesives.

[0005] However, epoxy resin itself is too brittle and has low strength, which limits its application range, and in particular, it has poor impact resistance at room temperature.

[0006] Meanwhile, hydrogenated sugars (also called “sugar alcohols”) are compounds obtained by adding hydrogen to the reducing end group of sugars, generally HOCH2(CHOH). nIt has the chemical formula CH2OH (where n is an integer from 2 to 5) and is classified into tetrintol, pentitol, hexitol, and heptitol (having 4, 5, 6, and 7 carbon atoms, respectively) depending on the number of carbon atoms. Among them, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

[0007] Anhydrosugar alcohol is a substance formed by removing one or more water molecules from the interior of hydrogenated sugar. When one water molecule is removed, it has the form of a tetraol with four hydroxyl groups in the molecule. When two water molecules are removed, it has the form of a diol with two hydroxyl groups in the molecule. It can be manufactured using hexitol derived from starch (e.g., Korean Patent Registration No. 10-1079518, Korean Patent Publication No. 10-2012-0066904). Anhydrosugar alcohol has been the subject of much interest for a long time and research on its manufacturing method has been conducted because it is an environmentally friendly substance derived from renewable natural resources. Among these anhydrosugar alcohols, isosorbide manufactured from sorbitol currently has the widest range of industrial applications.

[0008] Anhydrous alcohols have a wide range of applications, including treating heart and vascular diseases, as adhesives for patches, as pharmaceuticals such as mouthwashes, as solvents in cosmetics compositions, and as emulsifiers in the food industry. Furthermore, they can raise the glass transition temperature of polymers such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, improving their strength. As an eco-friendly material derived from natural resources, they are also very useful in the plastics industry, including bioplastics. Furthermore, they are known to be useful as eco-friendly solvents for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

[0009] As such, anhydrous alcohols are receiving much attention due to their diverse potential uses, and their use in actual industries is gradually increasing.

[0010] Therefore, there is a demand for the development of an environmentally friendly additive that utilizes anhydrous sugar alcohol and can complement the above-mentioned shortcomings of epoxy resin, especially an impact modifier that can improve shear strength and room temperature impact strength.

[0011] The purpose of the present invention is to provide a (meth)acryl-modified polyurethane composition and a method for producing the same, which is environmentally friendly because it uses anhydrous sugar alcohol, and which, in particular, can improve the shear strength and room temperature impact strength of an adhesive epoxy resin composition containing the same when used as an impact modifier for an epoxy resin, an impact modifier containing the (meth)acryl-modified polyurethane composition, an epoxy resin composition containing the impact modifier, and an adhesive composition containing the epoxy resin composition.

[0012] A first aspect of the present invention is a (meth)acrylic-modified polyurethane composition prepared by reacting an isocyanate prepolymer composition with a hydroxyalkyl (meth)acrylate,

[0013] The above isocyanate prepolymer composition is manufactured by reacting a polyol composition and a polyisocyanate with urethane,

[0014] The above polyol composition comprises an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol,

[0015] The above anhydrous sugar alcohol-alkylene glycol composition is prepared by addition reaction of an anhydrous sugar alcohol composition and an alkylene oxide,

[0016] The above anhydrous sugar alcohol composition comprises first to fifth polyol components, wherein the first polyol component is a monoanhydrous sugar alcohol, the second polyol component is a dianhydrous sugar alcohol, the third polyol component is a polysaccharide alcohol represented by the following chemical formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from a polysaccharide alcohol represented by the following chemical formula 1, and the fifth polyol component is at least one polymer selected from among the first to fourth polyol components.

[0017] The ratio of the OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition to the total OH equivalent of the polyol composition (OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalent of the polyol composition) is greater than 0.1 and less than 0.6,

[0018] The ratio of the total NCO equivalent of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalent of the polyisocyanate / total OH equivalent of the polyol composition) is greater than 1.4 and less than 2.0,

[0019] Provided is a (meth)acrylic-modified polyurethane composition:

[0020] [Chemical Formula 1]

[0021]

[0022] In the above chemical formula 1, n is an integer from 0 to 4.

[0023] A second aspect of the present invention is a method for producing a (meth)acrylic-modified polyurethane composition,

[0024] (1) a step of producing an isocyanate prepolymer composition having an isocyanate terminal by subjecting a polyol composition and a polyisocyanate to a urethane reaction; and

[0025] (2) a step of reacting the isocyanate prepolymer composition obtained from step (1) with hydroxyalkyl (meth)acrylate;

[0026] The above polyol composition comprises an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol,

[0027] The above anhydrous sugar alcohol-alkylene glycol composition is prepared by addition reaction of an anhydrous sugar alcohol composition and an alkylene oxide,

[0028] The above anhydrous sugar alcohol composition comprises first to fifth polyol components, wherein the first polyol component is a monoanhydrous sugar alcohol, the second polyol component is a dianhydrous sugar alcohol, the third polyol component is a polysaccharide alcohol represented by the above chemical formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the above chemical formula 1, and the fifth polyol component is at least one polymer selected from the above first to fourth polyol components.

[0029] The ratio of the OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition to the total OH equivalent of the polyol composition (OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalent of the polyol composition) is greater than 0.1 and less than 0.6,

[0030] The ratio of the total NCO equivalent of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalent of the polyisocyanate / total OH equivalent of the polyol composition) is greater than 1.4 and less than 2.0,

[0031] A method for producing a (meth)acrylic-modified polyurethane composition is provided.

[0032] A third aspect of the present invention provides an impact modifier comprising a (meth)acrylic-modified polyurethane composition according to the first aspect of the present invention.

[0033] A fourth aspect of the present invention provides an epoxy resin composition comprising an impact modifier according to the third aspect of the present invention; and an epoxy resin.

[0034] A fifth aspect of the present invention provides a two-component curable composition comprising a subject component comprising an epoxy resin composition according to the fourth aspect of the present invention; and a curing agent component.

[0035] A sixth aspect of the present invention provides an adhesive composition obtained by mixing a subject component including an epoxy resin composition according to the fourth aspect of the present invention and a curing agent component.

[0036] A seventh aspect of the present invention provides a method for producing an adhesive composition, comprising the step of mixing a subject component comprising an epoxy resin composition according to the fourth aspect of the present invention and a curing agent component.

[0037] The eighth aspect of the present invention provides an article to which the adhesive composition according to the seventh aspect of the present invention is applied.

[0038] When the (meth)acrylic-modified polyurethane composition according to the present invention is used as an impact modifier for an epoxy resin, it can improve the shear strength and room temperature impact strength of an adhesive epoxy resin composition containing the same.

[0039] In particular, according to the present invention, a room-temperature curing epoxy adhesive composition can be provided that exhibits a shear strength of 20 MPa or more, which is equivalent to or higher than that of a conventional room-temperature curing epoxy adhesive composition, while at the same time exhibiting excellent room-temperature impact resistance of about 22 N / mm or more, which is difficult to secure in a conventional composition.

[0040] In addition, since the (meth)acrylic-modified polyurethane composition according to the present invention is manufactured from an anhydrous sugar alcohol composition, which is a polyol composition obtained by utilizing a by-product obtained in the process of manufacturing an internal dehydration product of hydrogenated sugar, it can increase economic efficiency and improve environmental friendliness by solving the problem of by-product disposal.

[0041] 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.

[0042] Hereinafter, the present invention will be described in more detail.

[0043] [(Meth)acrylic-modified polyurethane composition and method for producing the same]

[0044] The (meth)acryl-modified polyurethane composition, which is a first aspect of the present invention, is prepared by reacting an isocyanate prepolymer composition with a hydroxyalkyl (meth)acrylate, wherein the isocyanate prepolymer composition is prepared by reacting a polyol composition with a polyisocyanate to form a urethane, the polyol composition comprises an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol, the anhydrous sugar alcohol-alkylene glycol composition is prepared by addition reacting an anhydrous sugar alcohol composition with an alkylene oxide, and the anhydrous sugar alcohol composition comprises first to fifth polyol components, wherein the first polyol component is a monoanhydrous sugar alcohol, the second polyol component is a dianhydrous sugar alcohol, the third polyol component is a polysaccharide alcohol represented by the following chemical formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from a polysaccharide alcohol represented by the following chemical formula 1, and the fifth polyol component comprises a polyol comprising the first to fourth polyol components. At least one polymer selected from among polyol components, wherein the ratio of the OH equivalent of the anhydrosugar alcohol-alkylene glycol composition to the total OH equivalent of the polyol composition (OH equivalent of the anhydrosugar alcohol-alkylene glycol composition / total OH equivalent of the polyol composition) is greater than 0.1 and less than 0.6, and the ratio of the total NCO equivalent of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalent of the polyisocyanate / total OH equivalent of the polyol composition) is greater than 1.4 and less than 2.0:

[0045] [Chemical Formula 1]

[0046]

[0047] In the above chemical formula 1, n is an integer from 0 to 4.

[0048] Anhydrous alcohol composition

[0049] At least one, preferably at least two, and more preferably all of the first polyol component, monoanhydrosugar alcohol, which is included in the above anhydrosugar alcohol composition; the second polyol component, dianhydrosugar alcohol; the third polyol component, polysaccharide alcohol; the fourth polyol component, an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol; and at least one polymer selected from the first to fourth polyol components, which are the fifth polyol components, can be obtained by a process of hydrogenating a glucose-containing saccharide composition (for example, a saccharide composition including a polysaccharide higher than a disaccharide, including glucose, mannose, fructose, and maltose) to produce a hydrogenated saccharide composition, heating the obtained hydrogenated saccharide composition in the presence of an acid catalyst to cause a dehydration reaction, and subjecting the obtained dehydration reaction product to thin film distillation. More specifically, all of the first to fifth polyol components included in the anhydrous sugar alcohol composition of the present invention may be byproducts remaining after thin film distillation of the obtained dehydration reaction product to obtain a thin film distillate.

[0050] The above first polyol component, monoanhydrosugar alcohol, is an anhydrosugar alcohol formed by removing one water molecule from the interior of hydrogenated sugar, and has a tetraol form with four hydroxyl groups in the molecule. In the present invention, the type of monoanhydrosugar alcohol is not particularly limited, but preferably, it may be monoanhydrosugar hexitol, and more specifically, it may be 1,4-anhydrohexitol, 3,6-anhydrohexitol, 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more thereof.

[0051] The second polyol component, dianhydrosugar alcohol, is an anhydrosugar alcohol formed by the removal of two water molecules from the interior of hydrogenated sugars. It has a diol form with two hydroxyl groups in the molecule, and can be manufactured using hexitol derived from starch. Since dianhydrosugar alcohol is an environmentally friendly substance derived from renewable natural resources, it has long been the subject of much interest and research into its manufacturing method. Among these dianhydrosugar alcohols, isosorbide, manufactured from sorbitol, currently has the widest range of industrial applications.

[0052] In the present invention, the type of the dianhydrosugar alcohol is not particularly limited, but preferably, it may be a dianhydrosugar hexitol, and more specifically, it may be 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

[0053] In one specific example, the polysaccharide alcohol represented by the chemical formula 1, which is the third polyol component, can be produced from a hydrogenation reaction of a polysaccharide higher than a disaccharide, including maltose.

[0054] In one specific example, the anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the fourth polyol component, the chemical formula 1, may be selected from a compound represented by the following chemical formula 2, a compound represented by the following chemical formula 3, or a mixture thereof:

[0055] [Chemical Formula 2]

[0056]

[0057] [Chemical Formula 3]

[0058]

[0059] In the above chemical formulas 2 and 3,

[0060] n is an integer from 0 to 4, each independently.

[0061] In one specific example, the at least one polymer selected from the first to fourth polyol components, which is the fifth polyol component, may include at least one selected from the group consisting of condensation polymers prepared from the following condensation polymerization reaction:

[0062] - Condensation polymerization reaction of the first polyol component,

[0063] - Condensation polymerization reaction of the second polyol component,

[0064] - Condensation polymerization reaction of the third polyol component,

[0065] - Condensation polymerization reaction of the fourth polyol component,

[0066] - Condensation polymerization reaction of the first polyol component and the second polyol component,

[0067] - Condensation polymerization reaction of the first polyol component and the third polyol component,

[0068] - Condensation polymerization reaction of the first polyol component and the fourth polyol component,

[0069] - Condensation polymerization reaction of the second polyol component and the third polyol component,

[0070] - Condensation polymerization reaction of the second polyol component and the fourth polyol component,

[0071] - Condensation polymerization reaction of the third polyol component and the fourth polyol component,

[0072] - Condensation polymerization reaction of the first polyol component, the second polyol component, and the third polyol component,

[0073] - Condensation polymerization reaction of the first polyol component, the second polyol component, and the fourth polyol component,

[0074] - Condensation polymerization reaction of the first polyol component, the third polyol component, and the fourth polyol component,

[0075] - Condensation polymerization reaction of the second polyol component, the third polyol component and the fourth polyol component, or

[0076] - Condensation polymerization reaction of the first polyol component, the second polyol component, the third polyol component, and the fourth polyol component.

[0077] In one specific example, the number average molecular weight (Mn: unit g / mol) of the anhydrous sugar alcohol composition may be 193 or more, 195 or more, 200 or more, 202 or more, 205 or more, or 208 or more, and may also be 1,589 or less, 1,560 or less, 1,550 or less, 1,520 or less, 1,500 or less, 1,490 or less, or 1,480 or less.

[0078] In one specific example, the number average molecular weight (Mn) of the anhydrous sugar alcohol composition may be 193 to 1,589, specifically 195 to 1,550, more specifically 200 to 1,520, even more specifically 202 to 1,500, and even more specifically 205 to 1,490. In this specific example, if the number average molecular weight of the anhydrous sugar alcohol composition is less than 193, compatibility between the anhydrous sugar alcohol-alkylene glycol composition manufactured therefrom and the polyisocyanate may be poor, and conversely, if the number average molecular weight of the anhydrous sugar alcohol composition exceeds 1,589, when a (meth)acrylic-modified polyurethane composition manufactured therefrom is used as an impact modifier for an epoxy resin, the viscosity becomes too high as the number average molecular weight increases, thereby deteriorating workability.

[0079] In one specific embodiment, the polydispersity index (PDI) of the anhydrous sugar alcohol composition may be 1.13 or greater, 1.15 or greater, 1.20 or greater, 1.23 or greater, or 1.25 or greater, and may also be 3.41 or less, 3.40 or less, 3.35 or less, 3.30 or less, 3.25 or less, 3.22 or less, or 3.19 or less.

[0080] In one specific example, the polydispersity index (PDI) of the anhydrous sugar alcohol composition may be 1.13 to 3.41, specifically 1.13 to 3.40, more specifically 1.15 to 3.35, even more specifically 1.20 to 3.25, and even more specifically 1.23 to 3.22. In this specific example, if the polydispersity index of the anhydrous sugar alcohol composition is less than 1.13, the compatibility between the anhydrous sugar alcohol-alkylene glycol composition prepared therefrom and the polyisocyanate may be poor, and conversely, if the polydispersity index of the anhydrous sugar alcohol composition exceeds 3.41, when the (meth)acrylic-modified polyurethane composition prepared therefrom is used as an impact modifier for an epoxy resin, the uniformity of the (meth)acrylic-modified polyurethane composition is lowered, so that the physical properties of the epoxy resin composition are lowered.

[0081] In one specific embodiment, the average number of -OH groups per molecule in the anhydrous sugar alcohol composition may be at least 2.54, at least 2.60, at least 2.65, at least 2.70, at least 2.75, or at least 2.78, and may also be at most 21.36, at most 21.30, at most 21.0, at most 20.5, at most 20.0, at most 19.95, or at most 19.92.

[0082] In one specific example, the average number of -OH groups per molecule in the anhydrous sugar alcohol composition may be 2.54 to 21.36, more specifically, 2.60 to 21.30, and even more specifically, 2.65 to 21.0. In this specific example, if the average number of -OH groups per molecule in the anhydrous sugar alcohol composition is less than 2.54, when the (meth)acrylic-modified polyurethane composition manufactured using the same is used as an impact modifier for an epoxy resin, a linear (meth)acrylic-modified polyurethane is manufactured, thereby deteriorating the physical properties of the epoxy resin composition. Conversely, if the average number of -OH groups per molecule in the anhydrous sugar alcohol composition exceeds 21.36, the compatibility between the anhydrous sugar alcohol-alkylene glycol composition manufactured therefrom and the polyisocyanate may deteriorate.

[0083] In a preferred embodiment, the anhydrous sugar alcohol composition satisfies the following i) to iii):

[0084] i) The number average molecular weight (Mn) of the anhydrous alcohol composition is 193 to 1,589 g / mol;

[0085] ii) the polydispersity index (PDI) of the anhydrous sugar alcohol composition is 1.13 to 3.41;

[0086] iii) The average number of -OH groups per molecule in the anhydrous alcohol composition is 2.54 to 21.36.

[0087] In one specific example, the anhydrous sugar alcohol composition may include, for example, 0.1 to 20 wt%, specifically 0.6 to 20 wt%, more specifically 0.7 to 15 wt% of the first polyol component, based on the total weight of the composition, 0.1 to 28 wt%, specifically 1 to 25 wt%, more specifically 3 to 20 wt% of the second polyol component, the total content of the third polyol component and the fourth polyol component may be 0.1 to 6.5 wt%, specifically 0.5 to 6.4 wt%, more specifically 1 to 6.3 wt%, and the fifth polyol component may include, but is not particularly limited to, 55 to 90 wt%, specifically 60 to 89.9 wt%, more specifically 70 to 89.9 wt%.

[0088] In one specific example, the anhydrous sugar alcohol composition may be prepared by hydrogenating a glucose-containing sugar composition (e.g., a sugar composition including a polysaccharide higher than a disaccharide, including glucose; mannose; fructose; and maltose) to produce a hydrogenated sugar composition, heating the obtained hydrogenated sugar composition in the presence of an acid catalyst to cause a dehydration reaction, and thin-film distilling the obtained dehydration reaction product. More specifically, the anhydrous sugar alcohol composition may be prepared by thin-film distilling the obtained dehydration reaction product to obtain a thin-film distillate, and then the remaining byproduct may be obtained.

[0089] More specifically, a hydrogenation reaction is performed on the glucose-containing sugar composition under hydrogen pressure conditions of 30 to 80 atm and heating conditions of 110 to 135°C to produce a hydrogenated sugar composition, a dehydration reaction of the obtained hydrogenated sugar composition is performed under reduced pressure conditions of 1 to 100 mmHg and heating conditions of 105 to 200°C to obtain a dehydration reaction product, and thin film distillation of the obtained dehydration reaction product can be performed under reduced pressure conditions of 2 mbar or less and heating conditions of 150 to 175°C, but is not limited thereto.

[0090] In one specific embodiment, the glucose content of the glucose-containing saccharide composition may be 41 wt% or more, 42 wt% or more, 45 wt% or more, 47 wt% or more, or 50 wt% or more, and 99.5 wt% or less, 99 wt% or less, 98.5 wt% or less, 98 wt% or less, 97.5 wt% or less, or 97 wt% or less, based on the total weight of the saccharide composition, for example, 41 to 99.5 wt%, 45 to 98.5 wt%, or 50 to 98 wt%.

[0091] When the glucose content in the above-mentioned sugar composition is less than 41 wt%, the number average molecular weight (Mn) of the anhydrous sugar alcohol composition becomes too high, so that when the (meth)acrylic-modified polyurethane composition manufactured using the same is used as an impact modifier for an epoxy resin, there is no additional property improvement effect, and the economic feasibility may decrease due to an increase in material cost, and when it exceeds 99.5 wt%, the number average molecular weight of the anhydrous sugar alcohol composition becomes too low, so that the strength characteristics of the (meth)acrylic-modified polyurethane composition manufactured using the same may deteriorate.

[0092] In one specific example, the content of the polysaccharide alcohol (a sugar alcohol higher than a disaccharide) included in the hydrogenated sugar composition may be 0.8 wt% or more, 1 wt% or more, 2 wt% or more, or 3 wt% or more, and may be 57 wt% or less, 55 wt% or less, 52 wt% or less, 50 wt% or less, or 48 wt% or less, based on the total dry weight of the hydrogenated sugar composition (wherein the dry weight means the weight of the solid content remaining after removing moisture from the hydrogenated sugar composition), for example, 0.8 to 57 wt%, 1 to 55 wt%, or 3 to 50 wt%.

[0093] When the content of polysaccharide alcohol in the hydrogenated sugar composition is less than 0.8 wt%, the effect of increasing fluidity due to polysaccharide alcohol and anhydrous sugar alcohol derived therefrom is minimal, so that the distillation yield of the dianhydrous sugar alcohol (e.g., isosorbide) may be low, and when it exceeds 57 wt%, there is a problem that the distillation yield of the dianhydrous sugar alcohol is significantly low when the dehydration reaction product of the hydrogenated sugar composition is subjected to thin film distillation.

[0094] In addition, when the polysaccharide alcohol content in the hydrogenated sugar composition is less than 0.8 wt%, when an anhydrous sugar alcohol composition is prepared using the hydrogenated sugar composition, an isocyanate prepolymer composition is prepared by applying the anhydrous sugar alcohol composition, and a (meth)acryl-modified polyurethane composition is prepared using the same, and when the same is used as an impact modifier for an epoxy resin, the adhesive properties of the epoxy resin composition may deteriorate, such as a decrease in adhesive strength to an adherend and surface peeling, and when the content exceeds 57 wt%, there is a problem that the composition is cured or gelled in the process of preparing an anhydrous sugar alcohol composition using the hydrogenated sugar composition, and using the same to prepare an isocyanate prepolymer composition or to prepare a (meth)acryl-modified polyurethane composition.

[0095] Addition reaction with alkylene oxide and anhydrous sugar alcohol composition

[0096] In the present invention, the anhydrous sugar alcohol-alkylene glycol composition means a composition obtained by addition reaction of the above-mentioned anhydrous sugar alcohol composition and an alkylene oxide, and accordingly, the anhydrous sugar alcohol-alkylene glycol composition includes an adduct obtained by reacting an alkylene oxide with a hydroxy group at one or more terminals of each of the first to fifth polyol components, and specifically, the anhydrous sugar alcohol-alkylene glycol composition includes an alkylene oxide adduct of the first polyol component (hereinafter referred to as the “first anhydrous sugar alcohol-alkylene glycol”), an alkylene oxide adduct of the second polyol component (hereinafter referred to as the “second anhydrous sugar alcohol-alkylene glycol”), an alkylene oxide adduct of the third polyol component (hereinafter referred to as the “third anhydrous sugar alcohol-alkylene glycol”), an alkylene oxide adduct of the fourth polyol component (hereinafter referred to as the “fourth anhydrous sugar alcohol-alkylene glycol”), and It includes an alkylene oxide adduct of the fifth polyol component (hereinafter referred to as “the fifth anhydrosugar alcohol-alkylene glycol”).

[0097] In one specific 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.

[0098] In one specific example, the amount of the alkylene oxide to be reacted may be from 100 parts by weight to 500 parts by weight per 100 parts by weight of the anhydrous sugar alcohol composition. If the amount of alkylene oxide added per 100 parts by weight of the anhydrous sugar alcohol composition is too low than the above level, the reactivity between the prepared anhydrous sugar alcohol-alkylene glycol composition and the polyisocyanate may decrease, so that their reaction may not occur, and thus the isocyanate prepolymer composition may not be provided. Conversely, if the amount of alkylene oxide added is too high than the above level, the mechanical properties (e.g., T-peel strength) of a (meth)acrylic-modified polyurethane composition prepared by utilizing the prepared anhydrous sugar alcohol-alkylene glycol composition may deteriorate when used as an impact modifier for an epoxy resin.

[0099] More specifically, the amount of the alkylene oxide reacted per 100 parts by weight of the anhydrous sugar alcohol composition may be, for example, 100 parts by weight or more, 120 parts by weight or more, 150 parts by weight or more, 170 parts by weight or more, or 200 parts by weight or more, and may also be 500 parts by weight or less, 480 parts by weight or less, 450 parts by weight or less, 430 parts by weight or less, or 400 parts by weight or less, but is not limited thereto.

[0100] In one specific example, the addition reaction of the anhydrous sugar alcohol composition and the alkylene oxide may be performed at a temperature of, for example, 100°C or higher, more specifically, 100°C to 140°C, for 1 hour or longer, more specifically, 1 hour to 5 hours, but is not limited thereto.

[0101] polyether polyol

[0102] In one embodiment, the polyether polyol may comprise a polyalkylene glycol, more specifically, a poly(C1-C6)alkylene glycol.

[0103] In one specific embodiment, the polyalkylene glycol may be selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, or combinations thereof.

[0104] In one specific example, the number average molecular weight (Mn: unit g / mol) of the polyether polyol may be 500 or more, 600 or more, 700 or more, 800 or more, 900 or more, or 1,000 or more, and may also be less than 4,000, 3,900 or less, 3,800 or less, 3,700 or less, 3,600 or less, 3,500 or less, 3,400 or less, 3,300 or less, 3,200 or less, 3,100 or less, or 3,000 or less, but is not limited thereto. Preferably, the number average molecular weight of the polyether polyol may be 500 or more to less than 4,000, or 1,000 to 3,000. If the number average molecular weight of the polyether polyol is too low compared to the above level, the reaction with polyisocyanate may not proceed, and conversely, if it is too high compared to the above level, there may be a problem in that the economic feasibility may be reduced due to an increase in material cost without any additional property improvement effect.

[0105] polyol composition

[0106] The above polyol composition comprises the anhydrous sugar alcohol-alkylene glycol composition described above and a polyether polyol.

[0107] In the present invention, the ratio of the OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition to the total OH equivalent of the polyol composition (OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalent of the polyol composition, hereinafter also referred to as “OH equivalent ratio”) is more than 0.1 and less than 0.6. When the OH equivalent ratio is 0.1 or less or 0.6 or more, when a (meth)acrylic-modified polyurethane composition manufactured by utilizing such a polyol composition is used as an impact modifier for an epoxy resin, the room temperature impact resistance of the cured product of the epoxy resin composition becomes very poor.

[0108] In one specific embodiment, the OH equivalent ratio of the anhydrosugar alcohol-alkylene glycol composition to the total OH equivalent of the polyol composition may be greater than 0.1, 0.11 or more, 0.12 or more, 0.13 or more, 0.14 or more, 0.15 or more, 0.16 or more, 0.17 or more, 0.18 or more, 0.19 or more, or 0.2 or more, and may also be less than 0.6, 0.59 or less, 0.58 or less, 0.57 or less, 0.56 or less, 0.55 or less, 0.54 or less, 0.53 or less, 0.52 or less, 0.51 or less, or 0.5 or less, but is not limited thereto.

[0109] In one specific example, the polyol composition may include 2.4 to 24.4 parts by weight of the anhydrous sugar alcohol-alkylene glycol composition and 75.6 to 97.6 parts by weight of the polyether polyol, based on 100 parts by weight of the polyol composition. If the contents of the anhydrous sugar alcohol-alkylene glycol composition and the polyether polyol in the polyol composition are each outside the above range, when a (meth)acrylic-modified polyurethane composition manufactured by utilizing such polyol composition is used as an impact modifier for an epoxy resin, the mechanical properties (e.g., shear strength and / or room temperature impact resistance) of a cured product of the epoxy resin composition may deteriorate.

[0110] More specifically, the content of the anhydrous sugar alcohol-alkylene glycol composition in the polyol composition may be 2.4 parts by weight or more, 2.5 parts by weight or more, 3.0 parts by weight or more, 3.5 parts by weight or more, 4.0 parts by weight or more, 4.5 parts by weight or more, 5.0 parts by weight or more, or 5.1 parts by weight or more, and may also be 24.4 parts by weight or less, 24 parts by weight or less, 23.5 parts by weight or less, 23 parts by weight or less, 22.5 parts by weight or less, 22 parts by weight or less, 21.5 parts by weight or less, 21 parts by weight or less, 20.5 parts by weight or less, 20 parts by weight or less, 19.5 parts by weight or less, 19 parts by weight or less, 18.5 parts by weight or less, 18 parts by weight or less, or 17.8 parts by weight or less, based on 100 parts by weight of the polyol composition.

[0111] In addition, more specifically, the polyether polyol content in the polyol composition may be 75.6 parts by weight or more, 76 parts by weight or more, 77 parts by weight or more, 78 parts by weight or more, 79 parts by weight or more, 80 parts by weight or more, 81 parts by weight or more, 82 parts by weight or more, or 82.2 parts by weight or more, based on 100 parts by weight of the polyol composition, and may also be 97.6 parts by weight or less, 97 parts by weight or less, 96 parts by weight or less, 95 parts by weight or less, or 94.9 parts by weight or less.

[0112] In one embodiment, the polyol composition may optionally further include a polyol component other than the anhydrous sugar alcohol-alkylene glycol composition and the polyether polyol.

[0113] In one specific example, the anhydrous sugar alcohol-alkylene glycol composition and the polyol component other than the polyether polyol may be selected from the group consisting of polyester polyol, polycaprolactone diol, a polymer polyol obtained by polymerizing these polyols with a vinyl compound, or a combination thereof. The vinyl compound is frequently used, such as acrylonitrile, styrene, and methyl methacrylonitrile, and typically, acrylonitrile may be used alone or in a mixture with styrene.

[0114] Urethane reaction with polyisocyanate and polyol composition

[0115] The isocyanate prepolymer composition used in the production of the (meth)acrylic-modified polyurethane composition of the present invention is produced by subjecting the polyol composition described above to a urethane reaction with polyisocyanate.

[0116] In the present invention, the polyisocyanate may be used without particular limitation as long as it can be used in the production of polyurethane. For example, a polyisocyanate selected from the group consisting of aliphatic polyisocyanate, cycloaliphatic polyisocyanate, araliphatic polyisocyanate, aromatic polyisocyanate, heterocyclic polyisocyanate, or a combination thereof may be used, and both unmodified polyisocyanate and modified polyisocyanate may be used.

[0117] In one embodiment, examples of the polyisocyanate include aromatic polyisocyanates such as methylenediphenyl diisocyanate (MDI) (e.g., 2,4- or 4,4'-methylenediphenyl diisocyanate), xylylene diisocyanate (XDI), m- or p-tetramethylxylylene 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'-dibenzyldiisocyanate; Aliphatic 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 polyisocyanate; or a combination thereof, but is not limited thereto.

[0118] In another specific embodiment, examples of the polyisocyanate include methylenediphenyl 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 mixed with 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 is not limited thereto.

[0119] More specifically, the polyisocyanate may be methylenediphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.

[0120] In one embodiment, the urethane reaction may be carried out in the presence of a catalyst, such as an amine catalyst, an organometallic catalyst, or a mixture thereof.

[0121] The type of the above amine catalyst is not particularly limited, but preferably, one or a mixture of two or more selected from among tertiary amine catalysts can be used, and more specifically, one selected from the group consisting of triethylene diamine, triethylamine, N-methyl morpholine, N-ethyl morpholine, or a combination thereof can be used.

[0122] The type of the above-mentioned organometallic catalyst is also not particularly limited, but for example, an organotin catalyst, more specifically, one selected from the group consisting of tin octylate, dibutyltin dilaurate (DBTDL), tin bis[2-ethylhexanoate], or a combination thereof, can be used.

[0123] In one specific example, the urethane reaction may be performed 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), but is not limited thereto.

[0124] In the present invention, the ratio of the total NCO equivalents of the polyisocyanate to the total OH equivalents of the polyol composition (total NCO equivalents of the polyisocyanate / total OH equivalents of the polyol composition, hereinafter also referred to as “NCO / OH index”) is greater than 1.4 and less than 2.0. When the NCO / OH index is 1.4 or less, when the (meth)acrylic-modified polyurethane composition manufactured by utilizing such a polyol composition and polyisocyanate is used as an impact modifier for an epoxy resin, the shear strength of the cured product of the epoxy resin composition becomes poor and the impact resistance at room temperature becomes very poor. On the other hand, when the NCO / OH index is 2.0 or more, when the (meth)acrylic-modified polyurethane composition manufactured by utilizing such a polyol composition and polyisocyanate is used as an impact modifier for an epoxy resin, the shear strength of the cured product of the epoxy resin composition becomes very poor and the impact resistance at room temperature becomes poor.

[0125] In one specific example, the NCO / OH index may be greater than 1.4, greater than 1.41, greater than 1.43, greater than 1.45, greater than 1.47, greater than 1.49, or greater than 1.5, and may also be less than 2.0, less than or equal to 1.99, less than or equal to 1.97, less than or equal to 1.95, less than or equal to 1.93, less than or equal to 1.91, or less than or equal to 1.9, but is not limited thereto.

[0126] In the present invention, by controlling the OH equivalent ratio of the anhydrous sugar alcohol-alkylene glycol composition to the total OH equivalent of the polyol composition described above and the NCO / OH index within a specific range, the number average molecular weight of the (meth)acrylic-modified polyurethane composition can be controlled within a specific range.

[0127] That is, when the amount of polyether polyol (e.g., polytetramethylene ether glycol (PTMEG)) in the polyol component increases and the amount of the anhydrosugar alcohol-alkylene glycol composition decreases, the number average molecular weight of the (meth)acryl-modified polyurethane composition increases. In addition, when the NCO / OH index decreases, the number average molecular weight of the (meth)acryl-modified polyurethane composition relatively increases, and conversely, when the NCO / OH index increases, the number average molecular weight of the (meth)acryl-modified polyurethane composition relatively decreases.

[0128] In one specific example, the number average molecular weight (Mn) of the (meth)acrylic-modified polyurethane composition may be greater than 5,500 g / mol and less than 7,500 g / mol. If the number average molecular weight of the (meth)acrylic-modified polyurethane composition is excessively lower than the above level or, conversely, excessively higher than the above level, workability may deteriorate. In addition, if the number average molecular weight is excessively lower than the above level, the viscosity of the epoxy resin composition including the (meth)acrylic-modified polyurethane composition may decrease, and thus, adhesive loss may occur when the epoxy resin composition is cured, and if the number average molecular weight is excessively higher than the above level, the epoxy resin composition including the (meth)acrylic-modified polyurethane composition may not be evenly adhered within the bonding section when applied as an adhesive.

[0129] More specifically, the number average molecular weight (Mn: g / mol) of the (meth)acrylic-modified polyurethane composition may be greater than 5,500, greater than 5,600, greater than 5,700, greater than 5,800, greater than 5,900, or greater than 6,000, and may be less than 7,500, less than 7,450, less than 7,400, less than 7,350, less than 7,300, or less than 7,250, but is not limited thereto.

[0130] Hydroxyalkyl (meth)acrylate and its reaction with isocyanate prepolymer composition

[0131] The (meth)acrylic-modified polyurethane composition of the present invention is prepared by reacting the isocyanate prepolymer composition described above with a hydroxyalkyl (meth)acrylate.

[0132] The above hydroxyalkyl (meth)acrylate 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, more specifically, a hydroxy-C 1-8 Alkyl (meth)acrylate, i.e. linear C having a hydroxy group 1-8 Alkyl acrylate, branched C with hydroxyl group 3-8 Alkyl acrylate, linear C with hydroxyl group 1-8 Alkyl methacrylate, branched C with hydroxy group 3-8 It may be an alkyl methacrylate or a combination thereof, and more specifically, it may be, but is not limited to, hydroxymethyl acrylate, 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.

[0133] 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.

[0134] In one embodiment, the reaction of the isocyanate prepolymer composition 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 period of time (e.g., 0.1 to 5 hours, preferably 0.5 to 3 hours).

[0135] A second aspect of the present invention comprises the steps of: (1) producing an isocyanate prepolymer composition having an isocyanate terminal by subjecting a polyol composition and a polyisocyanate to a urethane reaction; And (2) a step of reacting the isocyanate prepolymer composition obtained from the step (1) with a hydroxyalkyl (meth)acrylate; wherein the polyol composition comprises an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol, and the anhydrous sugar alcohol-alkylene glycol composition is prepared by addition reacting the anhydrous sugar alcohol composition with an alkylene oxide, and the anhydrous sugar alcohol composition comprises first to fifth polyol components, wherein the first polyol component is a monoanhydrous sugar alcohol, the second polyol component is a dianhydrous sugar alcohol, the third polyol component is a polysaccharide alcohol represented by the chemical formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the chemical formula 1, and the fifth polyol component is at least one polymer selected from among the first to fourth polyol components, and the total OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition is A method for producing a (meth)acrylic-modified polyurethane composition, wherein the ratio of OH equivalents (OH equivalents of anhydrous sugar alcohol-alkylene glycol composition / total OH equivalents of polyol composition) is greater than 0.1 and less than 0.6, and the ratio of total NCO equivalents of polyisocyanate to total OH equivalents of the polyol composition (total NCO equivalents of polyisocyanate / total OH equivalents of polyol composition) is greater than 1.4 and less than 2.0.

[0136] In the method for producing a (meth)acryl-modified polyurethane composition according to the present invention, the descriptions of the anhydrous sugar alcohol composition, alkylene oxide, anhydrous sugar alcohol-alkylene glycol composition, polyether polyol, polyisocyanate, isocyanate prepolymer composition and hydroxyalkyl (meth)acrylate are as described above.

[0137] In one specific example, in the method for producing a (meth)acryl-modified polyurethane composition, (1) the step of producing an isocyanate prepolymer composition having an isocyanate terminal by urethane reaction of a polyol composition and a polyisocyanate may 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 60 to 90° C.) for an appropriate time (e.g., 0.1 to 5 hours, preferably 0.5 to 3 hours), and (2) the step of reacting the isocyanate prepolymer composition obtained from step (1) with a hydroxyalkyl (meth)acrylate may 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 60 to 90° C.). It can be performed at 100°C, preferably 50 to 70°C) for an appropriate time (e.g., 0.1 to 5 hours, preferably 0.5 to 3 hours).

[0138] [Impact modifier, epoxy resin composition, two-component curable composition, adhesive composition, and article to which the adhesive composition is applied]

[0139] The present invention also provides an impact modifier comprising the (meth)acrylic-modified polyurethane composition of the present invention.

[0140] The present invention also provides an epoxy resin composition comprising the impact modifier of the present invention described above; and an epoxy resin.

[0141] The present invention also provides a two-component curable composition comprising a subject component comprising the epoxy resin composition of the present invention described above; and a curing agent component.

[0142] The present invention also provides an adhesive composition obtained by mixing a subject component including the epoxy resin composition of the present invention described above and a hardener component.

[0143] The present invention also provides a method for producing an adhesive composition, comprising a step of mixing a subject component including the epoxy resin composition of the present invention described above and a curing agent component.

[0144] The present invention also provides an article to which the adhesive composition of the present invention is applied.

[0145] In one specific example, the amount of the impact modifier included in the epoxy resin composition of the present invention may be more than 10 parts by weight and less than 35 parts by weight based on 100 parts by weight of the total epoxy resin composition. If the content of the impact modifier in 100 parts by weight of the epoxy resin composition is 10 parts by weight or less, the shear strength and room temperature impact resistance of the cured product of the epoxy resin composition may become very poor, and even if the content of the impact modifier is 35 parts by weight or more, the shear strength and room temperature impact resistance of the cured product of the epoxy resin composition may become very poor.

[0146] More specifically, the content of the impact modifier in 100 parts by weight of the epoxy resin composition may be more than 10 parts by weight, 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, or 15 parts by weight or more, and may also be less than 35 parts by weight, 34 parts by weight or less, 33 parts by weight or less, 32 parts by weight or less, 31 parts by weight or less, or 30 parts by weight or less.

[0147] The above epoxy resins can be solid, liquid, or semi-solid, and can have various reactivities depending on their intended use. The reactivity of epoxy resins is often measured in terms of their epoxy equivalent weight, which is the molecular weight of the resin containing a single reactive epoxy group. The lower the epoxy equivalent weight, the higher the reactivity of the epoxy resin.

[0148] In one specific example, the epoxy resin may be selected from the group consisting of, but is not limited to, a bisphenol A-type epoxy resin such as a bisphenol A-epichlorohydrin resin, a bisphenol A diglycidyl ether resin, a novolac-type epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, a glycidyl ester-type epoxy resin, a brominated epoxy resin, a bio-derived epoxy resin, an epoxidized soybean oil, or a combination thereof.

[0149] In another specific example, the epoxy resin may be a novolac-type epoxy resin such as a phenol novolac-type epoxy resin, a cresol novolac-type epoxy resin, a bisphenol-A-type epoxy resin (e.g., bisphenol A-epichlorohydrin resin, diglycidyl ether resin of bisphenol A, etc.), a bisphenol-F-type epoxy resin, an aromatic glycidylamine-type epoxy resin such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane-type glycidylamine, aminophenol-type glycidylamine, a hydroquinone-type epoxy resin, a biphenyl-type epoxy resin, a stilbene-type epoxy resin, a triphenolmethane-type epoxy resin, a triphenolpropane-type epoxy resin, an alkyl-modified triphenolmethane-type epoxy resin, a triazine nucleus-containing epoxy resin, a dicyclopentadiene-modified phenol-type epoxy resin, a naphthol-type epoxy resin, a naphthalene-type epoxy resin, a phenylene and / or Examples thereof include, but are not limited to, those selected from the group consisting of aralkyl epoxy resins such as phenol aralkyl epoxy resins having a biphenylene skeleton, naphthol aralkyl epoxy resins having a phenylene and / or biphenylene skeleton, aliphatic epoxy resins such as alicyclic epoxies such as vinylcyclohexene dioxide, dicyclopentadiene oxide, and alicyclic diepoxy-adipate, or combinations thereof.

[0150] In another specific example, the epoxy resin may be selected from the group consisting of bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin, naphthalene skeleton type epoxy resin, tetraphenylolethane type epoxy resin, diphenyl phosphate (DPP) type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, glycidyl ether having one epoxy group such as diglycidyl ether of bisphenol A ethylene oxide adduct, diglycidyl ether of bisphenol A propylene oxide adduct, diglycidyl ether of bisphenol A, phenyl glycidyl ether, cresyl glycidyl ether, a nuclear hydrogenated epoxy resin which is a nuclear hydrogenation product of these epoxy resins, or a combination thereof, but is not limited thereto.

[0151] In one specific example, in the two-component curable composition and the adhesive composition, the curing agent component may include a curing agent commonly used in this field.

[0152] In one specific example, the curing agent is an amine curing agent such as benzyldimethylamine, tris(dimethylaminomethyl)phenol, dimethylcyclohexylamine, polyetheramine, etc. (e.g., tertiary amine); an imidazole curing agent such as 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole; an organophosphorus curing agent such as triphenylphosphine, triphenyl phosphite; a quaternary phosphonium salt curing agent such as tetraphenylphosphonium bromide, tetra-n-butylphosphonium bromide; a diazabicycloalkene curing agent such as 1,8-diazabicyclo[5.4.0]undecene-7 or an organic acid salt thereof; an organometallic compound curing agent such as zinc octylate, tin octylate, or an aluminum acetylacetone complex; The curing agent may be at least one selected from the group consisting of, but is not limited to, quaternary ammonium salt-based curing agents such as tetraethylammonium bromide and tetrabutylammonium bromide; boron compound-based curing agents such as boron trifluoride and triphenylborate; metal halide-based curing agents such as zinc chloride and stannous chloride; latent curing agents (e.g., high-melting-point dispersion-type latent amine adducts obtained by adding dicyandiamide and amine to epoxy resin, etc.; microcapsule-type latent curing agents in which the surface of an imidazole-based, phosphorus-based, or phosphine-based accelerator is coated with a polymer; amine salt-type latent curing agents; high-temperature dissociation-type thermocationic polymerization-type latent curing agents such as Lewis acid salts and Bronsted acid salts, etc.) or combinations thereof.

[0153] More specifically, the curing agent may be an amine-based curing agent.

[0154] In one specific example, in the two-component curable composition and the adhesive composition, the curing agent component may further include an impact modifier other than the impact modifier comprising the (meth)acrylic-modified polyurethane composition of the present invention (hereinafter also referred to as “additional impact modifier”).

[0155] In one specific example, the additional impact modifier may be, for example, a rubber-based impact modifier such as carboxyl terminated butadiene acrylonitrile (CTBN), amine terminated butadiene acrylonitrile (ATBN), hydroxy terminated butadiene acrylonitrile (HTBN), epoxy terminated butadiene acrylonitrile (ETBN), polyethersulfone, polyetherimide, polycarbonate, polyimide, polyamide, acrylonitrile butadiene styrene (ABS), and methacrylate butadiene styrene. Thermoplastic polymer-based impact modifiers such as styrene, MBS, or mixtures thereof may be used, but are not limited thereto.

[0156] Since room temperature curing of epoxy resin usually requires a temperature of 15°C or higher and a curing time of 24 hours or more, rapid curing and low temperature curing are sometimes required. Therefore, in order to accelerate curing, the curing agent component in the two-component curable composition and the adhesive composition may additionally include a curing accelerator.

[0157] In one specific example, the curing accelerator may include, for example, a urea-based compound, a thiourea-based compound, a Lewis acid-based compound, a peroxide-based compound, or a mixture thereof, and specifically, may include, but is not limited to, butylated urea, butylated melamine, butylated thiourea, boron trifluoride, benzoyl peroxide, and the like.

[0158] When a curing accelerator is included in the above-mentioned curing agent component, the content thereof may be, for example, 0.01 to 5 parts by weight, or 0.05 to 4 parts by weight, or 0.08 to 3 parts by weight, based on 100 parts by weight of the total curing agent component, but is not limited thereto.

[0159] In one specific embodiment, in the two-component curable composition and the adhesive composition, the main component and / or the curing agent component may further include one or more additives selected from the group consisting of fillers, antioxidants, ultraviolet absorbers, resin modifiers, silane coupling agents, diluents, colorants, defoamers, defoamers, dispersants, viscosity modifiers, gloss modifiers, wetting agents, conductivity-imparting agents, or combinations thereof.

[0160] The above fillers are used primarily for the purpose of improving the mechanical properties of the cured product by mixing them with the main component and / or the curing agent component, and generally, the mechanical properties improve as the amount added increases. Inorganic fillers include extenders such as talc, sand, silica, talc, and calcium carbonate; reinforcing fillers such as mica, quartz, and glass fiber; and those with special purposes such as quartz powder, graphite, alumina, and Aerosil (for the purpose of imparting thixotropic properties). Metallic fillers include those that contribute to the coefficient of thermal expansion, wear resistance, thermal conductivity, and adhesiveness such as aluminum, aluminum oxide, aluminum hydroxide, iron, iron oxide, and copper; those that impart flame retardancy such as antimony oxide (Sb2O3); and barium titanate. Organic fillers include fillers for weight reduction such as fine plastic balls (phenolic resin, urea resin, etc.). In addition, various types of glass fibers or chemical fiber cloths can be treated as fillers in a broad sense in the production of laminated products as fillers with reinforcing properties. In order to impart thixotropic properties to the resin (thixotropy or thixotropy refers to the property of having a liquid state when flowing and a solid state when stationary so that the resin attached to a vertical surface or by the immersion method or impregnated into a laminated material does not flow or disappear during curing), fine particles with a large unit surface area are used. For example, colloidal silica (Aerosil) or bentonite-based clay materials are used.

[0161] In one specific example, the filler is not particularly limited, but may be selected from the group consisting of glass fiber, carbon fiber, titanium oxide, alumina, talc, mica, aluminum hydroxide, calcium carbonate, or a combination thereof. When the two-component curable composition and / or adhesive composition includes a filler, the content thereof may be, for example, 0.01 to 80 parts by weight, or 0.01 to 60 parts by weight, or 0.1 to 50 parts by weight, based on 100 parts by weight of the total composition, but is not limited thereto.

[0162] The above antioxidant can be used to further improve the heat resistance of the obtained cured product, and for example, it can be selected from the group consisting of phenol-based antioxidants (e.g., dibutylhydroxytoluene), sulfur-based antioxidants (e.g., mercaptopropionic acid derivatives), phosphorus-based antioxidants (e.g., 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), or combinations thereof. When the two-component curable composition and / or adhesive composition contains the antioxidant, the content thereof can be, for example, 0.01 to 10 parts by weight, or 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight based on 100 parts by weight of the total composition, but is not limited thereto.

[0163] As the above UV absorber, for example, a benzotriazole-based UV absorber such as TINUBIN P or TINUVIN 234 manufactured by BASF Japan Ltd.; a triazine-based UV absorber such as TINUVIN 1577ED; a hindered amine-based UV absorber such as CHIMASSOLV 2020FDL, or a combination thereof may be used, but is not limited thereto. When the two-component curable composition and / or adhesive composition includes the UV absorber, the content thereof may be, for example, 0.01 to 10 parts by weight, or 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight based on 100 parts by weight of the total composition, but is not limited thereto.

[0164] As the resin modifier, for example, a flexibility-imparting agent such as polypropylene glycidyl ether, polymerized fatty acid polyglycidyl ether, polypropylene glycol, or urethane prepolymer can be used, but is not limited thereto. When the two-component curable composition and / or adhesive composition includes a resin modifier, the content thereof can be, for example, 0.01 to 80 parts by weight, or 0.01 to 50 parts by weight, or 0.1 to 20 parts by weight, based on 100 parts by weight of the total composition, but is not limited thereto.

[0165] As the silane coupling agent, for example, chloropropyltrimethoxysilane, vinyltrichlorosilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. can be used, but are not limited thereto. When the silane coupling agent is included in the two-component curable composition and / or adhesive composition, the content thereof can be, for example, 0.01 to 20 parts by weight, or 0.05 to 10 parts by weight, or 0.1 to 5 parts by weight based on 100 parts by weight of the total composition, but is not limited thereto.

[0166] The above diluent is used primarily for the purpose of reducing viscosity by adding it to the main component and / or the curing agent component, and when used, it plays a role in improving flowability and defoaming, improving penetration into parts details, or enabling the effective addition of fillers. Unlike solvents, diluents generally do not volatilize, but remain in the cured product when the resin is cured, and are divided into reactive and non-reactive diluents. Here, a reactive diluent has one or more epoxy groups and participates in a reaction to enter a cross-linked structure in the cured product, and a non-reactive diluent is only physically mixed and dispersed in the cured product. Commonly used reactive diluents include butyl glycidyl ether (BGE), phenyl glycidyl ether (PGE), aliphatic glycidyl ether (C12-C14), modified-tert-carboxylic glycidyl ester, etc. Commonly used non-reactive diluents include dibutyl phthalate (DBP), dioctyl phthalate (DOP), nonyl phenol, and hysol. In one specific example, the diluent is not particularly limited, but may be selected from the group consisting of n-butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, vinylcyclohexene dioxide, diglycidyl aniline, glycerin triglycidyl ether, or a combination thereof, but is not limited thereto. When the two-component curable composition and / or adhesive composition includes a diluent, the content thereof may be, for example, 0.01 to 80 parts by weight, or 0.01 to 50 parts by weight, or 0.1 to 20 parts by weight, based on 100 parts by weight of the total composition, but is not limited thereto.

[0167] Pigments or dyes may be used as the above coloring agent, and examples thereof include, but are not limited to, titanium dioxide, cadmium red, shading green, carbon black, chrome green, chrome yellow, navy blue, shading blue, etc.

[0168] In addition, various additives can be used, such as antifoaming and defoaming agents used for the purpose of removing air bubbles in the resin, dispersing agents for increasing the dispersion effect between the epoxy resin and the colorant, wetting agents for improving the adhesion between the epoxy resin and the material, viscosity modifiers, gloss modifiers for controlling the gloss of the resin, viscosity-imparting agents for improving adhesiveness, and conductivity-imparting agents for imparting electrical properties.

[0169] In the two-component curable composition and adhesive composition of the present invention, the weight ratio between the main component and the curing agent component may be 1:0.5 to 1:1, but is not particularly limited thereto.

[0170] The two-component curable composition and adhesive composition of the present invention can be cured by mixing the main component and the curing agent component at room temperature (typically 15°C to 35°C), and the mixing of the main component and the curing agent component can be performed using a conventional method and equipment.

[0171] In one specific embodiment, the adhesive composition of the present invention may be used for bonding between similar materials, for example, between metal-metal materials, or between different 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 an article to which the adhesive composition of the present invention is applied may include such similar or different materials bonded by the adhesive composition. Application of the adhesive composition to a material may be performed using conventional methods and equipment.

[0172] Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, the scope of the present invention is not limited to these examples.

[0173] [Example]

[0174] <Preparation of anhydrous sugar alcohol composition containing first to fifth polyol components>

[0175] Manufacturing Example 1: Manufacturing of anhydrous sugar alcohol composition using 97 wt% glucose content

[0176] A glucose product having a purity of 97% was subjected to a hydrogenation reaction in the presence of a nickel catalyst and under a temperature of 125°C and a hydrogen pressure of 60 atm, thereby obtaining 1,819 g of a liquid hydrogenated sugar composition having a concentration of 55 wt% (96 wt% of sorbitol, 0.9 wt% of mannitol, and 3.1 wt% of polysaccharide alcohol higher than disaccharide based on solid content), which was placed in a batch reactor equipped with a stirrer and heated to 100°C to concentrate, thereby obtaining 1,000 g of a concentrated hydrogenated sugar composition.

[0177] 1,000 g of the above-mentioned concentrated hydrogenated sugar composition and 9.6 g of sulfuric acid were charged into the reactor. Thereafter, the internal temperature of the reactor was increased to approximately 135°C, and a dehydration reaction was performed under conditions of a reduced pressure of approximately 45 mmHg to convert it into anhydrous sugar alcohol. After the dehydration reaction was completed, the temperature of the reaction product was cooled to 110°C or lower, and approximately 15.7 g of a 50% aqueous sodium hydroxide solution was added to neutralize the reaction product. Thereafter, the temperature was cooled to below 100°C, and the reaction product was concentrated for more than 1 hour under conditions of a reduced pressure of 45 mmHg to remove residual moisture and low-boiling-point substances, thereby obtaining approximately 831 g of anhydrous sugar alcohol conversion solution. As a result of analyzing the obtained anhydrous sugar alcohol conversion solution by gas chromatography, the conversion content into isosorbide was 71.9 wt%, and through this, the molar conversion rate from sorbitol to isosorbide was calculated to be 77.6%.

[0178] 831 g of the obtained anhydrous sugar alcohol conversion solution was placed in a thin film distiller (SPD) and distilled. The distillation was performed at a temperature of 160°C and a vacuum pressure of 1 mbar, and approximately 589 g of distillate was obtained (distillation yield: approximately 70.9%). The purity of isosorbide in the distillate was measured to be 96.8%, and the distillation yield of isosorbide calculated from this was 95.3%. After separating the distillate, about 242 g of an anhydrosugar alcohol composition comprising 11.5 wt% of isosorbide (anhydrosugar alcohol) [second polyol component], 0.4 wt% of isomannide (anhydrosugar alcohol) [second polyol component], 7.4 wt% of sorbitan (anhydrosugar alcohol) [first polyol component], 2.5 wt% of a total of a polysaccharide alcohol represented by the above chemical formula 1 [third polyol component] and anhydrosugar alcohol derived therefrom (i.e., formed by removing water molecules from the polysaccharide alcohol) [fourth polyol component], and 78.2 wt% of a polymer thereof [fifth polyol component], wherein the number average molecular weight of the composition is 208 g / mol, the polydispersity index of the composition is 1.25, the hydroxyl value of the composition is 751 mg KOH / g, and the average number of -OH groups per molecule in the composition is 2.78. Obtained.

[0179] <Preparation of anhydrous alcohol-alkylene glycol composition>

[0180] Manufacturing Example 2: An anhydrous sugar alcohol-alkylene glycol composition manufactured by addition reaction of 300 parts by weight of propylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Manufacturing Example 1.

[0181] 100 parts by weight (100 g) of the anhydrous sugar alcohol composition obtained in the above Preparation Example 1 and 1 part by weight (1.0 g) of KOH were placed in a pressurized reactor, and the pressurization and exhaust processes with nitrogen were repeated 3 times. Thereafter, the temperature inside the reactor was raised to 100°C to remove moisture, and after all moisture was removed, 300 parts by weight (300 g) of propylene oxide was slowly injected and reacted at 100°C to 140°C. Thereafter, 4 g of a metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and the temperature inside the reactor was raised again and stirred at 100°C to 120°C for 1 to 5 hours while monitoring the metal content. When the metal was completely removed and no longer detected, the temperature inside the reactor was cooled to 60°C to 90°C and filtered. Afterwards, the filtrate was purified using an ion exchange resin (UPRM 200, Samyang Corporation) to obtain 350 g of an anhydrous sugar alcohol-alkylene glycol composition.

[0182] <Preparation of (meth)acrylic-modified polyurethane composition>

[0183] Example A1

[0184] According to the following method, an isocyanate prepolymer composition (total NCO equivalents of polyisocyanate / total OH equivalents of polyol composition=1.7) was prepared using a polyol composition including an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol (OH equivalents of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalents of the polyol composition=0.4) and a polyisocyanate, and a (meth)acrylic-modified polyurethane composition was prepared using the isocyanate prepolymer composition and 2-hydroxyethyl methacrylate (2-HEMA).

[0185] In a 250 ml four-necked glass reactor equipped with a nitrogen gas line, a stirrer, a thermometer, and a heater, 12.95 g of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example 2, 90.0 g of polytetramethylene ether glycol (number average molecular weight: 2,000 g / mol, Sigma-Aldrich), 28.34 g of isophorone diisocyanate, and 1.0 g of di-n-butyltin dilaurate as a catalyst were placed, and the internal temperature of the reactor was slowly increased to 75°C to 80°C, and then the urethane reaction was carried out with stirring under a nitrogen atmosphere for 3 hours, thereby preparing an isocyanate prepolymer composition. Subsequently, the internal temperature of the reactor was adjusted to 60°C. After measuring the isocyanate (NCO) content of the above-mentioned manufactured isocyanate prepolymer composition, 1.0 equivalent of 2-hydroxyethyl methacrylate was added to the reactor per 1 equivalent of NCO. After the addition of 2-hydroxyethyl methacrylate, the reaction was continued for an additional 2 hours. After the reaction, the infrared spectroscopy (FTIR) showed an emission line at approximately 2,270 cm -1 After confirming that the peak disappeared, the reaction was terminated. Thus, 150 g of a (meth)acrylic-modified polyurethane composition was obtained.

[0186] Example A2

[0187] According to the following method, an isocyanate prepolymer composition (total NCO equivalents of polyisocyanate / total OH equivalents of polyol composition=1.7) was prepared using a polyol composition including an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol (OH equivalents of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalents of the polyol composition=0.2) and a polyisocyanate, and a (meth)acrylic-modified polyurethane composition was prepared using this isocyanate prepolymer composition and 2-hydroxyethyl methacrylate (2-HEMA).

[0188] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that the content of the anhydrous sugar alcohol-alkylene glycol composition obtained in Manufacturing Example 2 was changed from 12.95 g to 5.61 g, the content of polytetramethylene ether glycol (number average molecular weight: 2,000 g / mol, Sigma-Aldrich (manufactured)) was changed from 90.0 g to 104.0 g, and the content of isophorone diisocyanate was changed from 28.34 g to 24.56 g, and 150 g of a (meth)acryl-modified polyurethane composition was obtained in the same manner as in Example A1.

[0189] Example A3

[0190] According to the following method, an isocyanate prepolymer composition (total NCO equivalents of polyisocyanate / total OH equivalents of polyol composition=1.7) was prepared using a polyol composition including an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol (OH equivalents of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalents of the polyol composition=0.5) and a polyisocyanate, and a (meth)acrylic-modified polyurethane composition was prepared using this isocyanate prepolymer composition and 2-hydroxyethyl methacrylate (2-HEMA).

[0191] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that the content of the anhydrous sugar alcohol-alkylene glycol composition obtained in Manufacturing Example 2 was changed from 12.95 g to 21.58 g, the content of polytetramethylene ether glycol (number average molecular weight: 2,000 g / mol, Sigma-Aldrich) was changed from 90.0 g to 100.0 g, and the content of isophorone diisocyanate was changed from 28.34 g to 37.79 g, and 150 g of a (meth)acryl-modified polyurethane composition was obtained in the same manner as in Example A1.

[0192] Example A4

[0193] According to the following method, an isocyanate prepolymer composition (total NCO equivalents of polyisocyanate / total OH equivalents of polyol composition=1.5) was prepared using a polyol composition including an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol (OH equivalents of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalents of the polyol composition=0.4) and a polyisocyanate, and a (meth)acrylic-modified polyurethane composition was prepared using this isocyanate prepolymer composition and 2-hydroxyethyl methacrylate (2-HEMA).

[0194] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that the content of the anhydrous sugar alcohol-alkylene glycol composition obtained in Manufacturing Example 2 was changed from 12.95 g to 15.54 g, the content of polytetramethylene ether glycol (number average molecular weight: 2,000 g / mol, Sigma-Aldrich) was changed from 90.0 g to 108.0 g, and the content of isophorone diisocyanate was changed from 28.34 g to 30.01 g, and 150 g of a (meth)acryl-modified polyurethane composition was obtained in the same manner as in Example A1.

[0195] Example A5

[0196] According to the following method, an isocyanate prepolymer composition (total NCO equivalents of polyisocyanate / total OH equivalents of polyol composition=1.9) was prepared using a polyol composition including an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol (OH equivalents of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalents of the polyol composition=0.4) and a polyisocyanate, and a (meth)acrylic-modified polyurethane composition was prepared using the isocyanate prepolymer composition and 2-hydroxyethyl methacrylate (2-HEMA).

[0197] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that the content of the anhydrous sugar alcohol-alkylene glycol composition obtained in Manufacturing Example 2 was changed from 12.95 g to 13.81 g, the content of polytetramethylene ether glycol (number average molecular weight: 2,000 g / mol, Sigma-Aldrich (manufactured)) was changed from 90.0 g to 96.0 g, and the content of isophorone diisocyanate was changed from 28.34 g to 33.79 g, and 150 g of a (meth)acryl-modified polyurethane composition was obtained in the same manner as in Example A1.

[0198] Comparative Example A1

[0199] According to the following method, an isocyanate prepolymer composition (total NCO equivalents of polyisocyanate / total OH equivalents of polyol composition=1.7) was prepared using a polyether polyol and a polyisocyanate, and a (meth)acrylic-modified polyurethane was prepared using this isocyanate prepolymer composition and 2-hydroxyethyl methacrylate (2-HEMA).

[0200] An isocyanate prepolymer was prepared in the same manner as in Example A1, except that the anhydrous sugar alcohol-alkylene glycol composition obtained in Manufacturing Example 2 was not used, the content of polytetramethylene ether glycol (number average molecular weight: 2,000 g / mol, Sigma-Aldrich (manufactured)) was changed from 90.0 g to 120.0 g, and the content of isophorone diisocyanate was changed from 28.34 g to 22.67 g, and 150 g of (meth)acryl-modified polyurethane was obtained in the same manner as in Example A1.

[0201] Comparative Example A2

[0202] According to the following method, an isocyanate prepolymer composition (total NCO equivalents of polyisocyanate / total OH equivalents of polyol composition=1.7) was prepared using a polyol composition including an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol (OH equivalents of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalents of the polyol composition=0.4) and a polyisocyanate, and an end-capped polyurethane composition was prepared using the isocyanate prepolymer composition and t-butyl phenol (t-BP).

[0203] An isocyanate prepolymer composition was prepared in the same manner as in Example A1. The internal temperature of the reactor was then adjusted to 60°C. After measuring the isocyanate (NCO) content of the prepared isocyanate prepolymer composition, 1.0 equivalent of t-butyl phenol (Sigma Aldrich) per 1 equivalent of NCO was added to the reactor, and the end-capping reaction was performed for an additional 2 hours while mixing under a nitrogen atmosphere. After the reaction, the temperature was measured at about 2,270 cm in an infrared spectroscopy (FTIR). -1 After confirming that the peak disappeared, the reaction was terminated. Thus, 150 g of an end-capped polyurethane composition was obtained.

[0204] Comparative Example A3

[0205] According to the following method, an isocyanate prepolymer composition (total NCO equivalents of polyisocyanate / total OH equivalents of polyol composition=1.7) was prepared using a polyol composition including an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol (OH equivalents of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalents of the polyol composition=0.6) and a polyisocyanate, and a (meth)acrylic-modified polyurethane composition was prepared using the isocyanate prepolymer composition and 2-hydroxyethyl methacrylate (2-HEMA).

[0206] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that the content of the anhydrous sugar alcohol-alkylene glycol composition obtained in Manufacturing Example 2 was changed from 12.95 g to 23.3 g, the content of polytetramethylene ether glycol (number average molecular weight: 2,000 g / mol, Sigma-Aldrich (manufactured)) was changed from 90.0 g to 72.0 g, and the content of isophorone diisocyanate was changed from 28.34 g to 34.01 g, and 150 g of a (meth)acryl-modified polyurethane composition was obtained in the same manner as in Example A1.

[0207] Comparative Example A4

[0208] According to the following method, an isocyanate prepolymer composition (total NCO equivalents of polyisocyanate / total OH equivalents of polyol composition=1.7) was prepared using a polyol composition including an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol (OH equivalents of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalents of the polyol composition=0.1) and a polyisocyanate, and a (meth)acrylic-modified polyurethane composition was prepared using this isocyanate prepolymer composition and 2-hydroxyethyl methacrylate (2-HEMA).

[0209] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that the content of the anhydrous sugar alcohol-alkylene glycol composition obtained in Manufacturing Example 2 was changed from 12.95 g to 2.59 g, the content of polytetramethylene ether glycol (number average molecular weight: 2,000 g / mol, Sigma-Aldrich (manufactured)) was changed from 90.0 g to 108.0 g, and the content of isophorone diisocyanate was changed from 28.34 g to 22.67 g, and 150 g of a (meth)acryl-modified polyurethane composition was obtained in the same manner as in Example A1.

[0210] Comparative Example A5

[0211] According to the following method, an isocyanate prepolymer composition (total NCO equivalents of polyisocyanate / total OH equivalents of polyol composition=1.4) was prepared using a polyol composition including an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol (OH equivalents of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalents of the polyol composition=0.4) and a polyisocyanate, and a (meth)acrylic-modified polyurethane composition was prepared using this isocyanate prepolymer composition and 2-hydroxyethyl methacrylate (2-HEMA).

[0212] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that the content of the anhydrous sugar alcohol-alkylene glycol composition obtained in Manufacturing Example 2 was changed from 12.95 g to 15.54 g, the content of polytetramethylene ether glycol (number average molecular weight: 2,000 g / mol, Sigma-Aldrich (manufactured)) was changed from 90.0 g to 108.0 g, and the content of isophorone diisocyanate was changed from 28.34 g to 28.01 g, and 150 g of a (meth)acryl-modified polyurethane composition was obtained in the same manner as in Example A1.

[0213] Comparative Example A6

[0214] According to the following method, an isocyanate prepolymer composition (total NCO equivalents of polyisocyanate / total OH equivalents of polyol composition=2.0) was prepared using a polyol composition including an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol (OH equivalents of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalents of the polyol composition=0.4) and a polyisocyanate, and a (meth)acrylic-modified polyurethane composition was prepared using the isocyanate prepolymer composition and 2-hydroxyethyl methacrylate (2-HEMA).

[0215] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that the content of the anhydrous sugar alcohol-alkylene glycol composition obtained in Manufacturing Example 2 was changed from 12.95 g to 13.81 g, the content of polytetramethylene ether glycol (number average molecular weight: 2,000 g / mol, Sigma-Aldrich) was changed from 90.0 g to 96.0 g, and the content of isophorone diisocyanate was changed from 28.34 g to 35.57 g, and 150 g of a (meth)acryl-modified polyurethane composition was obtained in the same manner as in Example A1.

[0216] <Measurement of physical properties of (meth)acrylic-modified polyurethane compositions>

[0217] The compositions and properties of the (meth)acrylic-modified polyurethane compositions prepared in Examples A1 to A5 and Comparative Examples A3 to A6, the (meth)acrylic-modified polyurethane prepared in Comparative Example A1, and the end-capped polyurethane composition prepared in Comparative Example A2 are shown in Table 1 below.

[0218] (1) Measurement of number average molecular weight (Mn, unit: g / mol) and polydispersity index (PDI)

[0219] Each of the (meth)acryl-modified polyurethane compositions manufactured in Examples A1 to A5 and Comparative Examples A3 to A6, the (meth)acryl-modified polyurethane manufactured in Comparative Example A1, and the end-capped polyurethane composition manufactured in Comparative Example A2 was dissolved in tetrahydrofuran (THF) in an amount of 1 to 3 parts by weight, and then the number average molecular weight (Mn) and polydispersity index (PD) were measured using a gel permeation chromatography apparatus (Agilent). The column used was a Mixed-D column (Agilent), the column temperature was 40°C, the developing solvent used was tetrahydrofuran (THF), and it was used by flowing at a rate of 0.5 ml / min. Polystyrene (Aldrich) was used as a standard material.

[0220]

[0221] As shown in Table 1 above, for the (meth)acrylic-modified polyurethane compositions of Examples A1 to A5, both the number average molecular weight (about 6,000 to 7,205) and the polydispersity index (2.41 to 2.67) were stable. On the other hand, in the case of Comparative Example A1, the viscosity was low due to reduced intermolecular entanglement because the polyurethane had a linear structure, in the case of Comparative Example A3, the viscosity increased significantly due to the high polydispersity index, in the case of Comparative Example A4, the viscosity was very low due to the low polydispersity index, in the case of Comparative Example A5, both the number average molecular weight and the polydispersity index were high, and in the case of Comparative Example A6, both the number average molecular weight and the polydispersity index were low.

[0222] <Preparation of epoxy resin composition, two-component curable composition, and room temperature curable adhesive composition>

[0223] Examples B1 to B7 and Comparative Examples B1 to B9

[0224] As epoxy resins, bisphenol A type epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) and fatty acid modified epoxy resin (YDPN-631, Kukdo Chemical Co., Ltd.) were mixed, each of the polyurethane components obtained in Examples A1 to A5 and Comparative Examples A1 to A6 was mixed as an impact modifier, calcium carbonate (OMYACARB 30-CN, OMYA Co., Ltd.) having a particle size of 21 to 33 μm was mixed as a filler, and phenyl glycidyl ether (PGE, Kukdo Chemical Co., Ltd.) as a reactive diluent was mixed as an additive in the composition shown in Table 2 below to prepare an epoxy resin composition. At this time, the sum of the parts by weight of all components included in the epoxy resin composition was 100 parts by weight.

[0225] As a curing agent for epoxy resin, an aliphatic modified amine (Polyether amine D 400, BASF), as an additional impact modifier, amine-terminated butadiene acrylonitrile (ATBN), as a filler, calcium carbonate (OMYACARB 30-CN, OMYA) having a particle size of 21 to 33 μm, and as a curing accelerator, benzoyl peroxide (BPO, Sigma-Aldrich) were mixed in the composition shown in Table 2 below to prepare a curing agent composition. At this time, the sum of the parts by weight of all components included in the curing agent composition was 100 parts by weight.

[0226] A two-component curable composition was prepared, which included the above-prepared epoxy resin composition as a main component and the above-prepared curing agent composition as a curing agent component.

[0227] Next, the main component and the curing agent component of the composition described in Table 2 below were quantitatively added to a 200 mL paste mixer PE bottle with separated upper and lower parts, and mixed for 10 minutes in a vacuum state of 30 KPa using a paste mixer (THINKY Co.), followed by defoaming mixing for 1 minute, thereby producing a room temperature curing adhesive composition. At this time, the main component and the curing agent component were mixed at a weight ratio of 2:1.

[0228]

[0229]

[0230] <Evaluation of physical properties of room temperature curing adhesive compositions>

[0231] The physical properties of the room temperature curing adhesive compositions manufactured in Examples B1 to B7 and Comparative Examples B1 to B9 were measured by the following methods, and the results are shown in Table 3 below.

[0232] (1) Measurement of shear strength (unit: MPa)

[0233] The shear strength was measured according to the ASTM D 1002 standard. Specifically, the room temperature curing adhesive compositions obtained in Examples B1 to B7 and Comparative Examples B1 to B9 were each applied to a rolled steel plate measuring 100 mm in length x 25 mm in width x 1 mm in thickness, and then a small amount of microbeads were laminated thereon to maintain a constant bonding thickness. Then, another rolled steel plate was covered and fixed thereon, and then cured at 80°C for 30 minutes. After curing, the shear strength was measured for the bonded specimens cooled to room temperature (25°C) using a universal testing machine (Instron 5967 product, Instron Co., Ltd.). The shear strength was measured by applying a load in a 180 degree direction at a tensile speed of 5 mm / min. A total of five shear strength measurements were performed for each bonded specimen, and their average value was calculated.

[0234] (2) Measurement of room temperature impact strength (unit: N / mm)

[0235] The room temperature impact strength was measured according to the ISO 11343 standard. Specifically, a steel specimen measuring 90 mm in length x 20 mm in width x 1 mm in thickness, with a 30 mm end portion used as the bonding surface and a tuning fork-shaped non-bonded end, was used. Each of the room temperature-curing adhesive compositions obtained in Examples B1 to B7 and Comparative Examples B1 to B9 was applied to the 30 mm end bonding surface, and a small amount of microbeads was laminated thereon to maintain a constant bonding thickness. Then, another steel specimen was covered and fixed thereon, and cured at 80°C for 30 minutes. After curing, the room temperature impact strength was measured for the bonded specimen cooled to room temperature (25°C) using a drop impact tester. The room temperature impact strength was measured so that the wedge fixture passed through the bonding portion of the bonding portion, and the impact speed was 2 m / s to 3 m / s. At this time, the room temperature impact strength was measured five times for each adhesive specimen and the average value was calculated.

[0236]

[0237] As shown in Table 3 above, the adhesive specimens of Examples B1 to B7 exhibited excellent adhesive properties and impact resistance, exhibiting a shear strength of 20 MPa or more and a room temperature impact strength of 22 N / mm or more. On the other hand, the adhesive specimens of Comparative Examples B1 to B9 had very poor shear strengths of less than 18.5 MPa, very poor room temperature impact strengths of less than 18 N / mm, or unstable cracks occurred, making it impossible to measure the room temperature impact strength.

[0238] (3) Evaluation of uniformity of physical properties

[0239] The uniformity of physical properties was evaluated for adhesive specimens using the (meth)acrylic-modified polyurethane composition according to the present invention as an impact modifier (adhesive specimen of Example B1) and adhesive specimens using the polyurethane composition end-capped with t-butyl phenol as an impact modifier (adhesive specimen of Comparative Example B5). Specifically, the shear strength and room temperature impact strength were measured five times each for the adhesive specimens of Example B1 and Comparative Example B5, and the average values ​​and standard deviations were calculated, and the results are shown in Table 4 below.

[0240]

[0241] As shown in Table 4 above, in the case of the room-temperature curing adhesive composition (Comparative Example B5) manufactured using a polyurethane composition end-capped with t-butyl phenol (Comparative Example A2) as an impact modifier, the shear strength and room-temperature impact strength were very poor compared to the room-temperature curing adhesive composition (Example B1) manufactured using a (meth)acrylic-modified polyurethane composition according to the present invention as an impact modifier, and furthermore, there was a relatively large difference in the standard deviation of each property for the five specimens.

[0242] These results are believed to be because, when the polyurethane composition end-capped with t-butyl phenol (Comparative Example A2) is used as an impact modifier in a two-component curable composition, the viscosity of the polyurethane composition end-capped with t-butyl phenol is too high, which reduces the miscibility between the main component and the curing agent component in the two-component curable composition, resulting in a large standard deviation of the physical properties. A large standard deviation of the physical properties of each specimen means that the uniformity of the physical properties is very poor.

Claims

1. A (meth)acrylic-modified polyurethane composition manufactured by reacting an isocyanate prepolymer composition with a hydroxyalkyl (meth)acrylate, The above isocyanate prepolymer composition is manufactured by reacting a polyol composition and a polyisocyanate with urethane, The above polyol composition comprises an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol, The above anhydrous sugar alcohol-alkylene glycol composition is prepared by addition reaction of an anhydrous sugar alcohol composition and an alkylene oxide, The above anhydrous sugar alcohol composition comprises first to fifth polyol components, wherein the first polyol component is a monoanhydrous sugar alcohol, the second polyol component is a dianhydrous sugar alcohol, the third polyol component is a polysaccharide alcohol represented by the following chemical formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from a polysaccharide alcohol represented by the following chemical formula 1, and the fifth polyol component is at least one polymer selected from among the first to fourth polyol components. The ratio of the OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition to the total OH equivalent of the polyol composition (OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalent of the polyol composition) is greater than 0.1 and less than 0.6, The ratio of the total NCO equivalent of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalent of the polyisocyanate / total OH equivalent of the polyol composition) is greater than 1.4 and less than 2.0, (Meth)acrylic-modified polyurethane composition: [Chemical Formula 1] In the above chemical formula 1, n is an integer from 0 to 4.

2. In the first paragraph, a (meth)acrylic-modified polyurethane composition wherein the first polyol component is a monoanhydrosugar hexitol; the second polyol component is a dianhydrosugar hexitol; and the fourth polyol component is selected from a compound represented by the following chemical formula 2, a compound represented by the following chemical formula 3, or a mixture thereof: [Chemical Formula 2] [Chemical Formula 3] In the above chemical formulas 2 and 3, n is an integer from 0 to 4, each independently.

3. In the first paragraph, a (meth)acrylic-modified polyurethane composition comprising at least one selected from the group consisting of condensation polymers prepared from the following condensation polymerization reaction: - Condensation polymerization reaction of the first polyol component, - Condensation polymerization reaction of the second polyol component, - Condensation polymerization reaction of the third polyol component, - Condensation polymerization reaction of the fourth polyol component, - Condensation polymerization reaction of the first polyol component and the second polyol component, - Condensation polymerization reaction of the first polyol component and the third polyol component, - Condensation polymerization reaction of the first polyol component and the fourth polyol component, - Condensation polymerization reaction of the second polyol component and the third polyol component, - Condensation polymerization reaction of the second polyol component and the fourth polyol component, - Condensation polymerization reaction of the third polyol component and the fourth polyol component, - Condensation polymerization reaction of the first polyol component, the second polyol component, and the third polyol component, - Condensation polymerization reaction of the first polyol component, the second polyol component, and the fourth polyol component, - Condensation polymerization reaction of the first polyol component, the third polyol component, and the fourth polyol component, - Condensation polymerization reaction of the second polyol component, the third polyol component and the fourth polyol component, or - Condensation polymerization reaction of the first polyol component, the second polyol component, the third polyol component, and the fourth polyol component.

4. In the first paragraph, a (meth)acrylic-modified polyurethane composition, wherein the anhydrous sugar alcohol composition satisfies the following i) to iii): i) The number average molecular weight (Mn) of the anhydrous alcohol composition is 193 to 1,589 g / mol; ii) the polydispersity index (PDI) of the anhydrous sugar alcohol composition is 1.13 to 3.41; iii) The average number of -OH groups per molecule in the anhydrous alcohol composition is 2.54 to 21.

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5. A (meth)acryl-modified polyurethane composition, wherein the anhydrous sugar alcohol composition is prepared by hydrogenating a glucose-containing sugar composition to produce a hydrogenated sugar composition, heating the obtained hydrogenated sugar composition in the presence of an acid catalyst to cause a dehydration reaction, and thin-film distilling the obtained dehydration reaction product.

6. A (meth)acrylic-modified polyurethane composition in claim 5, wherein the glucose-containing sugar composition contains 41 wt% to 99.5 wt% of glucose based on the total weight of the sugar composition.

7. In the first paragraph, the anhydrous sugar alcohol-alkylene glycol composition is a (meth)acrylic-modified polyurethane composition prepared by adding 100 to 500 parts by weight of alkylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition.

8. In the first paragraph, a (meth)acrylic-modified polyurethane composition comprising polyether polyol and polyalkylene glycol.

9. A (meth)acrylic-modified polyurethane composition according to claim 1, wherein the number average molecular weight of the (meth)acrylic-modified polyurethane composition is greater than 5,500 g / mol and less than 7,500 g / mol.

10. In paragraph 1, the hydroxyalkyl (meth)acrylate is hydroxy-C 1-8 A (meth)acrylic-modified polyurethane composition, which is an alkyl (meth)acrylate.

11. A method for producing a (meth)acrylic-modified polyurethane composition, (1) a step of producing an isocyanate prepolymer composition having an isocyanate terminal by subjecting a polyol composition and a polyisocyanate to a urethane reaction; and (2) a step of reacting the isocyanate prepolymer composition obtained from step (1) with hydroxyalkyl (meth)acrylate; The above polyol composition comprises an anhydrous sugar alcohol-alkylene glycol composition and a polyether polyol, The above anhydrous sugar alcohol-alkylene glycol composition is prepared by addition reaction of an anhydrous sugar alcohol composition and an alkylene oxide, The above anhydrous sugar alcohol composition comprises first to fifth polyol components, wherein the first polyol component is a monoanhydrous sugar alcohol, the second polyol component is a dianhydrous sugar alcohol, the third polyol component is a polysaccharide alcohol represented by the following chemical formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from a polysaccharide alcohol represented by the following chemical formula 1, and the fifth polyol component is at least one polymer selected from among the first to fourth polyol components. The ratio of the OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition to the total OH equivalent of the polyol composition (OH equivalent of the anhydrous sugar alcohol-alkylene glycol composition / total OH equivalent of the polyol composition) is greater than 0.1 and less than 0.6, The ratio of the total NCO equivalent of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalent of the polyisocyanate / total OH equivalent of the polyol composition) is greater than 1.4 and less than 2.0, Method for preparing (meth)acrylic-modified polyurethane composition: [Chemical Formula 1] In the above chemical formula 1, n is an integer from 0 to 4.

12. A method for producing a (meth)acrylic-modified polyurethane composition, wherein the anhydrous sugar alcohol composition satisfies the following i) to iii): i) The number average molecular weight (Mn) of the anhydrous alcohol composition is 193 to 1,589 g / mol; ii) the polydispersity index (PDI) of the anhydrous sugar alcohol composition is 1.13 to 3.41; iii) The average number of -OH groups per molecule in the anhydrous alcohol composition is 2.54 to 21.

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13. An impact modifier comprising a (meth)acrylic-modified polyurethane composition according to any one of claims 1 to 10.

14. An epoxy resin composition comprising the impact modifier of clause 13; and an epoxy resin.

15. An epoxy resin composition comprising the impact modifier in an amount of more than 10 parts by weight and less than 35 parts by weight, based on 100 parts by weight of the total epoxy resin composition, in claim 14.

16. An epoxy resin composition according to claim 14, wherein the epoxy resin is at least one selected from the group consisting of bisphenol A-epichlorohydrin resin, diglycidyl ether resin of bisphenol A, novolac-type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, dicyclic epoxy resin, glycidyl ester-type epoxy resin, brominated epoxy resin, bio-derived epoxy resin, epoxidized soybean oil, or a combination thereof.

17. A two-component curable composition comprising a subject component including the epoxy resin composition of claim 14; and a curing agent component.

18. An adhesive composition obtained by mixing a subject component including the epoxy resin composition of Article 14 and a hardener component.

19. A method for producing an adhesive composition, comprising a step of mixing a subject component including the epoxy resin composition of Article 14 and a hardener component.

20. Articles to which the adhesive composition of Article 18 is applied.

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