Isocyanate prepolymer composition using anhydrosugar alcohol-alkylene glycol and polyhydric alcohol, end-capped isocyanate prepolymer composition prepared from prepolymer composition, impact modifier comprising same, epoxy resin composition comprising impact modifier, and adhesive comprising same

Abstract

The present invention relates to an isocyanate prepolymer composition using anhydrosugar alcohol-alkylene glycol and polyhydric alcohol and uses thereof and, more specifically, relates to: an isocyanate prepolymer composition which is environmentally friendly, which is prepared by subjecting polyisocyanate to a urethane reaction with a polyol composition comprising polyhydric alcohol, polyether polyol, and anhydrosugar alcohol-alkylene glycol that is an alkylene oxide adduct of anhydrosugar alcohol, and, in particular, which can be used to prepare an end-capped isocyanate prepolymer composition, which in turn can be used as an impact modifier that can be applied to an adhesive epoxy resin composition so as to improve the T-peel strength and impact strength (particularly, impact strength at room temperature) thereof; an end-capped isocyanate prepolymer composition using the prepolymer composition; an impact modifier comprising same; an epoxy resin composition comprising the impact modifier; and an adhesive comprising same.

Description

An isocyanate prepolymer composition using an anhydrous sugar alcohol-alkylene glycol and a polyhydric alcohol, an end-capped isocyanate prepolymer composition prepared from the prepolymer composition and an impact modifier comprising the same, and an epoxy resin composition comprising the impact modifier and an adhesive comprising the same

[0001] The present invention relates to an isocyanate prepolymer composition using an anhydrous sugar alcohol-alkylene glycol and a polyhydric alcohol and its use, and more specifically, to an isocyanate prepolymer composition prepared by urethane reaction of a polyol composition including an anhydrous sugar alcohol-alkylene glycol, which is an alkylene oxide adduct of an anhydrous sugar alcohol, a polyether polyol and a polyhydric alcohol, and a polyisocyanate, which is environmentally friendly, and in particular, an end-capped isocyanate prepolymer composition prepared by using the same can improve the T-peel strength and impact strength (particularly, room temperature impact strength) of an adhesive epoxy resin composition applied as an impact modifier, an end-capped isocyanate prepolymer composition using the prepolymer composition and an impact modifier comprising the same, and an epoxy resin composition comprising the impact modifier and an adhesive comprising the same.

[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 scope of application. To supplement this, rubber additives or thermoplastic polymer additives used do not form chemical bonds with epoxy resin, which reduces corrosion resistance and environmental friendliness.

[0006] Hydrogenated sugars (also called “sugar alcohols”) are compounds obtained by adding hydrogen to the reducing end groups 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 sugar 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, 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 resins, improving their strength. Furthermore, as an eco-friendly material derived from natural products, 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. Due to their diverse applications, anhydrous sugar alcohols are attracting significant attention, and their industrial use is gradually increasing.

[0009] Therefore, there is a demand for the development of an impact modifier that is environmentally friendly by being manufactured using anhydrous sugar alcohol and can improve the strength of epoxy resin when added to a structural adhesive containing epoxy resin.

[0010] The purpose of the present invention is to provide an isocyanate prepolymer composition which is environmentally friendly because it uses anhydrous sugar alcohol, and in particular, an end-capped isocyanate prepolymer composition manufactured using the same can improve the T-peel strength and impact strength (particularly, room temperature impact strength) of an epoxy resin composition for adhesives applied as an impact modifier, an end-capped isocyanate prepolymer composition using the prepolymer composition and an impact modifier comprising the same, and an epoxy resin composition comprising the impact modifier and an adhesive comprising the same.

[0011] A first aspect of the present invention provides an isocyanate prepolymer composition prepared by urethane reaction of a polyol composition comprising an anhydrous sugar alcohol-alkylene glycol, a polyether polyol, and a trihydric or higher polyhydric alcohol, and a polyisocyanate, wherein, based on a total OH equivalent of the polyol composition, the OH equivalent ratio of the anhydrous sugar alcohol-alkylene glycol is greater than 0.05 and less than 0.4, the OH equivalent ratio of the polyether polyol is greater than 0.2 and less than 0.6, the OH equivalent ratio of the trihydric or higher polyhydric alcohol is greater than 0.2 and less than 0.6, and the NCO equivalent ratio of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalents / total OH equivalents) is greater than 1.5 and less than 2.0.

[0012] A second aspect of the present invention provides a method for producing an isocyanate prepolymer composition, comprising a step of urethane-reacting a polyol composition comprising an anhydrous sugar alcohol-alkylene glycol, a polyether polyol, and a trihydric or higher polyhydric alcohol with a polyisocyanate, wherein, based on a total OH equivalent of the polyol composition, the OH equivalent ratio of the anhydrous sugar alcohol-alkylene glycol is greater than 0.05 and less than 0.4, the OH equivalent ratio of the polyether polyol is greater than 0.2 and less than 0.6, the OH equivalent ratio of the trihydric or higher polyhydric alcohol is greater than 0.2 and less than 0.6, and the NCO equivalent ratio of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalents / total OH equivalents) is greater than 1.5 and less than 2.0.

[0013] A third aspect of the present invention provides an end-capped isocyanate prepolymer composition prepared by reacting the isocyanate prepolymer composition according to the first aspect of the present invention with a terminal capping agent.

[0014] A fourth aspect of the present invention provides an impact modifier comprising an end-capped isocyanate prepolymer composition according to the third aspect of the present invention.

[0015] A fifth aspect of the present invention provides an epoxy resin composition comprising an impact modifier according to the fourth aspect of the present invention; and an epoxy resin.

[0016] A sixth aspect of the present invention provides an adhesive comprising an epoxy resin composition according to the fifth aspect of the present invention.

[0017] The isocyanate prepolymer composition according to the present invention is environmentally friendly, and in particular, the end-capped isocyanate prepolymer composition manufactured using the same can significantly improve the T-peel strength and impact strength (particularly, room temperature impact strength) of an adhesive epoxy resin composition applied as an impact modifier, compared to existing structural adhesives.

[0018] In addition, the isocyanate prepolymer composition according to the present invention can improve the value of biomaterials and contribute to environmental friendliness by using anhydrous sugar alcohol, which is an environmentally friendly material, as a polyol raw material.

[0019] Hereinafter, the present invention will be described in more detail.

[0020] [Isocyanate prepolymer composition and method for producing the same]

[0021] The isocyanate prepolymer composition of the present invention is prepared by subjecting a polyol composition comprising an anhydrous sugar alcohol-alkylene glycol, a polyether polyol, and a trihydric or higher polyhydric alcohol to a urethane reaction with a polyisocyanate, wherein, based on the total OH equivalent of the polyol composition, the OH equivalent ratio of the anhydrous sugar alcohol-alkylene glycol is greater than 0.05 and less than 0.4, the OH equivalent ratio of the polyether polyol is greater than 0.2 and less than 0.6, the OH equivalent ratio of the trihydric or higher polyhydric alcohol is greater than 0.2 and less than 0.6, and the NCO equivalent ratio of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalents / total OH equivalents) is greater than 1.5 and less than 2.0.

[0022] In the present invention, when the OH equivalent ratio of the anhydrous sugar alcohol-alkylene glycol is 0.05 or less based on the total OH equivalent of the polyol composition, the molecular chain of the urethane reaction product becomes longer and the intermolecular entanglement is relatively reduced, and as a result, the T-peel strength of the epoxy resin adhesive including the terminal-capped isocyanate prepolymer composition manufactured using the same as an impact modifier is lowered, and the room temperature impact strength is also lowered, so that an unstable crack may occur when measuring the room temperature impact strength. Conversely, when the OH equivalent ratio of the anhydrous sugar alcohol-alkylene glycol is 0.4 or more based on the total OH equivalent of the polyol composition, the length of the alkyl chain, which is a soft segment in the structure of the urethane reaction product, is shortened, and as a result, the T-peel strength and room temperature impact strength of the epoxy resin adhesive including the terminal-capped isocyanate prepolymer composition manufactured using the same as an impact modifier are lowered.

[0023] In one specific example, based on the total OH equivalent of the polyol composition, the OH equivalent ratio of the anhydrosugar alcohol-alkylene glycol may be, for example, greater than 0.05, 0.051 or more, 0.055 or more, 0.06 or more, 0.065 or more, 0.07 or more, 0.075 or more, or 0.08 or more, and may also be less than 0.4, 0.39 or less, 0.38 or less, 0.37 or less, 0.36 or less, 0.35 or less, 0.34 or less, 0.33 or less, 0.32 or less, 0.31 or less, or 0.3 or less, but is not limited thereto.

[0024] In the present invention, when the OH equivalent ratio of the polyether polyol is 0.2 or less based on the total OH equivalent of the polyol composition, the T-peel strength and room temperature impact strength of the epoxy resin adhesive comprising the terminal-capped isocyanate prepolymer composition manufactured by utilizing the urethane reaction product as an impact modifier are reduced. Conversely, when the OH equivalent ratio of the polyether polyol is 0.6 or more based on the total OH equivalent of the polyol composition, the T-peel strength of the epoxy resin adhesive comprising the terminal-capped isocyanate prepolymer composition manufactured by utilizing the urethane reaction product as an impact modifier are reduced, and the room temperature impact strength is also reduced, so that an unstable crack may occur when measuring the room temperature impact strength.

[0025] In one specific example, based on the total OH equivalent of the polyol composition, the OH equivalent ratio of the polyether polyol may be, for example, greater than 0.2, greater than 0.21, greater than 0.22, greater than 0.23, greater than 0.24, greater than 0.25, greater than 0.26, greater than 0.27, greater than 0.28, greater than 0.29, or greater than 0.3, and may also be less than 0.6, less than 0.59, less than 0.58, less than 0.57, less than 0.56, less than 0.55, less than 0.54, less than 0.53, less than 0.52, less than 0.51, or less than 0.5, but is not limited thereto.

[0026] In the present invention, when the OH equivalent ratio of the trivalent or higher polyhydric alcohol is 0.2 or less based on the total OH equivalent of the polyol composition, the T-peel strength of the epoxy resin adhesive comprising the terminal-capped isocyanate prepolymer composition manufactured using the urethane reaction product as an impact modifier is reduced, and the room temperature impact strength is also reduced, so that an unstable crack may occur when measuring the room temperature impact strength. Conversely, when the OH equivalent ratio of the trivalent or higher polyhydric alcohol is 0.6 or more based on the total OH equivalent of the polyol composition, the T-peel strength and room temperature impact strength of the epoxy resin adhesive comprising the terminal-capped isocyanate prepolymer composition manufactured using the urethane reaction product as an impact modifier are reduced.

[0027] In one specific example, based on the total OH equivalent of the polyol composition, the OH equivalent ratio of the trihydric or higher polyhydric alcohol may be, for example, greater than 0.2, 0.21 or more, 0.22 or more, 0.23 or more, 0.24 or more, 0.25 or more, 0.26 or more, 0.27 or more, 0.28 or more, 0.29 or more, or 0.3 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.

[0028] In the present invention, if the NCO equivalent ratio of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalent / total OH equivalent) is 1.5 or less, the T-peel strength and room temperature impact strength of the epoxy resin adhesive comprising the end-capped isocyanate prepolymer composition manufactured by utilizing the urethane reaction product as an impact modifier are reduced. Conversely, if the NCO equivalent ratio of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalent / total OH equivalent) is 2.0 or more, the T-peel strength of the epoxy resin adhesive comprising the end-capped isocyanate prepolymer composition manufactured by utilizing the urethane reaction product as an impact modifier are reduced, and the room temperature impact strength is also reduced, so that an unstable crack may occur when measuring the room temperature impact strength.

[0029] In one specific embodiment, the NCO equivalent ratio of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalent / total OH equivalent) can be, for example, greater than 1.5, 1.51 or more, 1.52 or more, 1.53 or more, 1.54 or more, 1.55 or more, 1.56 or more, 1.57 or more, 1.58 or more, 1.59 or more, or 1.6 or more, and can also be, but is not limited to, less than 2.0, 1.99 or less, 1.98 or less, 1.97 or less, 1.96 or less, 1.95 or less, 1.94 or less, 1.93 or less, 1.92 or less, 1.91 or less, or 1.9 or less.

[0030] Each component used in the preparation of the isocyanate prepolymer composition of the present invention is described in more detail below.

[0031] Anhydrous alcohol-alkylene glycol

[0032] The above anhydrous sugar alcohol-alkylene glycol is an adduct obtained by reacting hydroxyl groups at both terminals or one terminal (preferably both terminals) of anhydrous sugar alcohol with an alkylene oxide.

[0033] The above anhydrosugar alcohol may be a monoanhydrosugar alcohol, a dianhydrosugar alcohol, or a combination thereof. A monoanhydrosugar alcohol is an anhydrosugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol form with four hydroxyl groups in the molecule. In the present invention, the type of the monoanhydrosugar alcohol is not particularly limited, but preferably, it may be a 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. A dianhydrosugar alcohol is an anhydrosugar alcohol formed by removing two water molecules from the inside of a hydrogenated sugar, and has a diol form with two hydroxyl groups in the molecule, and can be produced by utilizing a hexitol derived from starch. Isosorbide alcohols, derived from renewable natural resources, have long attracted considerable interest and research into their production methods has been ongoing. Among these isosorbide alcohols, produced from sorbitol, currently has the widest range of industrial applications.

[0034] In one specific embodiment, the anhydrosugar alcohol may be a di-anhydrosugar alcohol, more specifically a di-anhydrosugar hexitol, more specifically a 1,4:3,6-dianhydrohexitol, and more specifically may be selected from the group consisting of isosorbide, isomannide, isoidide or a combination thereof, and preferably isosorbide.

[0035] In one embodiment, the alkylene oxide may be a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, and more specifically, may be ethylene oxide, propylene oxide, or a combination thereof.

[0036] In one specific example, the anhydrous sugar alcohol-alkylene glycol may be a compound represented by the following chemical formula 1.

[0037] [Chemical Formula 1]

[0038]

[0039] In the above chemical formula 1,

[0040] R 1 and R 2 Each independently represents a linear or branched alkylene group having 2 to 8 carbon atoms,

[0041] m and n each independently represent an integer from 0 to 15, and m+n represents an integer from 1 to 30.

[0042] More specifically, in the chemical formula 1,

[0043] R 1 and R 2 Each independently represents an ethylene group, a propylene group or an isopropylene group, preferably R 1 and R 2 are identical to each other,

[0044] m and n each independently represent an integer from 1 to 14, provided that m+n represents an integer from 2 to 25, more specifically an integer from 3 to 20, and even more specifically an integer from 5 to 20.

[0045] In one specific example, the anhydrous alcohol-alkylene glycol may be isosorbide-propylene glycol, isosorbide-ethylene glycol, or a mixture thereof.

[0046] [Isosorbide-propylene glycol]

[0047]

[0048] In the above chemical formula, a and b each independently represent an integer from 0 to 15, provided that a+b is an integer from 1 to 30, and more preferably, a and b each independently represent an integer from 1 to 14, provided that a+b is an integer from 2 to 25, more specifically an integer from 3 to 20, and even more specifically an integer from 5 to 20.

[0049] [Isosorbide-ethylene glycol]

[0050]

[0051] In the above chemical formula, c and d each independently represent an integer from 0 to 15, provided that c+d may be an integer from 1 to 30, and more preferably, c and d each independently represent an integer from 1 to 14, provided that c+d may be an integer from 2 to 25, more specifically an integer from 3 to 20, and even more specifically an integer from 5 to 20.

[0052] In one specific example, the reaction molar ratio of the anhydrous sugar alcohol and the alkylene oxide is, for example, 1 mol or more, 2 mol or more, 3 mol or more, or 5 mol or more of the alkylene oxide per 1 mol of the anhydrous sugar alcohol, and also 30 mol or less, 25 mol or less, or 20 mol or less, and may be, for example, 1 to 30 mol, preferably 2 to 25 mol, and more preferably 3 to 20 mol, but is not limited thereto.

[0053] In one specific example, the addition reaction of the anhydrous sugar alcohol and the alkylene oxide may be performed, for example, in a high-pressure reactor capable of pressurization (for example, pressurization of 3 MPa or more), in the presence of a base catalyst (for example, a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide, or a hydroxide of an alkaline earth metal such as calcium hydroxide), at an elevated temperature (for example, 100°C to 180°C, or 120°C to 160°C), for, for example, 1 hour to 8 hours or 2 hours to 4 hours, but is not limited thereto.

[0054] polyether polyol

[0055] The above polyether polyol is a polyether polymer compound having two or more hydroxyl groups in the molecule.

[0056] In one specific embodiment, the polyether polyol may include one or more selected from the group consisting of polyalkylene glycol, polytetrahydrofuran, or combinations thereof.

[0057] In one embodiment, the polyalkylene glycol may be a poly(C1-C6)alkylene glycol, and more specifically may be selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, or combinations thereof.

[0058] In one specific example, the number average molecular weight (Mn: unit g / mol) of the polyether polyol may be 500 or more and less than 4,000. More specifically, the number average molecular weight 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 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.

[0059] polyhydric alcohols with three or more hydrocarbons

[0060] The above trivalent or higher polyhydric alcohol is a compound having three or more hydroxyl groups in the molecule.

[0061] In one specific example, the trivalent or higher polyhydric alcohol may be at least one selected from the group consisting of glycerol, trimethylolpropane, triethanolamine, pentaerythritol, xylitol, sorbitol, or a combination thereof, and more specifically, may be glycerol, triethanolamine, or a combination thereof, but is not limited thereto.

[0062] Any additional polyol

[0063] In one embodiment, the polyol composition may optionally further comprise a polyol component (“additional polyol component”) other than the anhydrous sugar alcohol-alkylene glycol, polyether polyol, and trihydric or higher polyhydric alcohol.

[0064] In one specific example, the additional polyol component may be selected from the group consisting of polyester polyol, polycaprolactone diol, polymer polyols obtained by polymerizing these polyols with vinyl compounds, or combinations thereof. Examples of the vinyl compounds commonly used include acrylonitrile, styrene, and methyl methacrylonitrile, and typically, acrylonitrile may be used alone or in a mixture with styrene.

[0065] Urethane reaction with polyisocyanate and polyol compositions

[0066] According to another aspect of the present invention, a method for producing an isocyanate prepolymer composition is provided, comprising a step of urethane-reacting a polyol composition comprising an anhydrous sugar alcohol-alkylene glycol, a polyether polyol, and a trihydric or higher polyhydric alcohol with a polyisocyanate, wherein, based on a total OH equivalent of 1 equivalent of the polyol composition, the OH equivalent ratio of the anhydrous sugar alcohol-alkylene glycol is greater than 0.05 and less than 0.4, the OH equivalent ratio of the polyether polyol is greater than 0.2 and less than 0.6, the OH equivalent ratio of the trihydric or higher polyhydric alcohol is greater than 0.2 and less than 0.6, and the NCO equivalent ratio of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalents / total OH equivalents) is greater than 1.5 and less than 2.0.

[0067] In the method for producing an isocyanate prepolymer composition according to the present invention, the description of the anhydrous sugar alcohol-alkylene glycol (including the anhydrous sugar alcohol and alkylene oxide used in the production thereof), polyether polyol, and trihydric or higher polyhydric alcohol is as described above.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] More specifically, the polyisocyanate may be methylenediphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] In one specific example, the urethane reaction may be performed at an elevated temperature (e.g., 50 to 100°C, preferably 50 to 80°C) for an appropriate time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours), but is not limited thereto.

[0076] [Terminal-capped isocyanate prepolymer composition, impact modifier, epoxy resin composition, and adhesive]

[0077] The present invention also provides an end-capped isocyanate prepolymer composition prepared by reacting the isocyanate prepolymer composition of the present invention described above with a terminal capping agent.

[0078] The present invention also provides an impact modifier comprising the terminal-capped isocyanate prepolymer composition described above.

[0079] The present invention also provides an epoxy resin composition comprising the above-described impact modifier; and an epoxy resin.

[0080] The present invention also provides an adhesive comprising the above-described epoxy resin composition.

[0081] In one specific embodiment, the terminal capping agent may be at least one selected from the group consisting of a phenolic compound, a triazine compound, an alcohol compound, an amine compound, a benzene compound, a dicarboxylic acid ester compound, a novolac compound, or a combination thereof, and more specifically, a phenolic compound (e.g., allylphenol, t-butylphenol, phenol, bisphenol A, bisphenol M, bisphenol F, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,2-dihydroxybenzene, phenolphthalein, o,o'-diallylbisphenol A, phenolphthalein, or a combination thereof), a benzene compound (e.g., fluoroglucinol, resorcinol, naphthoresorcinol, or a combination thereof), a dicarboxylic acid ester compound (e.g., gallic acid ester, maleic acid ester, or a combination thereof), a novolac compound It may be at least one selected from the group consisting of compounds (e.g., cresol novolac) or combinations thereof, and more specifically, it may be a phenolic compound.

[0082] 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.

[0083] In one specific example, the epoxy resin may be 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, but is not limited thereto.

[0084] 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 type epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, an aromatic glycidylamine type epoxy resin such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane type glycidylamine, and 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 phenol aralkyl type epoxy resin having a phenylene and / or biphenylene skeleton, and a phenylene and / or biphenylene skeleton. Examples thereof include, but are not limited to, those selected from the group consisting of aralkyl type epoxy resins such as naphthol aralkyl type epoxy resins, aliphatic epoxy resins such as alicyclic epoxy resins such as vinylcyclohexene dioxide, dicyclopentadiene oxide, and alicyclic diepoxy-adipate, or combinations thereof.

[0085] 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.

[0086] In one specific example, the reaction of the isocyanate prepolymer composition with the epoxy resin is a cyclization reaction of the isocyanate prepolymer composition with the epoxy resin, which may be performed in the presence of a catalyst, for example, a basic catalyst such as an organic ammonium salt compound, at an elevated temperature (for example, 100 to 200°C, preferably 120 to 180°C) for an appropriate time (for example, 0.1 to 5 hours, preferably 0.5 to 2 hours), but is not limited thereto.

[0087] In one embodiment, the impact modifier of the present invention may consist solely of the end-capped isocyanate prepolymer composition of the present invention.

[0088] In another specific embodiment, the impact modifier of the present invention may further include an additional impact modifier component in addition to the end-capped isocyanate prepolymer composition of the present invention, within the scope of achieving the purpose of the present invention, and such additional impact modifier components include, for example, rubber-based impact modifiers such as carboxyl terminated butadiene acrylonitrile (CTBN) and amine terminated butadiene acrylonitrile (ATBN), and thermoplastic polymer-based impact modifiers such as polyethersulfone, polyetherimide, polycarbonate, polyimide, polyamide, acrylonitrile butadiene styrene (ABS) and methacrylate butadiene styrene (MBS). Reinforcing agents, or mixtures thereof, may be used.

[0089] In one embodiment, the additional impact modifier may be in core-shell form.

[0090] In one specific example, the impact modifier of the present invention may be included in an amount of 2 to 65 parts by weight, more specifically 5 to 60 parts by weight, and even more specifically 10 to 55 parts by weight, within a total of 100 parts by weight of the epoxy resin composition of the present invention, but is not limited thereto.

[0091] In one specific embodiment, the epoxy resin composition of the present invention may further include, in addition to the impact modifier and epoxy resin of the present invention described above, one or more selected from a curing agent, a curing accelerator, a filler, an adhesion accelerator, or a combination thereof.

[0092] As the above curing agent, a curing agent commonly used in this field can be used alone or in combination of two or more, and examples thereof include amine compounds (e.g., tertiary amines) such as benzyldimethylamine, tris(dimethylaminomethyl)phenol, and dimethylcyclohexylamine; imidazole compounds such as 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-methylimidazole; organophosphorus compounds such as triphenylphosphine and triphenyl phosphite; quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide; diazabicycloalkenes such as 1,8-diazabicyclo[5.4.0]undecene-7 or organic acid salts thereof; organometallic compounds such as zinc octylate, tin octylate, and aluminum acetylacetone complex; Examples thereof include, but are not limited to, those selected from the group consisting of quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide; boron compounds such as boron trifluoride and triphenylborate; metal halides such as zinc chloride and tin chloride; latent curing agents (e.g., high-melting-point dispersion-type latent amine adducts obtained by adding dicyandiamide and amine to epoxy resins, 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.

[0093] In one specific example, the curing agent may be selected from the group consisting of an amine compound, an imidazole compound, an organophosphorus compound, a latent curing agent, or a combination thereof.

[0094] Since room temperature curing of epoxy resin usually requires a temperature of 15℃ or higher and a curing time of 24 hours or more, there are times when fast curing and low temperature curing are necessary.

[0095] Therefore, for the purpose of promoting curing, the epoxy resin composition of the present invention may additionally include a curing accelerator. Examples of the curing accelerator include urea-based compounds, thiourea-based compounds, Lewis acid-based compounds, or mixtures thereof, and specifically include but are not limited to butylated urea, butylated melamine, butylated thiourea, boron trifluoride, and the like.

[0096] When a curing accelerator is included in the epoxy resin composition of the present invention, the amount thereof may be 0.01 to 3 parts by weight, more specifically 0.05 to 2 parts by weight, and even more specifically 0.08 to 1.5 parts by weight, based on 100 parts by weight of the total of the epoxy resin and the curing agent, but is not limited thereto. If the amount of the curing accelerator used is too small, the curing reaction of the epoxy resin may not progress sufficiently, which may cause a problem of deterioration in mechanical properties and thermal properties, and conversely, if the amount of the curing accelerator used is too large, the curing reaction may progress slowly even during storage of the epoxy resin composition, which may cause a problem of increased viscosity.

[0097] The above fillers are mainly used to improve the mechanical properties of the cured product by mixing them with epoxy resin or a hardener, 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). Metals include aluminum, aluminum oxide, iron, iron oxide, and copper, which contribute to the coefficient of thermal expansion, wear resistance, thermal conductivity, and adhesiveness; antimony oxide (Sb2O3), which imparts flame retardancy; barium titanate, and organic fillers for lightweighting such as fine plastic spheres (phenolic resin, urea resin, etc.). In addition, various glass fibers and chemical fiber cloths, which are reinforcing fillers, can be treated as fillers in a broad sense in the manufacture of laminated products. To impart thixotropic properties to the resin (thixotropic: thixotropy or thixotropy refers to the property of having a liquid state when flowing and a solid state when stationary, so that the resin adhered to a vertical surface or by immersion or impregnated into a laminated material does not flow or run off during curing), fine particles with a large unit surface area are used. Examples include colloidal silica (Aerosil) and bentonite-based clays.

[0098] 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. The content of the filler in the composition may be 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 of the epoxy resin and the curing agent.

[0099] In one specific example, the adhesion promoter may be, but is not limited to, a polyurethane-modified epoxy resin, a polyurethane-modified silyl epoxy resin, or a combination thereof.

[0100] The epoxy resin composition of the present invention may further include one or more additive components commonly used in epoxy resin compositions, as needed.

[0101] As such additive components, for example, those selected from the group consisting of antioxidants, UV absorbers, resin modifiers, silane coupling agents, diluents, colorants, defoamers, defoamers, dispersants, viscosity modifiers, gloss modifiers, wetting agents, conductivity-imparting agents, or combinations thereof may be used.

[0102] The above antioxidant can be used to further improve the heat resistance stability of the obtained cured product, and is not particularly limited, but 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. The content of the antioxidant in the composition can be 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 of the epoxy resin and the curing agent.

[0103] The UV absorbent is not particularly limited, but may be selected from the group consisting of, for example, benzotriazole-based UV absorbers such as TINUBIN P or TINUVIN 234 manufactured by BASF Japan Ltd.; triazine-based UV absorbers such as TINUVIN 1577ED; hindered amine-based UV absorbers such as CHIMASSOLV 2020FDL, or combinations thereof. The content of the UV absorbent in the composition may be 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 of the epoxy resin and the curing agent.

[0104] The resin modifier is not particularly limited, but examples thereof include flexibility-imparting agents such as polypropylene glycidyl ether, polymerized fatty acid polyglycidyl ether, polypropylene glycol, and urethane prepolymer. The content of the resin modifier in the composition may be 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 of the epoxy resin and the curing agent.

[0105] The silane coupling agent is not particularly limited, but examples thereof include chloropropyltrimethoxysilane, vinyltrichlorosilane, γ-methacryloxypropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. The content of the silane coupling agent in the composition may be 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 of the epoxy resin and the curing agent.

[0106] The above diluent is mainly used to reduce viscosity by adding it to epoxy resin or hardener, and when used, it plays a role in improving flowability and defoaming, improving penetration into details of parts, or enabling effective addition of fillers. Unlike solvents, diluents generally do not volatilize, but remain in the cured product when the resin hardens, 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. The content of the diluent in the composition may be 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 of the epoxy resin and the curing agent.

[0107] Pigments or dyes are used as coloring agents to color resins. Commonly used pigments include titanium dioxide, cadmium red, charcoal green, carbon black, chrome green, chrome yellow, navy blue, and charcoal blue.

[0108] 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 resin and pigment, wetting agents for improving the adhesion between the epoxy resin and the material, viscosity regulators, gloss regulators for controlling the gloss of the resin, additives for improving adhesiveness, additives for imparting electrical properties, etc.

[0109] The curing method of the epoxy resin composition of the present invention is not particularly limited, and for example, a conventionally known curing device such as a sealed curing furnace or a tunnel furnace capable of continuous curing can be used. The heating method used for the curing is not particularly limited, and for example, a conventionally known method such as hot air circulation, infrared heating, or high-frequency heating can be used.

[0110] The curing temperature and curing time may range from 30 seconds to 10 hours at 80°C to 250°C. In one specific example, pre-curing may be performed at 80°C to 120°C for 0.5 hours to 5 hours, and then post-curing may be performed at 120°C to 180°C for 0.1 hours to 5 hours. In one specific example, for short-term curing, curing may be performed at 150°C to 250°C for 30 seconds to 30 minutes.

[0111] In one specific embodiment, the epoxy resin composition of the present invention may be stored separately as two or more components, for example, a component including a curing agent and a component including an epoxy resin, and these may be combined prior to curing. In another specific embodiment, the epoxy resin composition of the present invention may be stored as a thermosetting composition in which each component is blended and subjected to curing as is. When stored as a thermosetting composition, it may be stored at a low temperature (typically -40°C to 15°C).

[0112] 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.

[0113] [Example]

[0114] <Production of anhydrous alcohol>

[0115] Manufacturing Example A1: Manufacturing of anhydrous sugar alcohol using 97 wt% glucose and a thin film distiller

[0116] 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 then concentrated to obtain 1,000 g of a concentrated hydrogenated sugar composition.

[0117] 1,000 g of the above-mentioned concentrated hydrogenated sugar composition was placed in a batch reactor equipped with a stirrer, heated to 100°C, concentrated, and then 9.6 g of sulfuric acid was added. 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 completion of the dehydration reaction, the temperature of the reaction product was cooled to 110°C or lower, and approximately 15.7 g of a 50% sodium hydroxide aqueous solution was added to neutralize the reaction product. Thereafter, the temperature was cooled to 100°C or lower, and concentrated under conditions of a reduced pressure of 45 mmHg for more than 1 hour 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 to isosorbide was 71.9 wt%, and through this, the molar conversion rate from sorbitol to isosorbide was calculated to be 77.6%.

[0118] 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%.

[0119] The obtained anhydrous sugar alcohol distillate and 300 g of acetone (Samjeon Pure Chemicals) as a solvent were placed in a jacket-shaped reactor and mixed, and then crystallization was performed while lowering the temperature of the mixture from about 50°C to -10°C. After completion of crystallization, dehydration was performed, and anhydrous sugar alcohol crystals were recovered from the mixture solution, and the purity of the obtained anhydrous sugar alcohol crystals was at least 99.5%.

[0120] <Manufacture of anhydrous alcohol-alkylene glycol>

[0121] Manufacturing Example B1: Preparation of 5 mol isosorbide-ethylene oxide adduct

[0122] 100 g of isosorbide and 1.0 g of KOH obtained in the above Manufacturing Example A1 were placed in a pressurized reactor, and the pressurization and exhaust processes were repeated 3 times using nitrogen gas. Thereafter, the temperature was raised to 100°C to remove moisture inside the reactor, and when all moisture was removed, 150.7 g of ethylene oxide was slowly added into the reactor and the reaction was carried out at 100°C to 140°C for 5 hours. Upon completion of the reaction, the internal temperature of the reactor was cooled to 50°C, 4 g of Ambosol MP20 was added as an adsorbent to remove metals, and the reactor was heated again and stirred at a temperature of 100°C to 120°C for 1 to 5 hours to remove metal ions. At this time, the metal ion content was monitored, and when no more metal ions were detected, the internal temperature of the reactor was cooled to 60°C to 90°C, and then the residual byproducts were removed through filtration, thereby obtaining 240 g of a transparent liquid isosorbide-ethylene oxide 5 mol adduct.

[0123] Manufacturing Example B2: Preparation of 5 mol isosorbide-propylene oxide adduct

[0124] By performing the same method as in Preparation Example B1, except that 198.7 g of propylene oxide was used instead of 150.7 g of ethylene oxide, 290 g of a transparent liquid isosorbide-propylene oxide 5 mol adduct was obtained.

[0125] <Preparation of isocyanate prepolymer composition and end-capped isocyanate prepolymer composition>

[0126] Example A1: Preparation of an isocyanate prepolymer composition using a polyol composition comprising polytetrahydrofuran, isosorbide-ethylene oxide 5 mol adduct, and glycerol and a polyisocyanate (OH equivalent ratio of polytetrahydrofuran:isosorbide-ethylene oxide 5 mol adduct:glycerol = 0.5:0.1:0.4, NCO / OH equivalent ratio = 1.7)

[0127] As a polyol component, 2.78 g of the 5-mol isosorbide-ethylene oxide adduct obtained in the above Preparation Example B1, 75 g of polytetrahydrofuran and 1.84 g of glycerol, 28.34 g of isophorone diisocyanate as a polyisocyanate component, and 0.3 g of dibutyltin dilaurate (DBTDL) as a catalyst were placed in a reactor, and the internal temperature of the reactor was slowly increased to 80°C. After the reaction temperature reached 80°C, a urethane reaction was performed while stirring for 3 hours, thereby preparing an isocyanate prepolymer composition.

[0128] After the completion of the above urethane reaction, the reactor temperature was adjusted to 60°C, and the NCO content of the isocyanate prepolymer composition was measured. Then, 1.4 equivalents of t-butyl phenol based on 1 equivalent of NCO was added to the reactor. Thereafter, the NCO content was measured, and the reaction was terminated when the NCO content became 0%. After the completion of the reaction, the reaction product was cooled to room temperature, thereby obtaining 100 g of an end-capped isocyanate prepolymer composition.

[0129] Example A2: Preparation of an isocyanate prepolymer composition using a polyol composition comprising polytetrahydrofuran, isosorbide-ethylene oxide 5 mol adduct, and glycerol and a polyisocyanate (OH equivalent ratio of polytetrahydrofuran:isosorbide-ethylene oxide 5 mol adduct:glycerol = 0.3:0.3:0.4, NCO / OH equivalent ratio = 1.7)

[0130] An isocyanate prepolymer composition was prepared by performing the same method as Example A1, except that the content of the isosorbide-ethylene oxide 5 mol adduct obtained in the above Preparation Example B1 was changed from 2.78 g to 8.35 g and the content of polytetrahydrofuran was changed from 75 g to 45 g, and then an end-capping reaction was performed by the same method as Example A1, thereby obtaining 100 g of an end-capped isocyanate prepolymer composition.

[0131] Example A3: Preparation of an isocyanate prepolymer composition using a polyol composition comprising polytetrahydrofuran, isosorbide-ethylene oxide 5 mol adduct, and glycerol and a polyisocyanate (OH equivalent ratio of polytetrahydrofuran:isosorbide-ethylene oxide 5 mol adduct:glycerol = 0.5:0.1:0.4, NCO / OH equivalent ratio = 1.9)

[0132] An isocyanate prepolymer composition was prepared by performing the same method as in Example A1, except that the content of isophorone diisocyanate was changed from 28.34 g to 31.68 g, and then an end-capping reaction was performed by the same method as in Example A1, thereby obtaining 130 g of an end-capped isocyanate prepolymer composition.

[0133] Example A4: Preparation of an isocyanate prepolymer composition using a polyol composition comprising polytetrahydrofuran, 5 mol isosorbide-propylene oxide adduct, and glycerol and a polyisocyanate (OH equivalent ratio of polytetrahydrofuran: 5 mol isosorbide-propylene oxide adduct: glycerol = 0.5:0.1:0.4, NCO / OH equivalent ratio = 1.7)

[0134] An isocyanate prepolymer composition was prepared by performing the same method as Example A1, except that 3.28 g of the 5 mol isosorbide-propylene oxide adduct obtained in Preparation Example B2 was used instead of the 5 mol isosorbide-ethylene oxide adduct obtained in Preparation Example B1, and then an end-capping reaction was performed by the same method as Example A1, thereby obtaining 130 g of an end-capped isocyanate prepolymer composition.

[0135] Example A5: Preparation of an isocyanate prepolymer composition using a polyol composition comprising polytetrahydrofuran, 5 mol isosorbide-propylene oxide adduct, and glycerol and a polyisocyanate (OH equivalent ratio of polytetrahydrofuran: 5 mol isosorbide-propylene oxide adduct: glycerol = 0.3:0.3:0.4, NCO / OH equivalent ratio = 1.7)

[0136] An isocyanate prepolymer composition was prepared by performing the same method as Example A1, except that 9.84 g of the isosorbide-propylene oxide 5 mol adduct obtained in Preparation Example B2 was used instead of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example B1, and the content of polytetrahydrofuran was changed from 75 g to 45 g. Thereafter, an end-capping reaction was performed by the same method as Example A1, thereby obtaining 100 g of an end-capped isocyanate prepolymer composition.

[0137] Example A6: Preparation of an isocyanate prepolymer composition using a polyol composition comprising polytetrahydrofuran, 5 mol isosorbide-propylene oxide adduct, and glycerol and a polyisocyanate (OH equivalent ratio of polytetrahydrofuran: 5 mol isosorbide-propylene oxide adduct: glycerol = 0.5:0.1:0.4, NCO / OH equivalent ratio = 1.9)

[0138] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 3.28 g of the isosorbide-propylene oxide 5 mol adduct obtained in Preparation Example B2 was used instead of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example B1, and the content of isophorone diisocyanate was changed from 28.34 g to 31.68 g. Thereafter, an end-capping reaction was performed in the same manner as in Example A1, thereby obtaining 100 g of an end-capped isocyanate prepolymer composition.

[0139] Example A7: Preparation of an isocyanate prepolymer composition using a polyol composition comprising polytetrahydrofuran, 5 mol isosorbide-propylene oxide adduct, and glycerol and a polyisocyanate (OH equivalent ratio of polytetrahydrofuran: 5 mol isosorbide-propylene oxide adduct: glycerol = 0.5:0.1:0.4, NCO / OH equivalent ratio = 1.6)

[0140] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 3.5 g of the isosorbide-propylene oxide 5 mol adduct obtained in Preparation Example B2 was used instead of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example B1, the content of polytetrahydrofuran was changed from 75 g to 80 g, the content of glycerol was changed from 1.84 g to 1.96 g, and the content of isophorone diisocyanate was changed from 28.34 g to 28.45 g. Thereafter, an end-capping reaction was performed in the same manner as in Example A1, thereby obtaining 120 g of an end-capped isocyanate prepolymer composition.

[0141] Example A8: Preparation of an isocyanate prepolymer composition using a polyol composition comprising polypropylene glycol, 5 mol isosorbide-ethylene oxide adduct, and glycerol and a polyisocyanate (OH equivalent ratio of polypropylene glycol: 5 mol isosorbide-ethylene oxide adduct: glycerol = 0.5:0.1:0.4, NCO / OH equivalent ratio = 1.7)

[0142] An isocyanate prepolymer composition was prepared by performing the same method as in Example A1, except that 75 g of polypropylene glycol was used instead of polytetrahydrofuran and the content of isophorone diisocyanate was changed from 28.34 g to 28.45 g, and then an end-capping reaction was performed by the same method as in Example A1, thereby obtaining 110 g of an end-capped isocyanate prepolymer composition.

[0143] Example A9: Preparation of a polyol composition comprising polypropylene glycol, 5 mol isosorbide-propylene oxide adduct, and glycerol, and an isocyanate prepolymer composition using polyisocyanate (OH equivalent ratio of polypropylene glycol: 5 mol isosorbide-propylene oxide adduct: glycerol = 0.5:0.1:0.4, NCO / OH equivalent ratio = 1.7)

[0144] An isocyanate prepolymer composition was prepared by performing the same method as Example A1, except that 3.28 g of the isosorbide-propylene oxide 5 mol adduct obtained in Preparation Example B2 was used instead of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example B1, and 75 g of polypropylene glycol was used instead of polytetrahydrofuran. Thereafter, an end-capping reaction was performed by the same method as Example A1, thereby obtaining 110 g of an end-capped isocyanate prepolymer composition.

[0145] Example A10: Preparation of a polyol composition comprising polytetrahydrofuran, 5 mol isosorbide-propylene oxide adduct, and glycerol, and an isocyanate prepolymer composition using a polyisocyanate (OH equivalent ratio of polytetrahydrofuran: 5 mol isosorbide-propylene oxide adduct: glycerol = 0.58:0.12:0.3, NCO / OH equivalent ratio = 1.7)

[0146] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 3.94 g of the isosorbide-propylene oxide 5 mol adduct obtained in Preparation Example B2 was used instead of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example B1, the content of polytetrahydrofuran was changed from 75 g to 87 g, and the content of glycerol was changed from 1.84 g to 1.38 g. Thereafter, an end-capping reaction was performed in the same manner as in Example A1, thereby obtaining 120 g of an end-capped isocyanate prepolymer composition.

[0147] Example A11: Preparation of a polyol composition comprising polytetrahydrofuran, 5 mol isosorbide-propylene oxide adduct, and glycerol, and an isocyanate prepolymer composition using a polyisocyanate (OH equivalent ratio of polytetrahydrofuran: 5 mol isosorbide-propylene oxide adduct: glycerol = 0.42:0.08:0.5, NCO / OH equivalent ratio = 1.7)

[0148] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 2.62 g of the isosorbide-propylene oxide 5 mol adduct obtained in Preparation Example B2 was used instead of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example B1, the content of polytetrahydrofuran was changed from 75 g to 63 g, and the content of glycerol was changed from 1.84 g to 2.30 g. Thereafter, an end-capping reaction was performed in the same manner as in Example A1, thereby obtaining 110 g of an end-capped isocyanate prepolymer composition.

[0149] Example A12: Preparation of an isocyanate prepolymer composition using a polyol composition comprising polytetrahydrofuran, 5 mol isosorbide-propylene oxide adduct, and triethanolamine and a polyisocyanate (OH equivalent ratio of polytetrahydrofuran: 5 mol isosorbide-propylene oxide adduct: triethanolamine = 0.5:0.1:0.4, NCO / OH equivalent ratio = 1.7)

[0150] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 3.28 g of the isosorbide-propylene oxide 5 mol adduct obtained in Preparation Example B2 was used instead of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example B1, and 2.98 g of triethanolamine was used instead of glycerol. An end-capping reaction was then performed in the same manner as in Example A1, except that 1.4 equivalents of 2-allyl phenol was used instead of t-butyl phenol, thereby obtaining 110 g of an end-capped isocyanate prepolymer composition.

[0151] Comparative Example A1: Preparation of isocyanate prepolymer using polytetrahydrofuran and polyisocyanate (NCO / OH equivalent ratio = 1.7)

[0152] An isocyanate prepolymer composition was prepared by performing the same method as Example A1, except that the isosorbide-ethylene oxide 5 mol adduct and glycerol obtained in the above Preparation Example B1 were not used, only 100 g of polytetrahydrofuran was used as a polyol component, and the content of isophorone diisocyanate was changed from 28.34 g to 18.9 g. Thereafter, an end-capping reaction was performed by the same method as Example A1, thereby obtaining 100 g of an end-capped isocyanate prepolymer composition.

[0153] Comparative Example A2: Preparation of a polyol composition containing polytetrahydrofuran and glycerol and an isocyanate prepolymer composition using polyisocyanate (OH equivalent ratio of polytetrahydrofuran:glycerol = 0.6:0.4, NCO / OH equivalent ratio = 1.7)

[0154] An isocyanate prepolymer composition was prepared by performing the same method as Example A1, except that the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example B1 was not used and the content of polytetrahydrofuran was changed from 75 g to 90 g, and then an end-capping reaction was performed by the same method as Example A1, thereby obtaining 100 g of an end-capped isocyanate prepolymer composition.

[0155] Comparative Example A3: Preparation of a polyol composition containing polypropylene glycol and glycerol and an isocyanate prepolymer composition using polyisocyanate (OH equivalent ratio of polypropylene glycol:glycerol = 0.6:0.4, NCO / OH equivalent ratio = 1.7)

[0156] An isocyanate prepolymer composition was prepared by performing the same method as Example A1, except that the 5 mol isosorbide-ethylene oxide adduct obtained in Preparation Example B1 was not used and 90 g of polypropylene glycol was used instead of polytetrahydrofuran, and then an end-capping reaction was performed by the same method as Example A1, thereby obtaining 100 g of an end-capped isocyanate prepolymer composition.

[0157] Comparative Example A4: Preparation of an isocyanate prepolymer composition using a polyol composition comprising polytetrahydrofuran, isosorbide-ethylene oxide 5 mol adduct, and glycerol and a polyisocyanate (OH equivalent ratio of polytetrahydrofuran:isosorbide-ethylene oxide 5 mol adduct:glycerol = 0.5:0.1:0.4, NCO / OH equivalent ratio = 1.5)

[0158] An isocyanate prepolymer composition was prepared by performing the same method as in Example A1, except that the content of isophorone diisocyanate was changed from 28.34 g to 25.01 g, and then an end-capping reaction was performed by the same method as in Example A1, thereby obtaining 100 g of an end-capped isocyanate prepolymer composition.

[0159] Comparative Example A5: Preparation of an isocyanate prepolymer composition using a polyol composition comprising polytetrahydrofuran, isosorbide-ethylene oxide 5 mol adduct, and glycerol and a polyisocyanate (OH equivalent ratio of polytetrahydrofuran:isosorbide-ethylene oxide 5 mol adduct:glycerol = 0.5:0.1:0.4, NCO / OH equivalent ratio = 2.0)

[0160] An isocyanate prepolymer composition was prepared by performing the same method as in Example A1, except that the content of isophorone diisocyanate was changed from 28.34 g to 33.35 g, and then an end-capping reaction was performed by the same method as in Example A1, thereby obtaining 110 g of an end-capped isocyanate prepolymer composition.

[0161] Comparative Example A6: Preparation of an isocyanate prepolymer composition using a polyol composition comprising polytetrahydrofuran, isosorbide-ethylene oxide 5 mol adduct, and glycerol and a polyisocyanate (OH equivalent ratio of polytetrahydrofuran:isosorbide-ethylene oxide 5 mol adduct:glycerol = 0.2:0.4:0.4, NCO / OH equivalent ratio = 1.7)

[0162] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that the content of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example B1 was changed from 2.78 g to 11.88 g, the content of polytetrahydrofuran was changed from 75 g to 32 g, the content of glycerol was changed from 1.84 g to 1.96 g, and the content of isophorone diisocyanate was changed from 28.34 g to 30.23 g, and then an end-capping reaction was performed in the same manner as in Example A1, thereby obtaining 100 g of an end-capped isocyanate prepolymer composition.

[0163] Comparative Example A7: Preparation of a polyol composition comprising polytetrahydrofuran, 5 mol isosorbide-propylene oxide adduct, and glycerol, and an isocyanate prepolymer composition using a polyisocyanate (OH equivalent ratio of polytetrahydrofuran: 5 mol isosorbide-propylene oxide adduct: glycerol = 0.2:0.4:0.4, NCO / OH equivalent ratio = 1.7)

[0164] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 14.0 g of the isosorbide-propylene oxide 5 mol adduct obtained in Preparation Example B2 was used instead of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example B1, the content of polytetrahydrofuran was changed from 75 g to 32 g, the content of glycerol was changed from 1.84 g to 1.96 g, and the content of isophorone diisocyanate was changed from 28.34 g to 30.23 g, and then an end-capping reaction was performed in the same manner as in Example A1, thereby obtaining 100 g of an end-capped isocyanate prepolymer composition.

[0165] Comparative Example A8: Preparation of a polyol composition comprising polytetrahydrofuran, 5 mol isosorbide-propylene oxide adduct, and glycerol, and an isocyanate prepolymer composition using a polyisocyanate (OH equivalent ratio of polytetrahydrofuran: 5 mol isosorbide-propylene oxide adduct: glycerol = 0.55:0.05:0.4, NCO / OH equivalent ratio = 1.7)

[0166] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 1.75 g of the isosorbide-propylene oxide 5 mol adduct obtained in Preparation Example B2 was used instead of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example B1, the content of polytetrahydrofuran was changed from 75 g to 88.0 g, the content of glycerol was changed from 1.84 g to 1.96 g, and the content of isophorone diisocyanate was changed from 28.34 g to 30.23 g. Thereafter, an end-capping reaction was performed in the same manner as in Example A1, thereby obtaining 140 g of an end-capped isocyanate prepolymer composition.

[0167] Comparative Example A9: Preparation of a polyol composition comprising polytetrahydrofuran, 5 mol isosorbide-propylene oxide adduct, and glycerol, and an isocyanate prepolymer composition using a polyisocyanate (OH equivalent ratio of polytetrahydrofuran: 5 mol isosorbide-propylene oxide adduct: glycerol = 0.67:0.13:0.2, NCO / OH equivalent ratio = 1.7)

[0168] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 4.26 g of the isosorbide-propylene oxide 5 mol adduct obtained in Preparation Example B2 was used instead of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example B1, the content of polytetrahydrofuran was changed from 75 g to 100.5 g, and the content of glycerol was changed from 1.84 g to 0.92 g. Thereafter, an end-capping reaction was performed in the same manner as in Example A1, thereby obtaining 120 g of an end-capped isocyanate prepolymer composition.

[0169] Comparative Example A10: Preparation of a polyol composition comprising polytetrahydrofuran, 5 mol isosorbide-propylene oxide adduct, and glycerol, and an isocyanate prepolymer composition using a polyisocyanate (OH equivalent ratio of polytetrahydrofuran: 5 mol isosorbide-propylene oxide adduct: glycerol = 0.33:0.07:0.6, NCO / OH equivalent ratio = 1.7)

[0170] An isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 2.3 g of the isosorbide-propylene oxide 5 mol adduct obtained in Preparation Example B2 was used instead of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example B1, the content of polytetrahydrofuran was changed from 75 g to 49.5 g, and the content of glycerol was changed from 1.84 g to 2.76 g. Thereafter, an end-capping reaction was performed in the same manner as in Example A1, thereby obtaining 110 g of an end-capped isocyanate prepolymer composition.

[0171] <Manufacture of epoxy resin composition>

[0172] Examples B1 to B12 and Comparative Examples B1 to B10: Preparation of epoxy resin compositions

[0173] As an epoxy resin, 3.0 g of a diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.), 0.45 g of a hardener for epoxy resin (dicyandiamide (DICY), Evonik Co., Ltd., Dicyanex 1400F) and 0.05 g of a hardening accelerator for epoxy resin (urea derivative (DIURON), Evonik Co., Ltd., Amicure UR-D) to induce a hardening reaction at high temperatures and be stable at room temperature, 1.0 g of a filler having a particle size of 21 to 33 μm of calcium carbonate (CaCO3, OMYA Co., Ltd., OMYACARB 30-CN), 3.0 g of a core-shell rubber (KANEKA Co., Ltd., MX-154), as an additional impact modifier, and as a polyurethane-based impact modifier according to the present invention, Examples A1 to A12 and Each of the terminal-capped isocyanate prepolymer compositions obtained in Comparative Examples A1 to A10 was used in an amount of 2.5 g.

[0174] Epoxy resin compositions of Examples B1 to B12 and Comparative Examples B1 to B10 were prepared by mixing epoxy resin, hardener, hardening accelerator, filler, core-shell additional impact modifier, and polyurethane impact modifier in the compositions shown in Table 1 below.

[0175] Specifically, an epoxy resin composition was prepared by adding an epoxy resin, a curing agent, a curing accelerator, a filler, a core-shell additional impact modifier, and a polyurethane impact modifier according to the present invention to a paste mixer and mixing for 15 minutes.

[0176]

[0177]

[0178]

[0179]

[0180] <Evaluation of physical properties of epoxy resin compositions>

[0181] The epoxy resin compositions prepared in Examples B1 to B12 and Comparative Examples B1 to B10 were used as adhesives to measure the physical properties of adhesive specimens using the following method, and the results are shown in Table 2 below.

[0182] (1) Evaluation of T-peel strength (unit: N / 25 mm)

[0183] According to the ASTM D-1876 standard, the T-peel strength was measured, and the average value was calculated after measuring the results five times for each specimen.

[0184] (2) Evaluation of room temperature impact strength (unit: N / mm)

[0185] According to the ISO 11343 standard, the room temperature impact strength was measured, and the average value was calculated after measuring the results five times for each specimen.

[0186] [Ingredient Description]

[0187] - PTG: Polytetrahydrofuran

[0188] - PPG: Polypropylene Glycol

[0189] - Manufacturing Example B1: Isosorbide-ethylene oxide 5 mol adduct manufactured in Manufacturing Example B1

[0190] - Manufacturing Example B2: 5 mol isosorbide-propylene oxide adduct manufactured in Manufacturing Example B2

[0191] - IPDI: Isophorone diisocyanate

[0192] - Gly: glycerol

[0193] - TEA: Triethanolamine

[0194]

[0195]

[0196]

[0197] As shown in Table 2 above, in the case of Examples B1 to B12 according to the present invention, the adhesive strength was excellent with a T-peel strength of 360 N / 25 mm or more, and at the same time, the impact strength at room temperature was also excellent with a impact strength of 40 N / mm.

[0198] However, in the case of Comparative Example B1, where polyether polyol was used alone as the polyol component, surface peeling occurred in the adhesive specimen, and unstable cracks occurred during the room temperature impact strength measurement, resulting in very poor impact resistance. In addition, in the case of Comparative Examples B2 and B3, where anhydrous sugar alcohol-alkylene glycol was not used as the polyol component, the T-peel strength decreased, resulting in poor adhesiveness.

[0199] In the case of Comparative Example B4, the viscosity was too high, so the viscosity of the epoxy resin composition was increased, resulting in a low T-peel strength, which resulted in very poor adhesion, and the room temperature impact strength was also reduced, resulting in poor impact resistance. On the other hand, in the case of Comparative Example B5, the viscosity was too low, so the viscosity of the epoxy resin composition was reduced, resulting in a low T-peel strength, which resulted in very poor adhesion, and an unstable crack occurred during the measurement of the room temperature impact strength, resulting in very poor impact resistance.

[0200] For Comparative Examples B6 and B7, the T-peel strength was reduced, resulting in poor adhesion, and the room temperature impact strength was also reduced, resulting in poor impact resistance. In addition, for Comparative Example B8, the T-peel strength was reduced, resulting in very poor adhesion, and the room temperature impact strength was also reduced, resulting in very poor impact resistance.

[0201] In Comparative Example B9, a small amount of glycerol was added to the reaction, which resulted in reduced intermolecular entanglement and poor physical properties. On the other hand, in Comparative Example B10, the increased intermolecular entanglement resulted in an excessively high viscosity of the polyurethane itself, resulting in poor T-peel strength and room temperature impact strength.

Claims

1. An isocyanate prepolymer composition manufactured by reacting a polyol composition containing anhydrous alcohol-alkylene glycol, polyether polyol, and a polyhydric alcohol having a trihydric or higher alcohol with a polyisocyanate to form a urethane. Based on the total OH 1 equivalent of the above polyol composition, The OH equivalent ratio of the above anhydrous alcohol-alkylene glycol is greater than 0.05 and less than 0.4, The OH equivalent ratio of the above polyether polyol is greater than 0.2 and less than 0.6, The OH equivalent ratio of the above three or more polyhydric alcohols is greater than 0.2 and less than 0.6, The NCO equivalent ratio of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalent / total OH equivalent) is greater than 1.5 and less than 2.0, Isocyanate prepolymer composition.

2. An isocyanate prepolymer composition in the first paragraph, wherein the anhydrous sugar alcohol-alkylene glycol is an adduct obtained by reacting hydroxyl groups at both terminals or one terminal of the anhydrous sugar alcohol with an alkylene oxide.

3. An isocyanate prepolymer composition in the second paragraph, wherein the anhydrous sugar alcohol is an isocyanate hexitol.

4. An isocyanate prepolymer composition according to claim 2, wherein the alkylene oxide is a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms.

5. An isocyanate prepolymer composition according to claim 1, wherein the polyether polyol comprises at least one selected from the group consisting of polyalkylene glycol, polytetrahydrofuran, or a combination thereof.

6. An isocyanate prepolymer composition in claim 1, wherein the trivalent or higher polyhydric alcohol is at least one selected from the group consisting of glycerol, trimethylolpropane, triethanolamine, pentaerythritol, xylitol, sorbitol, or a combination thereof.

7. A step of reacting a polyol composition containing anhydrous alcohol-alkylene glycol, polyether polyol, and a polyhydric alcohol having a trihydric or higher alcohol with a polyisocyanate to form a urethane, Based on the total OH 1 equivalent of the above polyol composition, The OH equivalent ratio of the above anhydrous alcohol-alkylene glycol is greater than 0.05 and less than 0.4, The OH equivalent ratio of the above polyether polyol is greater than 0.2 and less than 0.6, The OH equivalent ratio of the above three or more polyhydric alcohols is greater than 0.2 and less than 0.6, The NCO equivalent ratio of the polyisocyanate to the total OH equivalent of the polyol composition (total NCO equivalent / total OH equivalent) is greater than 1.5 and less than 2.0, A method for preparing an isocyanate prepolymer composition.

8. A terminal-capped isocyanate prepolymer composition prepared by reacting the isocyanate prepolymer composition of any one of claims 1 to 6 with a terminal capping agent.

9. An end-capped isocyanate prepolymer composition in claim 8, wherein the end-capping agent is at least one selected from the group consisting of a phenol compound, a triazine compound, an alcohol compound, an amine compound, a benzene compound, a dicarboxylic acid ester compound, a novolak compound, or a combination thereof.

10. An impact modifier comprising the terminal-capped isocyanate prepolymer composition of claim 8.

11. An epoxy resin composition comprising the impact modifier of clause 10; and an epoxy resin.

12. An epoxy resin composition according to claim 11, wherein the epoxy resin is 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.

13. An epoxy resin composition according to claim 11, further comprising at least one selected from a curing agent, a curing accelerator, a filler, an adhesion accelerator, or a combination thereof.

14. An epoxy resin composition further comprising an additive selected from the group consisting of an antioxidant, a UV absorber, a resin modifier, a silane coupling agent, a diluent, a colorant, an antifoaming agent, a defoaming agent, a dispersant, a viscosity modifier, a gloss modifier, a wetting agent, a conductivity-imparting agent, or a combination thereof, in accordance with claim 11.

15. An adhesive comprising the epoxy resin composition of clause 11.

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