KR20220068183A - An isocyanate prepolymer composition using anhydrosugar alcohol-alkylene glycol composition, an end-capped isocyanate prepolymer composition using the prepolymer composition and an adhesion promoter for epoxy resin comprising the same, and an epoxy resin composition comprising the adhesion promoter and an adhesive comprising the same - Google Patents

Abstract

The present invention relates to an isocyanate prepolymer composition using an anhydrosugar alcohol-alkylene glycol composition and uses thereof and, more specifically, to: an isocyanate prepolymer composition which is eco-friendly, which is prepared by a urethane reaction of an anhydrosugar alcohol-alkylene glycol composition, a polyol composition comprising a polyether polyol, and a polyisocyanate, the anhydrosugar alcohol-alkylene glycol composition being obtained by adding an alkylene oxide to an anhydrosugar alcohol composition comprising monoanhydrosugar alcohol, dianhydrosugar alcohol, polysaccharide alcohol, polysaccharide alcohol-derived anhydrosugar alcohol, and a polymer of one or more thereof, and which can especially can enhance shear strength and T-peeling strength of an epoxy resin composition for adhesion to which an end-capped isocyanate prepolymer composition prepared using the isocyanate prepolymer composition is applied as an adhesion promoter for an epoxy resin; an end-capped isocyanate prepolymer composition using the prepolymer composition and an adhesion promoter comprising the same for an epoxy resin; and an epoxy resin composition comprising the adhesion promoter and an adhesive comprising the same epoxy resin composition.

Description

An isocyanate prepolymer composition using an anhydrosugar alcohol-alkylene glycol composition, an end-capped isocyanate prepolymer composition using the prepolymer composition and an adhesion promoter for an epoxy resin comprising the same, and an epoxy resin composition comprising the adhesion promoter and an adhesive comprising the same {An isocyanate prepolymer composition using anhydrosugar alcohol-alkylene glycol composition, an end-capped isocyanate prepolymer composition using the prepolymer composition and an adhesion promoter for epoxy resin comprising the same, and an epoxy resin composition comprising the adhesion promoter and an adhesive comprising the same }

The present invention relates to an isocyanate prepolymer composition using an anhydrosugar alcohol-alkylene glycol composition and a use thereof, and more particularly, to an anhydrosugar alcohol, an anhydrosugar alcohol, a polysaccharide alcohol, an anhydrosugar alcohol derived from a polysaccharide alcohol, and one of them. Anhydrous sugar alcohol-alkylene glycol composition in which an alkylene oxide is added to an anhydrosugar alcohol composition containing the above polymer, and a polyol composition containing a polyether polyol and a polyisocyanate are urethane-reacted, and environmentally friendly, in particular, utilizing this Isocyanate prepolymer composition capable of improving the shear strength and T-peel strength of an epoxy resin composition for adhesion in which the end-capped isocyanate prepolymer composition prepared by the above is applied as an adhesion promoter for an epoxy resin, and an end-capped isocyanate prepolymer composition using the prepolymer composition and an adhesion promoter for an epoxy resin comprising the same, and an epoxy resin composition including the adhesion promoter, and an adhesive comprising the same.

Epoxy resins have excellent heat resistance, mechanical properties, electrical properties and adhesion. Epoxy resin makes use of this characteristic and is used for sealing materials, such as a wiring board, a circuit board, the circuit board which multilayered these, a semiconductor chip, a coil, and an electric circuit. Alternatively, the epoxy resin is also used as a resin for adhesives, paints, and fiber-reinforced resins.

Epoxy resins can find widespread use as thermosetting resins in many applications. They are used as a thermosetting matrix in a prepreg consisting of fibers incorporated in a thermosetting matrix. They can also be used as materials for surface coatings, for bonding, forming and laminating due to their toughness, flexibility, adhesion and chemical resistance, all of which are used in aerospace, automotive, electronics, construction, furniture, green energy and sporting goods. Various applications can be found in a wide variety of industries such as industry.

A wide range of epoxy resins are readily available and may be used depending on their reactivity as required for a particular application. For example, resins may be solid, liquid, or semi-solid, and may have varying reactivity depending on the application to which they are applied. The reactivity of an epoxy resin is often measured in terms of epoxy equivalent, which is the molecular weight of a 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, but depend on whether they are present as a matrix for fiber reinforced prepregs, adhesive coatings, or structural adhesives.

However, the epoxy resin itself is too brittle and has weak strength, so its application range is limited. There is a problem of lowering the eco-friendliness. Accordingly, there is a demand for the development of an adhesion promoter capable of improving the strength of the epoxy resin while being environmentally friendly.

On the other hand, hydrogenated sugar (also referred to as “sugar alcohol”) refers to a compound obtained by adding hydrogen to a reducing end group of a saccharide, and is generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is 2 to 5) is an integer), and is classified into tetritol, pentitol, hexitol, and heptitol (with 4, 5, 6 and 7 carbon atoms, respectively) according to the number of carbon atoms. Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, and the like, and sorbitol and mannitol are particularly effective substances.

Anhydrosugar alcohol has the form of a diol having two hydroxyl groups in the molecule, and can be prepared by utilizing hexitol derived from starch (eg, Korean Patent No. 10-1079518, Korean Patent Application Laid-Open No. 10). -2012-0066904). Anhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, and research on its manufacturing method has been conducted with a lot of interest from a long time ago. Among these anhydrosugar alcohols, isosorbide prepared from sorbitol has the widest industrial application range.

The use of anhydrosugar alcohol is very diverse, such as treatment of heart and blood vessel diseases, adhesives for patches, pharmaceuticals such as mouth fresheners, solvents for compositions in the cosmetic industry, and emulsifiers in the food industry. In addition, it can raise the glass transition temperature of polymer materials such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, and has an effect of improving the strength of these materials. useful. In addition, it is known that it can be used as an eco-friendly solvent for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

As such, anhydrosugar alcohol has attracted a lot of attention due to its various application possibilities, and its use in actual industry is gradually increasing.

On the other hand, in the prior art, special uses such as simply using as a binder for a by-product obtained in the process of producing anhydrosugar alcohol by dehydrating hydrogenated sugar were not considered.

Therefore, there is a demand for development of useful uses for a by-product obtained in the process of preparing hydrogenated sugar from glucose and anhydrosugar alcohol from hydrogenated sugar.

An object of the present invention is eco-friendly because it uses anhydrosugar alcohol, and in particular, shear strength and T-peel strength of an epoxy resin composition for adhesion in which an end-capped isocyanate prepolymer composition prepared using this is applied as an adhesion promoter for an epoxy resin An isocyanate prepolymer composition capable of improving .

A first aspect of the present invention is an isocyanate prepolymer composition prepared by urethane reaction of a polyol composition comprising an anhydrosugar alcohol-alkylene glycol composition and a polyether polyol and a polyisocyanate, wherein the anhydrosugar alcohol-alkylene glycol composition is free It is prepared by addition reaction of more than 50 parts by weight to less than 2,000 parts by weight of an alkylene oxide per 100 parts by weight of the sugar alcohol composition, wherein the anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol The component is mono-anhydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, the third polyol component is a polysaccharide alcohol represented by the following formula (1), and the fourth polyol component is water from the polysaccharide alcohol represented by the following formula (1) It is an anhydrosugar alcohol formed by removing molecules, the fifth polyol component is at least one polymer selected from among the first to fourth polyol components, and the polyol composition is, based on 100 parts by weight of the polyol composition, the anhydrosugar An isocyanate prepolymer composition comprising 1 to 96.5 parts by weight of an alcohol-alkylene glycol composition and 3.5 to 99 parts by weight of the polyether polyol is provided:

[Formula 1]

In Formula 1, n is an integer of 0 to 4.

A second aspect of the present invention includes a step of urethane-reacting a polyol composition comprising an anhydrosugar alcohol-alkylene glycol composition and a polyether polyol with a polyisocyanate, wherein the anhydrosugar alcohol-alkylene glycol composition is anhydrosugar alcohol It is prepared by addition reaction of more than 50 parts by weight to less than 2,000 parts by weight of an alkylene oxide per 100 parts by weight of the composition, and the anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is A monohydric alcohol, the second polyol component is a dianhydrosugar alcohol, the third polyol component is the polysaccharide alcohol represented by Formula 1, and the fourth polyol component is a water molecule from the polysaccharide alcohol represented by Formula 1 Anhydrosugar alcohol formed by removing the fifth polyol component is at least one polymer selected from the first to fourth polyol components, and the polyol composition is, based on 100 parts by weight of the polyol composition, the anhydrosugar alcohol- It provides a method for preparing an isocyanate prepolymer composition comprising 1 to 96.5 parts by weight of an alkylene glycol composition and 3.5 to 99 parts by weight of the polyether polyol.

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 an end capping agent.

A fourth aspect of the present invention provides an adhesion promoter for an epoxy resin comprising the end-capped isocyanate prepolymer composition according to the third aspect of the present invention.

A fifth aspect of the present invention is an adhesion promoter for an epoxy resin according to the fourth aspect of the present invention; and an epoxy resin; it provides an epoxy resin composition comprising.

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

The isocyanate prepolymer composition according to the present invention is environmentally friendly, and in particular, the shear strength and T-peel strength of the epoxy resin composition for adhesion in which the end-capped isocyanate prepolymer composition prepared using the same is applied as an adhesion promoter for an epoxy resin Can be improved have.

In addition, since the isocyanate prepolymer composition according to the present invention is prepared from an anhydrosugar alcohol composition, which is a polyol composition obtained by utilizing a by-product obtained in the process of preparing an internal dehydrated product of hydrogenated sugar, it improves economic efficiency and eco-friendliness by resolving the by-product treatment problem can improve

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

[Isocyanate prepolymer composition and manufacturing method thereof]

The isocyanate prepolymer composition of the present invention is prepared by urethane reaction of a polyol composition comprising an anhydrosugar alcohol-alkylene glycol composition and a polyether polyol with a polyisocyanate, wherein the anhydrosugar alcohol-alkylene glycol composition is anhydrosugar alcohol composition 100 It is prepared by addition reaction of more than 50 parts by weight to less than 2,000 parts by weight of an alkylene oxide per part by weight, and the polyol composition is, based on 100 parts by weight of the polyol composition, 1 to 96.5 parts by weight of the anhydrosugar alcohol-alkylene glycol composition and 3.5 to 99 parts by weight of the polyether polyol.

Anhydrous sugar alcohol composition

The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is a monoanhydrosugar alcohol, the second polyol component is a dianhydrosugar alcohol, and the third polyol component has the following formula It is a polysaccharide alcohol represented by 1, the fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1 below, and the fifth polyol component is the first to fourth polyol components at least one polymer selected from among

[Formula 1]

In Formula 1, n is an integer of 0 to 4.

mono-anhydrosugar alcohol, which is the first polyol component included in the anhydrosugar alcohol composition of the present invention; dianhydride alcohol as a second polyol component; polysaccharide alcohol as a third polyol component; anhydrosugar alcohol formed by removing water molecules from polysaccharide alcohol, which is a fourth polyol component; and at least one polymer selected from among the first to fourth polyol components, which is a fifth polyol component, preferably at least two, more preferably all of which comprises a glucose-containing saccharide composition (eg, glucose , mannose, fructose, and maltose) are subjected to a hydrogenation reaction to prepare a hydrogenated sugar composition, and the obtained hydrogenated sugar composition is heated in the presence of an acid catalyst for a dehydration reaction, and the obtained dehydration reaction product It can be obtained in the process of preparing by thin film distillation. More specifically, all of the first to fifth polyol components included in the anhydrosugar alcohol composition of the present invention may be by-products remaining after thin film distillation is obtained by thin film distillation of the obtained dehydration reaction product.

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

The dianhydrosugar alcohol, which is the second polyol component, 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 hexitol derived from starch It can be manufactured using Since dianhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, research on its manufacturing method has been in progress with a lot of interest from a long time ago. Among these dianhydrosugar alcohols, isosorbide prepared from sorbitol currently has the widest industrial application range.

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

In one embodiment, the polysaccharide alcohol represented by Formula 1, which is the third polyol component, may be prepared by hydrogenation reaction of polysaccharides greater than or equal to disaccharides, including maltose.

In one embodiment, the anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1, which is the fourth polyol component, is a compound represented by the following Formula 2, a compound represented by the following Formula 3, or a mixture thereof can be selected from:

[Formula 2]

[Formula 3]

In Formulas 2 and 3,

n is each independently an integer from 0 to 4.

In one embodiment, the at least one polymer selected from the first to fourth polyol components, which is the fifth polyol component, includes at least one selected from the group consisting of a condensation polymer prepared from the following polycondensation reaction. can do:

- polycondensation reaction of the first polyol component,

- polycondensation reaction of the second polyol component,

- polycondensation reaction of the third polyol component,

- polycondensation reaction of the fourth polyol component,

- polycondensation reaction of the first polyol component and the second polyol component;

- polycondensation reaction of the first polyol component and the third polyol component;

- polycondensation reaction of the first polyol component and the fourth polyol component;

- polycondensation reaction of the second polyol component and the third polyol component;

- Polycondensation reaction of the second polyol component and the fourth polyol component,

- Polycondensation reaction of the third polyol component and the fourth polyol component;

- polycondensation reaction of the first polyol component, the second polyol component and the third polyol component;

- polycondensation reaction of the first polyol component, the second polyol component and the fourth polyol component;

- polycondensation reaction of the first polyol component, the third polyol component and the fourth polyol component;

- polycondensation reaction of the second polyol component, the third polyol component and the fourth polyol component, or

- Polycondensation reaction of the first polyol component, the second polyol component, the third polyol component and the fourth polyol component.

In one embodiment, the number average molecular weight (Mn: unit g / mol) of the anhydrosugar alcohol composition may be 193 or more, 195 or more, 200 or more, 202 or more, 205 or more, or 208 or more, and also 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.

In one embodiment, the number average molecular weight (Mn) of the anhydrosugar alcohol composition may be 193 to 1,589, specifically 195 to 1,550, more specifically 200 to 1,520, and even more specifically It may be 202 to 1,500, and more specifically, may be 205 to 1,490. In this embodiment, if the number average molecular weight of the anhydrosugar alcohol composition is less than 193, the compatibility between the anhydrosugar alcohol-alkylene glycol composition and polyisocyanate prepared therefrom may be poor, and on the contrary, the number average molecular weight of the anhydrosugar alcohol composition When this exceeds 1,589, when the end-capped isocyanate prepolymer composition prepared using the same is used as an adhesion promoter for an epoxy resin, there is no additional effect of improving physical properties, and economic efficiency is lowered as the material cost increases.

In one embodiment, the polydispersity index (PDI) of the anhydrosugar alcohol composition may be 1.13 or more, 1.15 or more, 1.20 or more, 1.23 or more, or 1.25 or more, and also 3.41 or less, 3.40 or less, 3.35 or less, 3.30 or less, 3.25 or more or less, 3.22 or less, or 3.19 or less.

In one embodiment, the polydispersity index (PDI) of the anhydrosugar alcohol composition may be 1.13 to 3.41, specifically 1.13 to 3.40, more specifically 1.15 to 3.35, and even more specifically may be 1.20 to 3.25, and more specifically, may be 1.23 to 3.22. In this embodiment, if the polydispersity index of the anhydrosugar alcohol composition is less than 1.13, compatibility between the anhydrosugar alcohol-alkylene glycol composition and the polyisocyanate prepared therefrom may be poor, and conversely, the polydispersity index of the anhydrosugar alcohol composition When is greater than 3.41, when using the end-capped isocyanate prepolymer composition prepared using the same as an adhesion promoter for an epoxy resin, there is no additional effect of improving physical properties, and economic efficiency is lowered due to an increase in material cost.

In one embodiment, the average number of -OH groups per molecule in the anhydrosugar alcohol composition may be 2.54 or more, 2.60 or more, 2.65 or more, 2.70 or more, 2.75 or more, or 2.78 or more, and also, 21.36 or more. or less, 21.30 or less, 21.0, 20.5 or less, 20.0 or less, 19.95 or less, or 19.92 or less.

In one embodiment, the average number of -OH groups per molecule in the anhydrosugar alcohol composition may be from 2.54 to 21.36, more specifically, from 2.60 to 21.30, and even more specifically from 2.65 to 21.0. can In this embodiment, if the average number of -OH groups per molecule in the anhydrosugar alcohol composition is less than 2.54, the end-capped isocyanate prepolymer composition prepared using this is used as an adhesion promoter for an epoxy resin. Economical efficiency decreases as the cost increases, and on the contrary, when the average number of -OH groups per molecule in the anhydrosugar alcohol composition exceeds 21.36, compatibility between the anhydrosugar alcohol-alkylene glycol composition and polyisocyanate prepared therefrom can fall

In a preferred embodiment, the anhydrosugar alcohol composition satisfies the following i) to iii):

i) the number average molecular weight (Mn) of the anhydrosugar alcohol composition is 193 to 1,589 g/mol;

ii) the polydispersity index (PDI) of the anhydrosugar alcohol composition is 1.13 to 3.41;

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

In one embodiment, in the anhydrosugar alcohol composition, based on the total weight of the composition, for example, the first polyol component is 0.1 to 20% by weight, specifically 0.6 to 20% by weight, more specifically 0.7 to 15% by weight may be included, and the second polyol component may be included in an amount of 0.1 to 28% by weight, specifically 1 to 25% by weight, more specifically 3 to 20% by weight, the third polyol component and the fourth polyol The total content of the components may be 0.1 to 6.5% by weight, specifically 0.5 to 6.4% by weight, more specifically 1 to 6.3% by weight, and the fifth polyol component is 55 to 90% by weight, specifically 60 to 89.9% by weight, more specifically 70 to 89.9% by weight may be included, but is not particularly limited thereto.

In one embodiment, the anhydrosugar alcohol composition is prepared by hydrogenating a glucose-containing saccharide composition (for example, glucose; mannose; fructose; and a saccharide composition including polysaccharides containing disaccharides or more including maltose), and , the obtained hydrogenated sugar composition is heated under an acid catalyst for a dehydration reaction, and the obtained dehydration reaction product may be prepared by thin film distillation, and more specifically, thin film distillate obtained by thin film distillation of the obtained dehydration reaction product. After that, it may be the remaining by-product.

More specifically, the hydrogenation reaction of the glucose-containing saccharide composition is carried out under a hydrogen pressure condition of 30 to 80 atm and a heating condition of 110 to 135 °C to prepare a hydrogenated sugar composition, and dehydration of the obtained hydrogenated sugar composition The reaction is carried out under reduced pressure conditions of 1 mmHg to 100 mmHg and heating conditions of 105° C. to 200° C. to obtain a dehydration reaction product, and thin film distillation of the obtained dehydration reaction product is carried out under reduced pressure conditions of 2 mbar or less and 150° C. to 175° C. It may be carried out under the heating conditions of, but is not limited thereto.

In one embodiment, the glucose content of the glucose-containing saccharide composition may be 41% by weight or more, 42% by weight or more, 45% by weight or more, 47% by weight or more, or 50% by weight or more, based on the total weight of the saccharide composition, 99.5 weight % 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, for example 41 to 99.5 wt%, 45 to 98.5 wt% or 50 to 98 wt% It can be %.

When the glucose content in the saccharide composition is less than 41% by weight, the number average molecular weight (Mn) of the anhydrosugar alcohol composition is too high, and an end-capped isocyanate prepolymer composition prepared using this is used as an adhesion promoter for an epoxy resin. However, economic feasibility may be reduced as the material cost increases, and when it exceeds 99.5 wt%, the number average molecular weight of the anhydrosugar alcohol composition is too low, and the strength characteristics of the end-capped isocyanate prepolymer composition prepared using it are poor. can get

In one embodiment, the content of polysaccharide alcohol (sugar alcohol greater than or equal to disaccharide) included in the hydrogenated sugar composition is the total dry weight of the hydrogenated sugar composition (here, the dry weight means the weight of solids remaining after removing moisture from the hydrogenated sugar composition) ), may be 0.8 wt% or more, 1 wt% or more, 2 wt% or 3 wt% or more, and 57 wt% or less, 55 wt% or less, 52 wt% or less, 50 wt% or less, or 48 wt% or less It may be, for example, 0.8 to 57% by weight, 1 to 55% by weight, or 3 to 50% by weight.

When the content of the polysaccharide alcohol in the hydrogenated sugar composition is less than 0.8% by weight, the effect of increasing fluidity due to the polysaccharide alcohol and the anhydrosugar alcohol derived therefrom is insignificant, so the distillation yield of the dianhydrosugar alcohol (eg, isosorbide) This may be lowered, and when it exceeds 57 wt%, there is a problem in that the distillation yield of the dianhydrosugar alcohol is significantly lowered when the result of the dehydration reaction of the hydrogenated sugar composition is thin film distilled.

In addition, when the polysaccharide alcohol content in the hydrogenated sugar composition is less than 0.8% by weight, an anhydrosugar alcohol composition is prepared using the hydrogenated sugar composition, and an isocyanate prepolymer composition is prepared by applying the anhydrosugar alcohol composition, and end-capped using the same An isocyanate prepolymer composition is prepared, and when it is used as an adhesion promoter for an epoxy resin, adhesive properties such as a decrease in the adhesion of the epoxy resin composition to an adherend and surface peeling may occur, and when it exceeds 57 wt% There is a problem in that the composition is cured or gelled in the process of preparing an anhydrosugar alcohol composition using such a hydrogenated sugar composition, and preparing an isocyanate prepolymer composition or an end-capped isocyanate prepolymer composition using the same.

Addition reaction with alkylene oxide and anhydrosugar alcohol composition

In the present invention, the anhydrosugar alcohol-alkylene glycol composition refers to a composition obtained by an addition reaction of the above-described anhydrosugar alcohol composition with an alkylene oxide, and accordingly, the anhydrosugar alcohol-alkylene glycol composition comprises the first to the first 5, including an adduct obtained by reacting at least one hydroxyl group with an alkylene oxide at one end of each polyol component, specifically, the anhydrosugar alcohol-alkylene glycol composition is an alkylene oxide adduct of the first polyol component (hereinafter referred to as “the second 1 anhydrosugar alcohol-alkylene glycol), an alkylene oxide adduct of the second polyol component (hereinafter referred to as “second anhydrosugar alcohol-alkylene glycol”), the third polyol component Alkylene oxide adduct (hereinafter referred to as “the third anhydrosugar alcohol-alkylene glycol”), an alkylene oxide adduct of the fourth polyol component (hereinafter “the fourth anhydrosugar alcohol-alkylene glycol”) ) and an alkylene oxide adduct of the fifth polyol component (hereinafter referred to as “the fifth anhydrosugar alcohol-alkylene glycol”).

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

In the present invention, the amount of the addition-reacted alkylene oxide per 100 parts by weight of the anhydrosugar alcohol composition is more than 50 parts by weight to less than 2,000 parts by weight. When the added amount of the alkylene oxide per 100 parts by weight of the anhydrosugar alcohol composition is 50 parts by weight or less, the reactivity between the prepared anhydrosugar alcohol-alkylene glycol composition and the polyisocyanate is reduced, so that their reaction does not occur, to provide an isocyanate prepolymer composition Conversely, if the added amount of the alkylene oxide is 2,000 parts by weight or more, the T-peel strength is reduced when the end-capped isocyanate prepolymer composition prepared using the prepared anhydrosugar alcohol-alkylene glycol composition is used as an adhesion promoter for an epoxy resin. get worse

In one embodiment, the amount of the addition-reacted alkylene oxide per 100 parts by weight of the anhydrosugar alcohol composition is, for example, more than 50 parts by weight, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, 90 parts by weight or more or It may be 100 parts by weight or more, and also less than 2,000 parts by weight, 1,900 parts by weight or less, 1,800 parts by weight or less, 1,700 parts by weight or less, 1,600 parts by weight or less, 1,500 parts by weight or less, 1,400 parts by weight or less, 1,300 parts by weight or less, 1,200 parts by weight It may be less than or equal to 1,100 parts by weight, or less than or equal to 1,000 parts by weight, but is not limited thereto.

In one embodiment, the addition reaction of the anhydrosugar alcohol composition and the alkylene oxide is, for example, at a temperature of 100° C. or more, more specifically 100° C. to 140° C., for 1 hour or more, more specifically 1 hour to It may be performed for 5 hours, but is not limited thereto.

polyether polyol

In one embodiment, the polyether polyol may include polyalkylene glycol, and more specifically, may include poly(C ₁ -C ₆ )alkylene glycol.

In one embodiment, the polyalkylene glycol may be selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, or a combination thereof.

In one embodiment, 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 also less than 4,000, 3,900 or less, It may be 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 less than 4,000, or 1,000 to 3,000. If the number average molecular weight of the polyether polyol is too lower than the above level, the reaction with polyisocyanate may not proceed. There may be problems.

polyol composition

The polyol composition includes 1 to 96.5 parts by weight of the anhydrosugar alcohol-alkylene glycol composition and 3.5 to 99 parts by weight of the polyether polyol, based on 100 parts by weight of the polyol composition. When the content of the anhydrosugar alcohol-alkylene glycol composition and the polyether polyol in the polyol composition are out of the above ranges, respectively, the end-capped isocyanate prepolymer composition prepared using the same is used as an adhesion promoter for an epoxy resin. Epoxy resin composition The shear strength and T-peel strength of the cured product are poor, and in particular, the T-peel strength becomes very poor.

In one embodiment, the content of the anhydrosugar alcohol-alkylene glycol composition in the polyol composition is 1 part by weight or more, 1.5 parts by weight or more, 1.6 parts by weight or more, 2 parts by weight or more, 3 parts by weight based on 100 parts by weight of the polyol composition. It may be at least 4 parts by weight, or at least 5 parts by weight, and may be 96.5 parts by weight or less, 96 parts by weight or less, 95.5 parts by weight or less, or 95 parts by weight or less.

Further, in one embodiment, the polyether polyol content in the polyol composition may be 3.5 parts by weight or more, 4 parts by weight or more, 4.5 parts by weight or more, or 5 parts by weight or more, and also 99 parts by weight based on 100 parts by weight of the polyol composition. parts by weight or less, 98.5 parts by weight or less, 98.4 parts by weight or less, 98 parts by weight or less, 97 parts by weight or less, 96 parts by weight or less, or 95 parts by weight or less.

In one embodiment, the polyol composition may optionally further include a polyol component other than the anhydrosugar alcohol-alkylene glycol composition and the polyether polyol.

In one embodiment, as a polyol component other than the anhydrosugar alcohol-alkylene glycol composition and polyether polyol, polyester polyol, polycaprolactone diol, a polymer polyol obtained by polymerizing these polyols and a vinyl compound, or a combination thereof One selected from the group consisting of may be used. As the vinyl compound, acrylonitrile, styrene, methyl methacrylonitrile, etc. are frequently used, and generally, acrylnitrile may be used alone or in combination with styrene.

Urethane Reaction with Polyisocyanate and Polyol Composition

According to another aspect of the present invention, anhydrosugar alcohol-alkylene glycol composition and a polyol composition comprising a polyether polyol and a polyisocyanate are urethane-reacted, wherein the anhydrosugar alcohol-alkylene glycol composition is anhydrosugar alcohol It is prepared by addition reaction of more than 50 parts by weight to less than 2,000 parts by weight of an alkylene oxide per 100 parts by weight of the composition, and the anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is A water molecule is obtained from the polysaccharide alcohol represented by the following formula (1), the second polyol component is a dianhydrosugar alcohol, the third polyol component is a polysaccharide alcohol represented by the following formula (1), and the fourth polyol component is a polysaccharide alcohol represented by the following formula (1) Anhydrosugar alcohol formed by removing the fifth polyol component is at least one polymer selected from the first to fourth polyol components, and the polyol composition is, based on 100 parts by weight of the polyol composition, the anhydrosugar alcohol- There is provided a method for preparing an isocyanate prepolymer composition comprising 1 to 96.5 parts by weight of an alkylene glycol composition and 3.5 to 99 parts by weight of the polyether polyol:

[Formula 1]

In Formula 1, n is an integer of 0 to 4.

In the method for preparing the isocyanate prepolymer composition according to the present invention, the description of the anhydrosugar alcohol composition, the alkylene oxide, the anhydrosugar alcohol-alkylene glycol composition, and the polyether polyol is the same as described above.

In the present invention, the polyisocyanate may be used without any particular limitation as long as it can be used in the production of polyurethane. For example, polyisocyanates selected from the group consisting of aliphatic polyisocyanates, cycloaliphatic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, heterocyclic polyisocyanates or combinations thereof may be used, and also, unmodified polyisocyanates may be used. Both isocyanates or modified polyisocyanates can be used.

In one embodiment, examples of the polyisocyanate include methylenediphenyl diisocyanate (MDI) (eg, 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 (eg, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate), naphthalene diisocyanate (NDI), or 4,4'-dibenzyl diisocyanate, etc. aromatic polyisocyanates; 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) (eg 1,6-hexamethylene diisocyanate), dimer fatty acid diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate (eg cyclohexane-1,4-diisocyanate) or ethylene diisocyanate aliphatic polyisocyanates such as; Or it may be a combination thereof, but is not limited thereto.

In another embodiment, examples of the polyisocyanate include methylenediphenyl diisocyanate (MDI), ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane di Isocyanate, 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 .

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

In one embodiment, the urethane reaction may be performed in the presence of a catalyst, such as an amine catalyst, an organometallic catalyst, or a mixture thereof.

The type of the amine catalyst is not particularly limited, but preferably one or a mixture of two or more selected from tertiary amine catalysts may be used, and more specifically, triethylene diamine, triethylamine , N-methyl morpholine (N-Methyl morpholine), N-ethyl morpholine (N-Ethyl morpholine), or one selected from the group consisting of a combination thereof may be used.

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

In one embodiment, the urethane reaction is performed under elevated temperature (eg, at 50 to 100° C., preferably at 50 to 70° C.) for a suitable time (eg, 0.1 to 5 hours, preferably 0.5 to 2 hours). However, the present invention is not limited thereto.

In one embodiment, the equivalent ratio of NCO groups in the polyisocyanate compound / OH groups in the polyol composition in the urethane reaction is greater than 0.1, 0.15 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more , 0.9 or more, 1.0 or more, 1.5 or more, or 2.0 or more, and may be less than 8.0, 7.85 or less, 7.8 or less, 7.6 or less, 7.5 or less, 7.0 or less, or 6.5 or less, for example greater than 0.1 to less than 8.0, 0.15 to 7.85 , 0.5 to 7.6, 1.0 to 7.5, 1.5 to 7.0, or 2.0 to 6.5.

The equivalent ratio of the NCO group / OH group is 0.1 or less or 8.0 In this case, when the end-capped isocyanate prepolymer composition prepared by utilizing the prepared isocyanate prepolymer composition is used as an adhesion promoter for an epoxy resin, the effect of improving the T-peel strength may be insignificant.

[End-capped isocyanate prepolymer composition, adhesion promoter for epoxy resin, epoxy resin composition, and adhesive]

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

The present invention also provides an adhesion promoter for an epoxy resin comprising the above-described end-capped isocyanate prepolymer composition.

The present invention also provides an adhesion promoter for the above-mentioned epoxy resin; and an epoxy resin; it provides an epoxy resin composition comprising.

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

In one embodiment, the end capping agent is one selected from the group consisting of a phenol-based compound, a triazine-based compound, an alcohol compound, an amine-based compound, a benzene-based compound, a dicarboxylic acid ester-based compound, a novolak-based compound, or a combination thereof More specifically, phenolic compounds (eg, allylphenol, t-butylphenol, phenol, bisphenol A, bisphenol M, bisphenol F, 1,3-dihydroxybenzene, 1,4-dihydroxy Benzene, 1,2-dihydroxybenzene, phenolphthalein, o,o'-diallylbisphenol A, phenolphthalein, or a combination thereof), benzene-based compounds (eg, fluoroglucinol, resorcinol, naphthorezo) lecinol, or a combination thereof), a dicarboxylic acid ester-based compound (eg, a gallic acid ester, a maleic acid ester, or a combination thereof), a novolac-based compound (eg, cresol novolac), or a combination thereof It may be one or more, and more specifically, may be a phenol-based compound.

The epoxy resin may be solid, liquid or semi-solid, and may have various reactivity depending on the application to which they are applied. The reactivity of an epoxy resin is often measured in terms of epoxy equivalent, which is the molecular weight of a resin containing a single reactive epoxy group. The lower the epoxy equivalent weight, the higher the reactivity of the epoxy resin.

In one embodiment, as the epoxy resin, bisphenol A-epichlorohydrin resin, diglycidyl ether resin of bisphenol A, novolak-type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, bi-cyclic epoxy resin, A glycidyl ester type epoxy resin, a brominated epoxy resin, a bio-derived epoxy resin, epoxidized soybean oil, or a combination thereof may be selected from the group consisting of, but is not limited thereto.

In another embodiment, as the epoxy resin, novolak-type epoxy resins such as phenol novolak-type epoxy resins and cresol novolak-type epoxy resins, bisphenol-type epoxy resins such as bisphenol A-type epoxy resins and bisphenol F-type epoxy resins; Aromatic glycidylamine type epoxy resin such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane type glycidylamine, aminophenol type glycidylamine, hydro Quinone-type epoxy resin, biphenyl-type epoxy resin, stilbene-type epoxy resin, triphenolmethane-type epoxy resin, triphenolpropane-type epoxy resin, alkyl-modified triphenolmethane-type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene Modified phenol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, phenol aralkyl type epoxy resin having a phenylene and/or biphenylene skeleton, naphthol aralkyl type epoxy resin having a phenylene and/or biphenylene skeleton, etc. of aliphatic epoxy resins such as alicyclic epoxy resins such as aralkyl type epoxy resins, vinylcyclohexene dioxide, dicyclopentadiene oxide, and alicyclic diepoxy-adipide, or those selected from the group consisting of combinations thereof, However, the present invention is not limited thereto.

In another embodiment, as the epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin, naphthalene Skeletal type epoxy resin, tetraphenylolethane type epoxy resin, diphenyl phosphate (DPP) type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadienephenol type epoxy resin, diglycy of bisphenol A ethylene oxide adduct Glycidyl ether having one epoxy group, such as diglycidyl ether, diglycidyl ether of bisphenol A propylene oxide adduct, diglycidyl ether of bisphenol A, phenyl glycidyl ether, crezyl glycidyl ether, and these It may be selected from the group consisting of a nuclear hydrogenated epoxy resin, which is a nuclear hydrogenated epoxy resin, or a combination thereof, but is not limited thereto.

In one embodiment, 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 is a catalyst, for example, in the presence of a basic catalyst such as an organoammonium salt compound, under elevated temperature (eg, 100 to 200° C., preferably 120 to 180° C.) for a suitable time (eg, 0.1 to 5 hours, preferably 0.5 to 2 hours), but is not limited thereto.

In one embodiment, the adhesion promoter for an epoxy resin of the present invention may consist solely of the end-capped isocyanate prepolymer composition of the present invention.

In another embodiment, the adhesion promoter for an epoxy resin of the present invention may further include an additional adhesion promoter component in addition to the end-capped isocyanate prepolymer composition of the present invention, within the scope capable of achieving the object of the present invention, , As this additional adhesion promoter component, an adhesion promoter component usable for epoxy resins can be used.

In one embodiment, the additional adhesion promoter component may be a polyurethane-modified epoxy resin, a polyurethane-modified silyl epoxy resin, or a combination thereof, but is not limited thereto.

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

As the curing agent, one type of curing agent commonly used in this field may be used alone or in combination of two or more types, for example, amines such as benzyldimethylamine, tris(dimethylaminomethyl)phenol, dimethylcyclohexylamine, etc. compounds (eg, tertiary amines); 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 and organic acid salts thereof; organometallic compounds such as zinc octylate, tin octylate, and aluminum acetylacetone complex; quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide; boron compounds such as boron trifluoride and triphenyl borate; metal halides such as zinc chloride and stannous chloride; A latent curing agent (eg, dicyandiamide, a high melting point dispersion type latent amine adduct obtained by adding an amine to an epoxy resin, etc.; a microcapsule type latent curing agent 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 thermal cation polymerization-type latent curing agents such as Lewis acid salts and Bronsted acid salts) or combinations thereof, but is not limited thereto.

In one embodiment, 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.

Room temperature curing of epoxy resins usually requires a temperature of 15°C or higher, and curing time is 24 hours or longer.

Therefore, for the curing promoting effect, the epoxy resin composition of the present invention may further include a curing accelerator. Examples of the curing accelerator include a urea-based compound, a thiourea-based compound, a Lewis acid-based compound, or a mixture thereof. Specifically, butylated urea, butylated melamine, butylated thiourea, boron trifluoride, and the like are used. but is not limited thereto.

When the curing accelerator is included in the epoxy resin composition of the present invention, the amount used may be 0.01 to 1.0 parts by weight, more specifically, 0.05 to 0.5 parts by weight, based on 100 parts by weight of the total of the epoxy resin and the curing agent. may be, and more specifically, may be 0.08 parts by weight to 0.2 parts by weight, 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 proceed sufficiently, and there may be a problem in that mechanical properties and thermal properties are lowered. Since this progresses slowly, there may be a problem in that the viscosity increases.

The filler is used for the main purpose of improving the mechanical properties of the cured product by mixing it with an epoxy resin or a curing agent, and in general, the mechanical properties are improved as the amount added increases. Examples of the inorganic filler include extenders such as talc, sand, silica, talc, and calcium carbonate; reinforcing fillers such as mica, quartz, and glass fiber; Some have special uses such as quartz powder, graphite, alumina, and aerosil (for the purpose of imparting thixotropic properties). As metals, aluminum, aluminum oxide, iron, iron oxide, copper, etc. contribute to thermal expansion coefficient, abrasion resistance, thermal conductivity, and adhesion. There are those that provide flame retardancy such as antimony oxide (SB2O3), barium titanate, and fillers for weight reduction such as fine plastic spheres (phenolic resin, urea resin, etc.) as organic materials. In addition, as fillers with reinforcing properties, various glass fibers or chemical fiber cloths can be treated as fillers in a broad sense in the manufacture of laminates. Thixotropic (thixotropic: thixotropic or thixotropic refers to the properties of a liquid in a flowing state and a solid state in a stationary state so that the resin attached or impregnated in a laminated material by means of a vertical plane or immersion method does not flow down or lose during curing). It uses fine particles with a large unit surface area to impart For example, colloidal silica (Aerosil) or bentonite-type clay is used.

In one embodiment, the filler is not particularly limited, but for example, glass fiber, carbon fiber, titanium oxide, alumina, talc, mica, aluminum hydroxide, calcium carbonate, or a combination thereof. can 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.

The impact modifier is one of the modifiers used to improve the performance of the material and is added during the preparation of the epoxy resin composition to improve physical properties such as impact strength and workability.

In one embodiment, the impact modifier includes, for example, a rubber-based impact modifier such as carboxyl terminated butadiene acrylonitrile (CTBN) and amine terminated butadiene acrylonitrile (ATBN), poly Ethersulfone, polyetherimide, polycarbonate, polyimide, polyamide, acrylonitrile butadiene styene (ABS) and methacrylate butadiene styrene ( A thermoplastic polymer-based impact modifier such as methacrylate butadiene styrene (MBS), or a mixture thereof may be used.

When the impact modifier is included in the epoxy resin composition of the present invention, the content of the impact modifier in the composition may be 2 parts by weight to 40 parts by weight, more specifically 5 parts by weight, based on 100 parts by weight of the total of the epoxy resin and the curing agent. It may be in an amount of parts by weight to 35 parts by weight, and more specifically, 10 parts by weight to 30 parts by weight, but is not limited thereto. If the content of the impact modifier is too less than the above level, mechanical properties and thermal properties may be reduced due to insufficient toughness of the cured product of the epoxy resin composition. This deteriorates, the curing level of the epoxy resin composition becomes poor, the manufacturing cost of the epoxy resin composition increases, and there are problems in that the viscosity of the epoxy resin composition increases.

The epoxy resin composition of the present invention may further include one or more additive components commonly used in the epoxy resin composition, if necessary.

Such additive components include, for example, 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. One selected from can be used.

The antioxidant may be used to further improve the heat resistance stability of the obtained cured product, and is not particularly limited, but, for example, a phenol-based antioxidant (dibutylhydroxytoluene, etc.), a sulfur-based antioxidant (mercaptopropionic acid derivative, etc.) , phosphorus-based antioxidants (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.) or combinations thereof may be used. The content of the antioxidant 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.

Although it does not specifically limit as said UV absorber, For example, benzotriazole-type UV absorber represented by TINUBIN P by BASF Japan Ltd. or TINUVIN 234; triazine-based UV absorbers such as TINUVIN 1577ED; A hindered amine-based UV absorber such as CHIMASSOLV 2020FDL or one selected from the group consisting of a combination thereof may be used. The content of the UV absorber 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.

Although it does not specifically limit as said resin modifier, For example, Flexibility-imparting agents, such as polypropylene glycidyl ether, a polymerization fatty acid polyglycidyl ether, polypropylene glycol, and a urethane prepolymer, etc. are mentioned. 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.

Although it does not specifically limit as said silane coupling agent, For example, chloropropyl trimethoxysilane, vinyl trichlorosilane, gamma methacryloxypropyl trimethoxysilane, gamma aminopropyl triethoxysilane, etc. are mentioned. . 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 in total of the epoxy resin and the curing agent.

The diluent is used for the main purpose of lowering the viscosity by adding it to the epoxy resin or curing agent, and serves to improve flowability and defoaming properties, improve penetration into details of parts, etc. or to effectively add a filler . Unlike solvents, diluents generally do not volatilize and remain in the cured product when the resin is cured, and are divided into reactive and non-reactive diluents. Here, the reactive diluent has one or more epoxy groups and participates in the reaction to enter a cross-linked structure in the cured product, and the 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), and Aliphatic Glycidyl Ether (C12 -C14). , Modified-tert-Carboxylic Glycidyl Ester, and the like. Commonly used non-reactive diluents include dibutyl phthalate (DiButylPhthalate, DBP), dioctyl phthalate (DiOctylPhthalate, DOP), nonyl phenol (Nonyl-Phenol), hysol (Hysol), and the like. In one embodiment, the diluent is not particularly limited, but for example, n-butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, vinylcyclohexene dioxide, diglycidyl aniline, One selected from the group consisting of glycerin triglycidyl ether or a combination thereof may be used. 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.

Pigments or dyes are used as colorants for adding color to the resin. Commonly used pigments include colorants such as titanium dioxide, cadmium red, shanning green, carbon black, chrome green, chrome yellow, navy blue, and shanning blue.

In addition, an antifoaming agent and defoaming agent used for the purpose of removing air bubbles from the resin, a dispersing agent for increasing the dispersion effect between the resin and the pigment, a wetting agent for improving the adhesion between the epoxy resin and the material, and a viscosity adjusting agent , a gloss control agent for controlling the glossiness of the resin, an additive for improving adhesion, an additive for imparting electrical properties, and the like, various additives can be used.

The curing method of the epoxy resin composition of the present invention is not particularly limited, and, for example, a conventionally known curing apparatus such as a closed curing furnace or a tunnel furnace capable of continuous curing can be used. Although the heating method used for this hardening is not specifically limited, For example, hot air circulation, infrared heating, high frequency heating, etc. can perform conventionally well-known methods.

The curing temperature and curing time may be in the range of 30 seconds to 10 hours at 80°C to 250°C. In one embodiment, after pre-curing at 80° C. to 120° C., for 0.5 hours to 5 hours, post-curing at 120° C. to 180° C. for 0.1 hours to 5 hours. In one embodiment, for short-time curing, it may be cured under conditions of 150° C. to 250° C., 30 seconds to 30 minutes.

In one embodiment, the epoxy resin composition of the present invention is divided into two or more components, for example, a component containing a curing agent and a component containing an epoxy resin, and preserved, and these may be combined before curing. In another embodiment, the epoxy resin composition of the present invention may be stored as a thermosetting composition containing each component and subjected to curing as it is. When storing as a thermosetting composition, it can be stored at a low temperature (normally -40°C to 15°C).

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 thereto.

[Example]

<Preparation of anhydrosugar alcohol composition comprising the first to fifth polyol components>

Preparation Example A1: Preparation of anhydrosugar alcohol composition using glucose in an amount of 97% by weight

A liquid hydrogenated sugar composition having a concentration of 55% by weight by hydrogenating a glucose product having a purity of 97% in the presence of a nickel catalyst and at a temperature of 125°C and a hydrogen pressure of 60 atm (Sorbitol 96% by weight, mannitol 0.9% by weight based on solid content) % and 3.1% by weight of polysaccharide alcohol greater than or equal to disaccharide) to obtain 1,819 g, put it in a batch reactor equipped with a stirrer, and concentrated by heating to 100° C. to obtain 1,000 g of a concentrated hydrogenated sugar composition.

1,000 g of the concentrated hydrogenated sugar composition and 9.6 g of sulfuric acid were added to the reactor. Thereafter, the temperature inside the reactor was raised to about 135° C., and a dehydration reaction was performed under a reduced pressure of about 45 mmHg to convert to anhydrosugar alcohol. After completion of the dehydration reaction, the temperature of the reaction product was cooled to 110° C. or less, and about 15.7 g of a 50% aqueous sodium hydroxide solution was added to neutralize the reaction product. Thereafter, the temperature was cooled to 100° C. or less, and the resultant solution was concentrated under reduced pressure of 45 mmHg for 1 hour or more to remove residual moisture and low boiling point substances, thereby obtaining about 831 g of anhydrosugar-alcohol conversion solution. As a result of analyzing the obtained anhydrosugar-alcohol conversion solution by gas chromatography, the conversion content to isosorbide was 71.9% by weight, and the molar conversion rate from sorbitol to isosorbide was calculated to be 77.6%.

831 g of the obtained anhydrosugar-alcohol conversion solution was put into a thin film distiller (SPD) to proceed with distillation. At this time, the distillation was carried out at a temperature of 160° C. and a vacuum pressure of 1 mbar, to obtain about 589 g of a distillate (distillation yield: about 70.9%). At this time, the purity of isosorbide in the distillate was measured to be 96.8%, and the distillation yield of isosorbide calculated therefrom was 95.3%. After separation of the distillate, isosorbide (dianhydrosugar alcohol) [second polyol component] 11.5 wt%, isomannide (dianhydrosugar alcohol) [second polyol component] 0.4 wt%, sorbitan (monoanhydride) alcohol) [first polyol component] 7.4% by weight, polysaccharide alcohol represented by the above formula (1) [third polyol component] and anhydrosugar alcohol derived therefrom (that is, formed by removing water molecules from polysaccharide alcohol) [agent a total of 2.5% by weight of the polyol component of 4] and 78.2% by weight of a polymer thereof [the fifth polyol component], the number average molecular weight of the composition is 208 g/mol, the polydispersity index of the composition is 1.25, and the composition About 242 g of anhydrosugar alcohol composition having a hydroxyl value of 751 mg KOH/g and an average number of -OH groups per molecule in the composition of 2.78 was obtained.

Preparation A2: Preparation of anhydrosugar alcohol composition using a saccharide composition containing 85.2 wt% of glucose

Preparation Example Except for using a saccharide composition containing 85.2% by weight of glucose (85.2% by weight of glucose and 14.8% by weight of mannose, fructose, and polysaccharides (disaccharides or higher saccharides such as maltose) in place of the 97% pure glucose product) The hydrogenation reaction was performed in the same manner as in A1 to obtain 1,852 g of a liquid hydrogenated sugar composition having a concentration of 54 wt% (based on solids, 84.1 wt% of sorbitol, 2.8 wt% of mannitol, and 13.1 wt% of a polysaccharide alcohol greater than or equal to disaccharide) with a stirrer Concentrated by heating to 100 ℃ in a batch reactor with attached, to obtain a concentrated hydrogenated sugar composition 1,000g.

The same method as in Preparation Example A1 for 1,000 g of the concentrated hydrogenated sugar composition, except that the content of sulfuric acid was changed from 9.6 g to 8.4 g and the content of 50% aqueous sodium hydroxide solution was changed from 15.7 g to 13.7 g was converted to anhydrosugar alcohol by performing a dehydration reaction. The anhydrous sugar-alcohol conversion solution obtained as a result of the dehydration reaction was about 846 g, and as a result of gas chromatography analysis of the obtained anhydrosugar-alcohol conversion solution, the conversion content to isosorbide was 61.7 wt%, through which sorbitol to isosorbate The molar conversion to beads was calculated to be 77.4%.

Thin film distillation was performed on 846 g of the obtained anhydrosugar-alcohol conversion solution in the same manner as in Example 1 to obtain about 528 g of a distillate (distillation yield: about 62.4%). At this time, the purity of isosorbide in the distillate was measured to be 96.5%, and the distillation yield of isosorbide calculated therefrom was 97.6%. After separation of the distillate, isosorbide (dianhydrosugar alcohol) 4.0% by weight, isomannide (dianhydrosugar alcohol) 1.6% by weight, sorbitan (monoanhydrosugar alcohol) 2.1% by weight, polysaccharide alcohol represented by Formula 1 and a total of 5.1% by weight of anhydrosugar alcohols derived therefrom (i.e., formed by removing water molecules from the polysaccharide alcohol) and 87.2% by weight of their polymers, wherein the composition has a number average molecular weight of 720 g/mol, and About 318 g of anhydrosugar alcohol composition having a polydispersity index of 2.54, a hydroxyl value of the composition of 754 mg KOH/g, and an average number of -OH groups per molecule in the composition of 9.68 was obtained.

Preparation A3: Preparation of anhydrosugar alcohol composition using saccharide composition containing 50.2 wt% of glucose

Preparation Example Except for using a saccharide composition containing 50.2% by weight of glucose (50.2% by weight of glucose and 49.8% by weight of mannose, fructose and polysaccharides (disaccharides or higher saccharides such as maltose) in place of the 97% pure glucose product) Hydrogenation reaction was performed in the same manner as in A1 to obtain 1,819 g of a liquid hydrogenated sugar composition having a concentration of 55 wt% (based on solid content, sorbitol 48.5 wt%, mannitol 3.6 wt%, disaccharide or higher polysaccharide alcohol 47.9 wt%), and this was stirred Concentrated by heating to 100 ℃ in a batch reactor with attached, to obtain a concentrated hydrogenated sugar composition 1,000g.

The concentrated hydrogenated sugar composition 1,000, except that the content of sulfuric acid was changed from 9.6 g to 4.85 g, the content of 50% aqueous sodium hydroxide solution was changed from 15.7 g to 7.9 g, and the reaction temperature was changed to 120 ° C. g was converted to anhydrosugar alcohol by performing a dehydration reaction in the same manner as in Preparation Example A1. The anhydrous sugar-alcohol conversion solution obtained as a result of the dehydration reaction was about 890 g, and as a result of analyzing the obtained anhydrous sugar-alcohol conversion solution by gas chromatography, the conversion content of isosorbide was 33.7 wt%, and through this, The molar conversion of the beads was calculated to be 77.1%.

Thin film distillation was performed on 890 g of the obtained anhydrosugar-alcohol conversion solution in the same manner as in Preparation Example A1 to obtain about 304 g of a distillate (distillation yield: about 34.2%). At this time, the purity of isosorbide in the distillate was measured to be 96.9%, and the distillation yield of isosorbide calculated therefrom was 98.3%. After separating the distillate, isosorbide (dianhydrosugar alcohol) 0.9% by weight, isomannide (dianhydrosugar alcohol) 2.1% by weight, sorbitan (monoanhydrosugar alcohol) 0.9% by weight, polysaccharide alcohol represented by Formula 1 and a total of 6.2% by weight of anhydrosugar alcohols derived therefrom (i.e., formed by removing water molecules from the polysaccharide alcohol) and 89.9% by weight of their polymers, wherein the composition has a number average molecular weight of 1,480 g/mol, and About 586 g of anhydrosugar alcohol composition having a polydispersity index of 3.19, a hydroxyl value of 755 mg KOH/g of the composition, and an average number of -OH groups per molecule in the composition of 19.92 was obtained.

<Preparation of anhydrous sugar alcohol-alkylene glycol composition>

Preparation B1: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

100 parts by weight (200 g) of the anhydrosugar-alcohol composition obtained in Preparation Example A1 and 0.4 g of KOH were placed in a pressurized reactor, and the process of pressurizing and evacuating with nitrogen was repeated three times. Thereafter, the temperature inside the reactor was raised to 100° C. to remove moisture, and after all the moisture was removed, 100 parts by weight (200 g) of ethylene oxide was slowly injected and reacted at 100° C. to 140° C. After that, 4 g of a metal adsorbent (Ambosol MP20) is added to remove metals and by-products, the temperature inside the reactor is raised again, and the metal content is monitored while stirring at 100° C. to 120° C. for 1 hour to 5 hours, and then the metal is completely removed. If not detected, the temperature inside the reactor was cooled to 60°C to 90°C and filtered. Then, 395 g of anhydrosugar alcohol-alkylene glycol composition was obtained by purifying the filtrate using an ion exchange resin (UPRM 200, Samyang Corporation).

Preparation B2: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 300 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

The content of the anhydrosugar alcohol composition obtained in Preparation Example A1 was changed from 100 parts by weight (200 g) to 100 parts by weight (100 g), and 300 parts by weight (300 g) of propylene oxide was used instead of ethylene oxide, except that, 396 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1.

Preparation B3: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 1,000 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

The content of the anhydrosugar alcohol composition obtained in Preparation Example A1 was changed from 100 parts by weight (200g) to 100 parts by weight (40g), and the added content of ethylene oxide was changed from 100 parts by weight (200g) to 1,000 parts by weight (400g) Except for the changes, 431 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1.

Preparation B4: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

100 parts by weight (200 g) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 100 parts by weight (200 g) of propylene oxide was used instead of ethylene oxide Then, in the same manner as in Preparation Example B1, 394 g of anhydrosugar alcohol-alkylene glycol composition was obtained.

Preparation B5: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 300 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

100 parts by weight (100 g) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the added content of ethylene oxide was added from 100 parts by weight (200 g) to 300 parts by weight ( 300 g) was carried out in the same manner as in Preparation Example B1, except that anhydrosugar alcohol-alkylene glycol composition 392 g was obtained.

Preparation B6: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 1,000 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

100 parts by weight (40 g) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 1,000 parts by weight (400 g) of propylene oxide was used instead of ethylene oxide except that And, 432 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1.

Preparation B7: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

Anhydrosugar alcohol-alkyl in the same manner as in Preparation Example B1, except that 100 parts by weight (200 g) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1. 392 g of ren glycol composition were obtained.

Preparation B8: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 500 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

100 parts by weight (70 g) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 500 parts by weight (350 g) of propylene oxide was used in place of ethylene oxide. and 413 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1.

Preparation B9: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 1,000 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

100 parts by weight (40 g) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the added content of ethylene oxide was 100 parts by weight (200 g) to 1,000 parts by weight ( 400 g), the same method as in Preparation Example B1 was performed to obtain 426 g of anhydrosugar alcohol-alkylene glycol composition.

Preparation B10: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 50 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

The content of the anhydrosugar alcohol composition obtained in Preparation Example A1 was changed from 100 parts by weight (200 g) to 100 parts by weight (280 g), and the added content of ethylene oxide was changed from 100 parts by weight (200 g) to 50 parts by weight (140 g). Except for the changes, the same method as in Preparation Example B1 was performed to obtain 407 g of anhydrosugar alcohol-alkylene glycol composition.

Preparation B11: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 2,000 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

100 parts by weight (20 g) of the anhydrosugar-alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar-alcohol composition obtained in Preparation Example A1, and 2,000 parts by weight (400 g) of propylene oxide was used in place of ethylene oxide And, 403 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1.

Preparation B12: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 3,000 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

100 parts by weight (13 g) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the added content of ethylene oxide was adjusted from 100 parts by weight (200 g) to 3,000 parts by weight ( 390 g), except that it was changed to 388 g of anhydrosugar alcohol-alkylene glycol composition in the same manner as in Preparation Example B1.

Preparation B13: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 1,500 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

The content of the anhydrosugar alcohol composition obtained in Preparation Example A1 was changed from 100 parts by weight (200g) to 100 parts by weight (50g), and 1,500 parts by weight (750g) of propylene oxide was used instead of ethylene oxide, In the same manner as in Preparation Example B1, 720 g of anhydrosugar alcohol-alkylene glycol composition was obtained.

<Preparation of isocyanate prepolymer composition>

Example A1: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 82 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 and 18 parts by weight of a polyether polyol and polyisocyanate

28 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 6 g of polytetramethylene ether glycol (number average molecular weight: 1,000 g/mol, Sigma Aldrich (produced)), 56 g of isophorone diisocyanate and di-n-butyl Put 0.2 g of tin dilaurate into a 250 ml four-necked glass reactor equipped with a nitrogen gas pipe, stirrer, thermometer and heater, raise the internal temperature of the reactor to 75-80 ° C. proceeded. After completion of the reaction, 88 g of an isocyanate prepolymer composition was prepared by cooling the reaction product to room temperature. As a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed as 11.7 ± 0.2 mass% _NCO level.

Example A2: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 49 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 and 51 parts by weight of a polyether polyol and polyisocyanate

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 28 g to 24 g, and the content of polytetramethylene ether glycol (number average molecular weight: 1,000 g/mol, Sigma-Aldrich (agent)) was changed from 6 g 102 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that it was changed to 25 g. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed as 10.1 ± 0.1 mass% _NCO level.

Example A3: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 26.5 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B1 and 73.5 parts by weight of a polyether polyol and polyisocyanate

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 28 g to 18 g, and polyethylene glycol (number average molecular weight: 1,000 g/mol, Sigma Aldrich (produced)) instead of polytetramethylene ether glycol 121 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 50 g was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 8.5 ± 0.1 mass% _NCO level.

Example A4: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 14 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 and 86 parts by weight of a polyether polyol and polyisocyanate

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 28 g to 12 g, and polyethylene glycol (number average molecular weight: 1,000 g/mol, Sigma Aldrich (produced)) instead of polytetramethylene ether glycol 140 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 75 g was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 7.4 ± 0.1 mass% _NCO level.

Example A5: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 6 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 and 94 parts by weight of a polyether polyol and polyisocyanate

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 28 g to 6 g, and polypropylene glycol (number average molecular weight: 1,000 g/mol, Sigma-Aldrich (Product)) instead of polytetramethylene ether glycol ), 158 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 100 g was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed as 6.5 ± 0.1 mass% _NCO level.

Example A6: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 5 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B1 and 95 parts by weight of a polyether polyol and polyisocyanate

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 28 g to 5 g, and polypropylene glycol (number average molecular weight: 1,000 g/mol, Sigma-Aldrich (Product)) instead of polytetramethylene ether glycol ), 152 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 95 g was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed as 6.0 ± 0.1 mass% _NCO level.

Example A7: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 90 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B2 and 10 parts by weight of a polyether polyol and polyisocyanate

114 g of isocyanate prepolymer composition in the same manner as in Example A1, except that 55 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was prepared. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed as 9.0 ± 0.1 mass% _NCO level.

Example A8: Preparation of an isocyanate prepolymer composition using a polyol composition and polyisocyanate comprising 50 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B2 and 50 parts by weight of a polyether polyol

46 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation B2 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polytetramethylene ether glycol (number average molecular weight: 1,000 g/mol , 124 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that the content of Sigma Aldrich (Production)) was changed from 6 g to 46 g. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 8.3 ± 0.1 mass% _NCO level.

Example A9: Preparation of isocyanate prepolymer composition using polyol composition and polyisocyanate comprising 41 parts by weight of anhydrosugar alcohol-alkylene glycol composition of Preparation B2 and 59 parts by weight of polyether polyol

35 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polypropylene glycol (number average Molecular weight: 1,000 g/mol, 137 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1 except that 50 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 7.5 ± 0.1 mass% _NCO level.

Example A10: Preparation of isocyanate prepolymer composition using polyol composition and polyisocyanate comprising 23.5 parts by weight of anhydrosugar alcohol-alkylene glycol composition of Preparation B2 and 76.5 parts by weight of polyether polyol

23 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polypropylene glycol (number average Molecular weight: 1,000 g/mol, 151 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 75 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 6.8 ± 0.1 mass% _NCO level.

Example A11: Preparation of isocyanate prepolymer composition using polyol composition comprising 11 parts by weight of anhydrosugar alcohol-alkylene glycol composition and 89 parts by weight of polyether polyol of Preparation B2 and polyisocyanate

12 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 164 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 100 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed as 6.3 ± 0.1 mass% _NCO level.

Example A12: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 5 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B2 and 95 parts by weight of a polyether polyol and polyisocyanate

5 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 152 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 95 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.9 ± 0.1 mass% _NCO level.

Example A13: Preparation of an isocyanate prepolymer composition using a polyol composition and polyisocyanate comprising 95 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B3 and 5 parts by weight of a polyether polyol

181 g of the isocyanate prepolymer composition in the same manner as in Example A1, except that 123 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was prepared. As a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition at this time, it was confirmed to be 5.7 ± 0.1 mass% _NCO level.

Example A14: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 80.5 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B3 and 19.5 parts by weight of a polyether polyol and polyisocyanate

103 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation B3 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polytetramethylene ether glycol (number average molecular weight: 1,000 g/mol , Sigma Aldrich) was prepared in the same manner as in Example A1, except for changing the content of 6g to 25g isocyanate prepolymer composition 180g. As a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition at this time, it was confirmed to be 5.7 ± 0.1 mass% _NCO level.

Example A15: Preparation of an isocyanate prepolymer composition using a polyol composition and polyisocyanate comprising 61 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B3 and 39 parts by weight of a polyether polyol

In place of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 78 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used, and polypropylene glycol (number average Molecular weight: 1,000 g/mol, 179 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 50 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. As a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition at this time, it was confirmed to be 5.7 ± 0.1 mass% _NCO level.

Example A16: Preparation of an isocyanate prepolymer composition using a polyol composition and polyisocyanate comprising 41 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B3 and 59 parts by weight of a polyether polyol

52 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used in place of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polypropylene glycol (number average Molecular weight: 1,000 g/mol, 179 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 75 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.8 ± 0.1 mass% _NCO level.

Example A17: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 21 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B3 and 79 parts by weight of a polyether polyol and polyisocyanate

In place of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 26 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 178 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 100 g of Sigma Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.8 ± 0.1 mass% _NCO level.

Example A18: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 5 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B3 and 95 parts by weight of a polyether polyol and polyisocyanate

6 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, Sigma-Aldrich) 119 g, and a mixture of 28 g isophorone diisocyanate and 22 g toluene diisocyanate was used instead of 56 g isophorone diisocyanate. 172 g of the composition was prepared. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.8 ± 0.1 mass% _NCO level.

Example A19: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 68 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B4 and 32 parts by weight of a polyether polyol and polyisocyanate

In place of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 28 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B4 was used, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, Sigma Aldrich) 13 g, and a mixture of 28 g isophorone diisocyanate and 22 g toluene diisocyanate was used instead of 56 g isophorone diisocyanate. In the same manner as in Example A1, an isocyanate prepolymer was used. 86 g of the composition were prepared. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed as 10.9 ± 0.1 mass% _NCO level.

Example A20: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 29 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B5 and 71 parts by weight of a polyether polyol and polyisocyanate

26 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B5 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, Sigma Aldrich) 63 g, and a mixture of 28 g of isophorone diisocyanate and 22 g of toluene diisocyanate was used instead of 56 g of isophorone diisocyanate. In the same manner as in Example A1, an isocyanate prepolymer was used. 131 g of the composition was prepared. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 7.3 ± 0.1 mass% _NCO level.

Example A21: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 12 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B6 and 88 parts by weight of a polyether polyol and polyisocyanate

15 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B6 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, Sigma Aldrich) 113 g, and a mixture of 28 g isophorone diisocyanate and 22 g toluene diisocyanate was used instead of 56 g isophorone diisocyanate. In the same manner as in Example A1, an isocyanate prepolymer was used. 168 g of the composition were prepared. As a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition at this time, it was confirmed to be 5.7 ± 0.1 mass% _NCO level.

Example A22: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 68 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B7 and 32 parts by weight of a polyether polyol and polyisocyanate

In place of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 27 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B7 was used, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, Sigma Aldrich) 13 g, and a mixture of 28 g isophorone diisocyanate and 22 g toluene diisocyanate was used instead of 56 g isophorone diisocyanate. In the same manner as in Example A1, an isocyanate prepolymer was used. 84 g of the composition were prepared. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed as 11.1 ± 0.1 mass% _NCO level.

Example A23: Preparation of an isocyanate prepolymer composition using polyisocyanate and a polyol composition comprising 39 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B8 and 61 parts by weight of a polyether polyol

Instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 41 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B8 was used, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, Sigma Aldrich) 63 g, and a mixture of 28 g of isophorone diisocyanate and 22 g of toluene diisocyanate was used instead of 56 g of isophorone diisocyanate. In the same manner as in Example A1, an isocyanate prepolymer was used. 146 g of the composition were prepared. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 6.6 ± 0.1 mass% _NCO level.

Example A2 4 : Preparation of an isocyanate prepolymer composition using a polyol composition comprising 10 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B9 and 90 parts by weight of a polyether polyol and polyisocyanate

13 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B9 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, Sigma Aldrich) 113 g, and a mixture of 28 g isophorone diisocyanate and 22 g toluene diisocyanate was used instead of 56 g isophorone diisocyanate. In the same manner as in Example A1, an isocyanate prepolymer was used. 166 g of the composition was prepared. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.8 ± 0.1 mass% _NCO level.

Example A2 5 : Preparation of an isocyanate prepolymer composition using a polyol composition comprising 20 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B13 and 80 parts by weight of a polyether polyol and polyisocyanate

30 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B13 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, Sigma-Aldrich) 119 g, and a mixture of 28 g isophorone diisocyanate and 22 g toluene diisocyanate was used instead of 56 g isophorone diisocyanate. 188 g of the composition were prepared. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.2 ± 0.1 mass% _NCO level.

Example A26: Preparation of isocyanate prepolymer composition using polyol composition and polyisocyanate comprising 1.6 parts by weight of anhydrosugar alcohol-alkylene glycol composition of Preparation B3 and 98.4 parts by weight of polyether polyol

2 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, Sigma-Aldrich) 123 g, and a mixture of 28 g isophorone diisocyanate and 22 g toluene diisocyanate was used instead of 56 g isophorone diisocyanate. In the same manner as in Example A1, an isocyanate prepolymer was used. 166 g of the composition was prepared. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.8 ± 0.1 mass% _NCO level.

Comparative Example A1: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 0.8 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 and 99.2 parts by weight of a polyether polyol and polyisocyanate

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 28 g to 1 g, and the content of polytetramethylene ether glycol (number average molecular weight: 1,000 g/mol, Sigma Aldrich (agent)) was 6 g 174 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that it was changed to 121 g. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.9 ± 0.1 mass% _NCO level.

Comparative Example A2: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 97 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B1 and 3 parts by weight of a polyether polyol and polyisocyanate

The content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 28 g to 97 g, and the content of polytetramethylene ether glycol (number average molecular weight: 1,000 g/mol, Sigma-Aldrich (agent)) was increased from 6 g 152 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that it was changed to 3 g. As a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition at this time, it was confirmed as 11.9 ± 0.1 mass% _NCO level.

Comparative Example A3: Preparation of an isocyanate prepolymer composition using a polyol composition containing 0.8 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B2 and 99.2 parts by weight of a polyether polyol and polyisocyanate

In place of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 1 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used, and polypropylene glycol (number average Molecular weight: 1,000 g/mol, 176 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 123 g of Sigma-Aldrich (manufactured by Sigma Aldrich)) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.9 ± 0.1 mass% _NCO level.

Comparative Example A4: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 98 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B2 and 2 parts by weight of a polyether polyol and polyisocyanate

In place of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 98 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used, and polypropylene glycol (number average Molecular weight: 1,000 g/mol, 152 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 2 g of Sigma-Aldrich (Production)) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed as 9.2 ± 0.1 mass% _NCO level.

Comparative Example A5: Preparation of an isocyanate prepolymer composition using a polyol composition containing 0.8 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B3 and 99.2 parts by weight of a polyether polyol and polyisocyanate

1 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation B3 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 177 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 124 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.8 ± 0.1 mass% _NCO level.

Comparative Example A6: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 99.2 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B3 and 0.8 parts by weight of a polyether polyol and polyisocyanate

In place of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 128 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 181 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 1 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. As a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition at this time, it was confirmed to be 5.7 ± 0.1 mass% _NCO level.

Comparative Example A7: Preparation of isocyanate prepolymer using polyether polyol and polyisocyanate

177 g of an isocyanate prepolymer composition in the same manner as in Example A1, except that the polytetramethylene ether glycol content was changed from 6 g to 125 g without using the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1. prepared. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.8 ± 0.1 mass% _NCO level.

Comparative Example A8: Preparation of an isocyanate prepolymer composition using anhydrosugar alcohol-alkylene glycol composition and polyisocyanate of Preparation B1

111 g of isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that polytetramethylene ether glycol was not used and the content of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was changed from 28 g to 58 g. prepared. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed as 9.3 ± 0.1 mass% _NCO level.

Comparative Example A9: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 10 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B10 and 90 parts by weight of a polyether polyol and polyisocyanate

9 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B10 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 131 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 80 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 7.3 ± 0.1 mass% _NCO level.

Comparative Example A10: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 50 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B11 and 50 parts by weight of a polyether polyol and polyisocyanate

85 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B11 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 210 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 86 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed as 4.6 ± 0.1 mass% _NCO level.

Comparative Example A11: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 90 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B12 and 10 parts by weight of a polyether polyol and polyisocyanate

265 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B12 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 327 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 30 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed as 3.0 ± 0.1 mass% _NCO level.

Comparative Example A12: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 0.8 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B10 and 99.2 parts by weight of a polyether polyol and polyisocyanate

1 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B10 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 162 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 120 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.9 ± 0.1 mass% _NCO level.

Comparative Example A13: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 96.7 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B10 and 3.3 parts by weight of a polyether polyol and polyisocyanate

In place of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 29 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B10 was used, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 73 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 1 g of Sigma-Aldrich (Production)) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed as 13.1 ± 0.1 mass% _NCO level.

Comparative Example A14: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 0.8 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B11 and 99.2 parts by weight of a polyether polyol and polyisocyanate

1 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B11 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 166 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 125 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.8 ± 0.1 mass% _NCO level.

Comparative Example A15: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 98 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B11 and 2 parts by weight of a polyether polyol and polyisocyanate

261 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B11 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 301 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 6 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 3.2 ± 0.1 mass% _NCO level.

Comparative Example A16: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 0.8 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B12 and 99.2 parts by weight of a polyether polyol and polyisocyanate

In place of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 1 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B12 was used, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 166 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 125 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 5.8 ± 0.1 mass% _NCO level.

Comparative Example A17: Preparation of an isocyanate prepolymer composition using a polyol composition comprising 99.2 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B12 and 0.8 parts by weight of a polyether polyol and polyisocyanate

353 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B12 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and polyethylene glycol (number average molecular weight) was used instead of polytetramethylene ether glycol. : 1,000 g/mol, 373 g of an isocyanate prepolymer composition was prepared in the same manner as in Example A1, except that 3 g of Sigma-Aldrich (manufactured by Sigma Aldrich) was used. At this time, as a result of confirming the isocyanate content of the prepared isocyanate prepolymer composition, it was confirmed to be 2.6 ± 0.1 mass% _NCO level.

<Preparation of end-capped isocyanate prepolymer composition>

Example B1: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A1 and an end capping agent

88 g of the isocyanate prepolymer composition obtained in Example A1 and 6 g of allyl phenol (Sigma-Aldrich (Co.) It was mixed while heating. While the reaction was proceeding, the reaction was terminated when the NCO peak near 2,300 cm ^-1 disappeared using the FT-IR spectrum. After completion of the reaction, the reaction product was cooled to room temperature to obtain 89 g of an end-capped isocyanate prepolymer composition.

Example B2: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A2 and an end capping agent

102 g of the isocyanate prepolymer composition obtained in Example A2 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 8 g of tertiary butyl phenol (Sigma-Aldrich Co., Ltd.) was used instead of allyl phenol as an end capping agent. Except for that, 104 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Example B3: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A3 and an end capping agent

Example B1 and Example B1, except that 102 g of the isocyanate prepolymer composition obtained in Example A3 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 10 g In the same manner, 112 g of an end-capped isocyanate prepolymer composition was obtained.

Example B4: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A4 and an end capping agent

Example B1 and Example B1, except that 140 g of the isocyanate prepolymer composition obtained in Example A4 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 13 g In the same manner, 145 g of an end-capped isocyanate prepolymer composition was obtained.

Example B5: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A5 and an end capping agent

158 g of the isocyanate prepolymer composition obtained in Example A5 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 18 g of tertiary butyl phenol (Sigma Aldrich Co., Ltd.) was used instead of allyl phenol as an end capping agent. Except for that, 168 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Example B6: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A6 and an end capping agent

Example B1 and Example B1, except that 172 g of the isocyanate prepolymer composition obtained in Example A6 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 24 g In the same manner, 187 g of an end-capped isocyanate prepolymer composition was obtained.

Example B7: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A7 and an end capping agent

114 g of the isocyanate prepolymer composition obtained in Example A7 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 7 g of tertiary butyl phenol (Sigma Aldrich Co., Ltd.) was used instead of allyl phenol as an end capping agent. Except that, 115 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Example B8: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A8 and an end capping agent

Example B1 and Example B1 except that 124 g of the isocyanate prepolymer composition obtained in Example A8 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 9 g In the same manner, 126 g of an end-capped isocyanate prepolymer composition was obtained.

Example B9: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A9 and an end capping agent

137 g of the isocyanate prepolymer composition obtained in Example A9 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 11 g of tertiary butyl phenol (Sigma Aldrich Co.) was used instead of allyl phenol as an end capping agent. Except for that, 141 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Example B10: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A10 and an end capping agent

Example B1 and Example B1 except that 151 g of the isocyanate prepolymer composition obtained in Example A10 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 14 g In the same manner, 157 g of an end-capped isocyanate prepolymer composition was obtained.

Example B11: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A11 and an end capping agent

164 g of the isocyanate prepolymer composition obtained in Example A11 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 19 g of tertiary butyl phenol (Sigma Aldrich Co., Ltd.) was used instead of allyl phenol as an end capping agent. Except for that, 174 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Example B12: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A12 and an endcapping agent

Example B1 and Example B1, except that 174 g of the isocyanate prepolymer composition obtained in Example A12 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 24 g In the same manner, 188 g of an end-capped isocyanate prepolymer composition was obtained.

Example B13: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A13 and an end capping agent

181 g of the isocyanate prepolymer composition obtained in Example A13 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 11 g of tertiary butyl phenol (Sigma Aldrich Co., Ltd.) was used instead of allyl phenol as an end capping agent. Except that, 183 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Example B14: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A14 and an end capping agent

Example B1 and Example B1, except that 180 g of the isocyanate prepolymer composition obtained in Example A14 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 12 g In the same manner, 183 g of an end-capped isocyanate prepolymer composition was obtained.

Example B15: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A15 and an end capping agent

179 g of the isocyanate prepolymer composition obtained in Example A15 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 14 g of tertiary butyl phenol (Sigma Aldrich Co., Ltd.) was used instead of allyl phenol as an end capping agent. Except that, 184 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Example B16: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A16 and an end capping agent

Example B1 and Example B1, except that 179 g of the isocyanate prepolymer composition obtained in Example A16 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 17 g In the same manner, 186 g of an end-capped isocyanate prepolymer composition was obtained.

Example B17: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A17 and an end capping agent

178 g of the isocyanate prepolymer composition obtained in Example A17 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 21 g of tertiary butyl phenol (Sigma Aldrich Co.) was used instead of allyl phenol as an end capping agent. Except that, 189 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Example B18: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A18 and an end capping agent

Example B1 and Example B1, except that 177 g of the isocyanate prepolymer composition obtained in Example A18 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 25 g In the same manner, 192 g of an end-capped isocyanate prepolymer composition was obtained.

Example B19: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A19 and an end capping agent

86 g of the isocyanate prepolymer composition obtained in Example A19 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 6 g of tertiary butyl phenol (Sigma Aldrich Co.) was used in place of allyl phenol as an end capping agent. Except that, 87 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Example B20: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A20 and an end capping agent

131 g of the isocyanate prepolymer composition obtained in Example A20 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 12 g of tertiary butyl phenol (Sigma Aldrich Co., Ltd.) was used in place of allyl phenol as an end capping agent. Except that, 136 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Example B21: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A21 and an end capping agent

Example B1 and Example B1, except that 168 g of the isocyanate prepolymer composition obtained in Example A21 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 23 g In the same manner, 182 g of an end-capped isocyanate prepolymer composition was obtained.

Example B22: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A22 and an end capping agent

84 g of the isocyanate prepolymer composition obtained in Example A22 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 6 g of tertiary butyl phenol (Sigma-Aldrich Co., Ltd.) was used in place of allyl phenol as an end capping agent. Except that, 86 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Example B23: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A23 and an end capping agent

Example B1 and Example B1, except that 146 g of the isocyanate prepolymer composition obtained in Example A23 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 14 g In the same manner, 151 g of an end-capped isocyanate prepolymer composition was obtained.

Example B24: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A24 and an end capping agent

166 g of the isocyanate prepolymer composition obtained in Example A24 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 23 g of tertiary butyl phenol (Sigma Aldrich Co.) was used instead of allyl phenol as an end capping agent. Except that, 180 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Example B25: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A25 and an end capping agent

Example B1 and Example B1, except that 188 g of the isocyanate prepolymer composition obtained in Example A25 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 28 g In the same manner, 205 g of an end-capped isocyanate prepolymer composition was obtained.

Example B26: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Example A26 and an end capping agent

166 g of the isocyanate prepolymer composition obtained in Example A26 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 26 g of tertiary butyl phenol (Sigma Aldrich Co., Ltd.) was used in place of allyl phenol as an end capping agent. Except that, 182 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Comparative Example B1: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A1 and an end capping agent

Example B1 and Example B1 except that 174 g of the isocyanate prepolymer composition obtained in Comparative Example A1 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 25 g In the same manner, 189 g of an end-capped isocyanate prepolymer composition was obtained.

Comparative Example B2: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A2 and an end capping agent

Example B1, except that 86 g of the isocyanate prepolymer composition obtained in Comparative Example A2 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 5 g In the same manner, 87 g of an end-capped isocyanate prepolymer composition was obtained.

Comparative Example B3: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A3 and an end capping agent

176 g of the isocyanate prepolymer composition obtained in Comparative Example A3 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 26 g of tertiary butyl phenol (Sigma Aldrich Co.) was used instead of allyl phenol as an end capping agent. Except that, 191 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Comparative Example B4: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A4 and an end capping agent

Example B1 and Example B1 except that 112 g of the isocyanate prepolymer composition obtained in Comparative Example A4 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 7 g In the same manner, 113 g of an end-capped isocyanate prepolymer composition was obtained.

Comparative Example B5: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A5 and an end capping agent

177 g of the isocyanate prepolymer composition obtained in Comparative Example A5 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 26 g of tertiary butyl phenol (Sigma Aldrich Co., Ltd.) was used instead of allyl phenol as an end capping agent. Except that, 193 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Comparative Example B6: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A6 and an end capping agent

Example B1 and Example B1, except that 181 g of the isocyanate prepolymer composition obtained in Comparative Example A6 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 11 g In the same manner, 183 g of an end-capped isocyanate prepolymer composition was obtained.

Comparative Example B7: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A7 and an end capping agent

177 g of the isocyanate prepolymer composition obtained in Comparative Example A7 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 27 g of tertiary butyl phenol (Sigma Aldrich Co.) was used instead of allyl phenol as an end capping agent. Except that, 193 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Comparative Example B8: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A8 and an end capping agent

Example B1 and Example B1 except that 111 g of the isocyanate prepolymer composition obtained in Comparative Example A8 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 7 g In the same manner, 112 g of an end-capped isocyanate prepolymer composition was obtained.

Comparative Example B9: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A9 and an end capping agent

131 g of the isocyanate prepolymer composition obtained in Comparative Example A9 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 14 g of tertiary butyl phenol (Sigma-Aldrich Co., Ltd.) was used instead of allyl phenol as an end capping agent. Except that, 138 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Comparative Example B10: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A10 and an end capping agent

Example B1 and Example B1 except that 210 g of the isocyanate prepolymer composition obtained in Comparative Example A10 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 23 g In the same manner, 221 g of an end-capped isocyanate prepolymer composition was obtained.

Comparative Example B11: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A11 and an end capping agent

327 g of the isocyanate prepolymer composition obtained in Comparative Example A11 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 24 g of tertiary butyl phenol (Sigma Aldrich Co.) was used instead of allyl phenol as an end capping agent. Except for that, 334 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Comparative Example B12: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A12 and an end capping agent

Example B1 and Example B1, except that 162 g of the isocyanate prepolymer composition obtained in Comparative Example A12 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 25 g In the same manner, 177 g of an end-capped isocyanate prepolymer composition was obtained.

Comparative Example B13: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A13 and an end capping agent

71 g of the isocyanate prepolymer composition obtained in Comparative Example A13 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 5 g of tertiary butyl phenol (Sigma Aldrich Co., Ltd.) was used in place of allyl phenol as an end capping agent. Except that, 72 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Comparative Example B14: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A14 and an end capping agent

Example B1 and Example B1, except that 166 g of the isocyanate prepolymer composition obtained in Comparative Example A14 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 27 g In the same manner, 183 g of an end-capped isocyanate prepolymer composition was obtained.

Comparative Example B15: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A15 and an end capping agent

301 g of the isocyanate prepolymer composition obtained in Comparative Example A15 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 20 g of tertiary butyl phenol (Sigma Aldrich Co.) was used instead of allyl phenol as an end capping agent. Except that, 305 g of an end-capped isocyanate prepolymer composition was obtained in the same manner as in Example B1.

Comparative Example B16: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A16 and an end capping agent

Example B1 and Example B1, except that 166 g of the isocyanate prepolymer composition obtained in Comparative Example A16 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 27 g In the same manner, 183 g of an end-capped isocyanate prepolymer composition was obtained.

Comparative Example B17: Preparation of an end-capped isocyanate prepolymer composition using the isocyanate prepolymer composition of Comparative Example A17 and an end capping agent

373 g of the isocyanate prepolymer composition obtained in Comparative Example A17 was used in place of the isocyanate prepolymer composition obtained in Example A1, and the content of allyl phenol as an end capping agent was changed from 6 g to 24 g. In the same manner, 377 g of an end-capped isocyanate prepolymer composition was obtained.

<Preparation of epoxy resin composition>

Examples C1 to C26 and Comparative Examples C1 to C17: Preparation of an epoxy resin composition

As an epoxy resin, 45 parts by weight of a diglycidyl ether (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical Co., Ltd.) of bisphenol A, a curing agent for epoxy resins ( dicyandiamide (DICY), Evonik (produced), Dicyanex 1400F) 4.9 parts by weight and a curing accelerator for epoxy resin (urea derivative (DIURON), Evonik (produced), Amicure UR-D) 0.1 parts by weight, as a filler, 21~ 25 parts by weight of calcium carbonate (CaCO3, OMYA (manufactured), OMYACARB 30-CN) having a particle size of 33 μm, 10 parts by weight of a core-shell rubber (KANEKA (manufactured), MX-154) as an impact modifier, epoxy As the adhesion promoter for the resin, 15 parts by weight of each of the end-capped isocyanate prepolymer compositions obtained in Examples B1 to B26 and Comparative Examples B1 to B17 above were used.

Epoxy resin compositions of Examples C1 to C26 and Comparative Examples C1 to C17 were prepared by mixing an epoxy resin, a curing agent, a curing accelerator, a filler, a septum reinforcing agent and an adhesion promoter in the compositions shown in Table 1 below.

Specifically, an epoxy resin, an impact modifier, and a toughener were put into a 250 mL reactor in which the upper and lower parts were separated, and the mixture was first stirred at 80° C. for 20 minutes. Then, an epoxy resin composition was prepared by adding a curing agent, a curing accelerator, and a filler according to a predetermined composition, and performing secondary stirring for 20 minutes under the same conditions.

<Evaluation of physical properties of epoxy resin composition>

Using the epoxy resin compositions prepared in Examples C1 to C26 and Comparative Examples C1 to C17 as an adhesive, the physical properties of the adhesive specimens were measured in the following manner, and the results are shown in Table 2 below.

(1) Evaluation of single lap shear strength (unit: MPa)

A cold rolled steel sheet (CR) having a size of 100 mm in length × 25 mm in width × 1 mm in thickness was washed using ethanol. Each of the epoxy resin compositions obtained in Examples C1 to C26 and Comparative Examples C1 to C17 as an adhesive on one surface of the washed cold rolled steel sheet was applied to a surface having a length of 12.5 mm × width of 25 mm, and then a constant adhesive thickness was maintained thereon In order to do this, a small amount of microbeads was laminated. Thereafter, another cold rolled steel sheet was covered and fixed thereon, and then hardened at 180° C. for 20 minutes. Shear strength was measured using a universal testing machine for the adhesive specimen cooled to 23° C. after curing. At this time, the shear strength was measured while applying a load in the 180 degree direction at a tensile rate of 5 mm/min.

(2) T-peel strength (unit: N/25 mm) evaluation

A cold-rolled steel sheet having a size of 150 mm in length × 25 mm in width × 1 mm in thickness was bent at right angles, and after bending, the lengths of each side were 70 mm and 80 mm. After applying each of the epoxy resin compositions obtained in Examples C1 to C26 and Comparative Examples C1 to C17 as an adhesive on a surface of 80 mm in length × 25 mm in width, a small amount of microbeads was laminated thereon to maintain a constant adhesive thickness. . Thereafter, another cold rolled steel sheet was covered and fixed thereon, and then hardened at 180° C. for 20 minutes. After curing, the T-peel strength was measured for the adhesive specimen cooled to 23° C. using a universal testing machine. At this time, the measurement of the T-peel strength was performed while applying a load in the 180 degree direction at a tensile rate of 50 mm/min.

As shown in Table 2, the adhesive specimens of Examples C1 to C26 according to the present invention exhibited a shear strength of 36 MPa or more and a T-peel strength of 200 N/25 mm or more, thereby implementing excellent adhesive properties in various aspects. did.

However, an end-capped isocyanate prepolymer composition prepared by end-capping an isocyanate prepolymer composition prepared using a polyol composition that deviates from a specific weight ratio between the anhydrosugar alcohol-alkylene glycol composition and the polyether polyol is applied as an adhesion promoter for an epoxy resin or , End-capped isocyanate prepolymer composition prepared by end-capping an isocyanate prepolymer composition prepared using a polyol composition comprising an anhydrosugar alcohol-alkylene glycol composition outside a specific weight ratio between the anhydrosugar alcohol composition and the alkylene oxide Epoxy the end-capped isocyanate prepolymer composition The adhesive specimens of Comparative Examples C1 to C17 applied as adhesion promoters for resins were very poor compared to the adhesive specimens of Examples.

Specifically, in the case of the adhesive specimens of Comparative Examples C2, C4, C6, C8, C10, C11, C14, C15, C16 and C17, the shear strength was 28 MPa or less, and the T-peel strength was 180 N/25 mm or less. It was very poor compared to the adhesive specimens of Examples, and in the case of the adhesive specimens of Comparative Examples C1, C3, C5, C7, C9, C12 and C13, surface peeling occurred, making it difficult to measure shear strength and T-peel strength. In this case, the surface peeling refers to the case where the adhesive interface is peeled off.

Claims (17)

An isocyanate prepolymer composition prepared by urethane-reacting a polyol composition comprising an anhydrosugar alcohol-alkylene glycol composition and a polyether polyol with a polyisocyanate, comprising:
The anhydrosugar alcohol-alkylene glycol composition is prepared by addition reaction of more than 50 parts by weight to less than 2,000 parts by weight of an alkylene oxide per 100 parts by weight of anhydrosugar alcohol composition,
The anhydrosugar alcohol composition includes first to fifth polyol components,
here,
The first polyol component is monosugar alcohol,
The second polyol component is dianhydrosugar alcohol,
The third polyol component is a polysaccharide alcohol represented by the following formula (1),
The fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1),
The fifth polyol component is at least one polymer selected from the first to fourth polyol components,
The polyol composition, based on 100 parts by weight of the polyol composition, comprises 1 to 96.5 parts by weight of the anhydrosugar alcohol-alkylene glycol composition and 3.5 to 99 parts by weight of the polyether polyol,
Isocyanate prepolymer composition:
[Formula 1]

In Formula 1, n is an integer of 0 to 4. According to claim 1,
the first polyol component is monohydrate hexitol;
the second polyol component is hexitol dianhydride;
The isocyanate prepolymer composition, wherein the fourth polyol component is selected from a compound represented by the following formula (2), a compound represented by the following formula (3), or a mixture thereof:
[Formula 2]

[Formula 3]

In Formulas 2 and 3,
n is each independently an integer from 0 to 4. The isocyanate prepolymer composition of claim 1 , wherein the fifth polyol component comprises at least one selected from the group consisting of a condensation polymer prepared from the following polycondensation reaction:
- polycondensation reaction of the first polyol component,
- polycondensation reaction of the second polyol component,
- polycondensation reaction of the third polyol component,
- polycondensation reaction of the fourth polyol component,
- polycondensation reaction of the first polyol component and the second polyol component;
- polycondensation reaction of the first polyol component and the third polyol component;
- polycondensation reaction of the first polyol component and the fourth polyol component;
- polycondensation reaction of the second polyol component and the third polyol component;
- Polycondensation reaction of the second polyol component and the fourth polyol component,
- Polycondensation reaction of the third polyol component and the fourth polyol component;
- polycondensation reaction of the first polyol component, the second polyol component and the third polyol component;
- polycondensation reaction of the first polyol component, the second polyol component and the fourth polyol component;
- polycondensation reaction of the first polyol component, the third polyol component and the fourth polyol component;
- polycondensation reaction of the second polyol component, the third polyol component and the fourth polyol component, or
- Polycondensation reaction of the first polyol component, the second polyol component, the third polyol component and the fourth polyol component. The isocyanate prepolymer composition according to claim 1, wherein the anhydrosugar alcohol composition satisfies the following i) to iii):
i) the number average molecular weight (Mn) of the anhydrosugar alcohol composition is 193 to 1,589 g/mol;
ii) the polydispersity index (PDI) of the anhydrosugar alcohol composition is 1.13 to 3.41;
iii) The average number of -OH groups per molecule in the anhydrosugar alcohol composition is 2.54 to 21.36. The method according to claim 1, wherein the anhydrosugar alcohol composition is subjected to a hydrogenation reaction of a glucose-containing saccharide composition to prepare a hydrogenated sugar composition, the obtained hydrogenated sugar composition is heated under an acid catalyst for dehydration reaction, and the obtained dehydration reaction product is subjected to a hydrogenation reaction. An isocyanate prepolymer composition prepared by thin film distillation. 6. The isocyanate prepolymer composition of claim 5, wherein the glucose-containing saccharide composition contains from 41% to 99.5% by weight of glucose, based on the total weight of the saccharide composition. The isocyanate prepolymer composition of claim 1 , wherein the polyether polyol comprises a polyalkylene glycol. A polyol composition comprising anhydrosugar alcohol-alkylene glycol composition and polyether polyol, comprising the step of urethane-reacting a polyisocyanate,
The anhydrosugar alcohol-alkylene glycol composition is prepared by addition reaction of more than 50 parts by weight to less than 2,000 parts by weight of an alkylene oxide per 100 parts by weight of anhydrosugar alcohol composition,
The anhydrosugar alcohol composition includes first to fifth polyol components,
here,
The first polyol component is monosugar alcohol,
The second polyol component is dianhydrosugar alcohol,
The third polyol component is a polysaccharide alcohol represented by the following formula (1),
The fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1),
The fifth polyol component is at least one polymer selected from the first to fourth polyol components,
The polyol composition, based on 100 parts by weight of the polyol composition, comprises 1 to 96.5 parts by weight of the anhydrosugar alcohol-alkylene glycol composition and 3.5 to 99 parts by weight of the polyether polyol,
A method for preparing an isocyanate prepolymer composition:
[Formula 1]

In Formula 1, n is an integer of 0 to 4. The method for preparing an isocyanate prepolymer composition according to claim 8, wherein the anhydrosugar alcohol composition satisfies the following i) to iii):
i) the number average molecular weight (Mn) of the anhydrosugar alcohol composition is 193 to 1,589 g/mol;
ii) the polydispersity index (PDI) of the anhydrosugar alcohol composition is 1.13 to 3.41;
iii) The average number of -OH groups per molecule in the anhydrosugar alcohol composition is 2.54 to 21.36. An end-capped isocyanate prepolymer composition prepared by reacting the isocyanate prepolymer composition of any one of claims 1 to 7 with an end capping agent. The method according to claim 10, wherein the end capping agent is at least one selected from the group consisting of a phenol-based compound, a triazine-based compound, an alcohol compound, an amine-based compound, a benzene-based compound, a dicarboxylic acid ester-based compound, a novolak-based compound, or a combination thereof. , an end-capped isocyanate prepolymer composition. An adhesion promoter for an epoxy resin comprising the end-capped isocyanate prepolymer composition of claim 10 . The adhesion promoter for the epoxy resin of claim 12; and an epoxy resin; containing, an epoxy resin composition. 14. The method according to claim 13, wherein the epoxy resin is bisphenol A-epichlorohydrin resin, diglycidyl ether resin of bisphenol A, novolak-type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, bi-cyclic epoxy resin, glycidyl An epoxy resin composition selected from the group consisting of a dill ester type epoxy resin, a brominated epoxy resin, a bio-derived epoxy resin, an epoxidized soybean oil, or a combination thereof. 14. The epoxy resin composition of claim 13, further comprising at least one selected from a curing agent, a curing accelerator, a filler, an impact modifier, or a combination thereof. 14. The method of claim 13, wherein the agent is 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. Further comprising an additive to be, the epoxy resin composition. An adhesive comprising the epoxy resin composition of claim 13.