KR20220067148A - An isocyanate prepolymer composition derived from anhydrosugar alcohol-alkylene glycol composition, a polyurethane-modified epoxy resin composition using the prepolymer composition and a toughening agent for epoxy resin comprising the same, and an epoxy resin composition comprising the toughening agent and an adhesive comprising the same - Google Patents

Abstract

The present invention relates to an isocyanate prepolymer composition derived from an anhydrosugar alcohol-alkylene glycol composition and a use thereof and, more specifically, to an isocyanate prepolymer composition, a polyurethane modified epoxy resin composition using the same prepolymer composition, a toughening agent for an epoxy resin including the same, an epoxy resin composition including the toughening agent, and an adhesive comprising the same, wherein the isocyanate prepolymer composition is manufactured by a urethane reaction between an isocynate prepolymer and an anhydrosugar alcohol-alkylene glycol composition in which alkylene oxide is added to an anhydrosugar alcohol composition including monohydrosugar alcohol, anhydrosugar alcohol, polysaccharide alcohol, polysaccharide alcohol-derived anhydrosugar alcohol, and at least one polymer thereof, is environmentally friendly, and particularly, the polyurethane modified epoxy resin composition manufactured by using the same is applied as a toughening agent for an epoxy resin, thereby improving impact strength of an adhesive epoxy resin composition.

Description

An isocyanate prepolymer composition derived from anhydrosugar alcohol-alkylene glycol composition, a polyurethane-modified epoxy resin composition using the prepolymer composition, a toughening agent for an epoxy resin comprising the same, and an epoxy resin composition comprising the toughening agent and an adhesive comprising the same {An isocyanate prepolymer composition derived from anhydrosugar alcohol-alkylene glycol composition, a polyurethane-modified epoxy resin composition using the prepolymer composition and a toughening agent for epoxy resin comprising the same, and an epoxy resin composition comprising the toughening agent and an adhesive comprising the same}

The present invention relates to an isocyanate prepolymer composition derived from 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 alkylene oxide is added to anhydrosugar alcohol composition containing the above polymer is prepared by urethane reaction with polyisocyanate, and is environmentally friendly, and in particular, polyurethane-modified epoxy resin composition manufactured using the same An isocyanate prepolymer composition capable of improving the impact strength of an epoxy resin composition for adhesion applied as a toughening agent for an epoxy resin, a polyurethane-modified epoxy resin composition using the prepolymer composition, a toughening agent for an epoxy resin comprising the same, and this toughening agent It relates to an epoxy resin composition comprising a, 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, epoxy resins are too brittle on their own to somewhat limit their scope of application. Therefore, to improve the fracture toughness of epoxy resins, rubber components such as carboxyl-terminated poly(butadiene co-acrylonitrile) (CTBN), amine-terminated poly(butadiene co-acrylonitrile) (ATBN) )), inorganic hard particles (e.g. aluminum trihydrate, glass beads), and high-performance thermoplastic polymers (e.g. polyethersulfone (PES), polyetherimide (PEI), polyetherketone (PEK), polyphenylene oxide ( PPO)), etc., as an additive to the epoxy resin, has been studied.

However, since the rubber additive improves the toughness of the epoxy resin, but has a low glass transition temperature, there is a problem in that the use of the epoxy resin at a high temperature is limited and mechanical properties are deteriorated. In addition, the high-performance thermoplastic polymer additive improves the thermal stability and mechanical properties of the epoxy resin, but the improvement in toughness is insufficient compared to the rubber additive. There is a problem of falling off.

Therefore, the development of a toughening agent capable of improving the impact strength of an epoxy resin while being environmentally friendly has been requested.

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 that it is environmentally friendly because it uses anhydrosugar alcohol, and in particular, the polyurethane-modified epoxy resin composition prepared using this can improve the impact strength of the epoxy resin composition for adhesion applied as a toughening agent for the epoxy resin. , an isocyanate prepolymer composition, a polyurethane-modified epoxy resin composition using the prepolymer composition, a toughening agent for an epoxy resin comprising the same, and an epoxy resin composition including the toughening agent, and an adhesive comprising the same.

A first aspect of the present invention is an isocyanate prepolymer composition prepared by urethane reaction of an anhydrosugar alcohol-alkylene glycol composition and a polyisocyanate, wherein the anhydrosugar alcohol-alkylene glycol composition is an alkylene oxide per 100 parts by weight of anhydrosugar alcohol composition It is prepared by addition reaction of more than 50 parts by weight to less than 2,000 parts by weight, and the anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is a monoanhydrosugar alcohol, and the second The 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 an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1) , wherein the fifth polyol component is at least one polymer selected from the first to fourth polyol components above:

[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 an anhydrosugar alcohol-alkylene glycol composition and a polyisocyanate, wherein the anhydrosugar alcohol-alkylene glycol composition is an anhydrosugar alcohol-alkylene glycol composition by weight per 100 parts by weight of the anhydrosugar-alcohol composition by weight of an alkylene oxide It is prepared by addition reaction of more than part to less than 2,000 parts by weight, and the anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is a monoanhydrosugar alcohol, and the second polyol The component is dianhydrosugar alcohol, the third polyol component is a polysaccharide alcohol represented by the following formula (1), and the fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the formula (1), It provides a method for preparing an isocyanate prepolymer composition, wherein the polyol component of 5 is at least one polymer selected from the first to fourth polyol components.

A third aspect of the present invention provides a polyurethane-modified epoxy resin composition prepared by reacting the isocyanate prepolymer composition according to the first aspect of the present invention and an epoxy resin.

A fourth aspect of the present invention provides a toughening agent for an epoxy resin comprising the polyurethane-modified epoxy resin composition according to the third aspect of the present invention.

A fifth aspect of the present invention, a toughening agent 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 polyurethane-modified epoxy resin composition prepared using the same is applied as a toughening agent for an epoxy resin. can

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 manufacturing an internal dehydrated product of hydrogenated sugar, it improves economic efficiency and at the same time improves the eco-friendliness by solving 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 anhydrosugar alcohol-alkylene glycol composition and polyisocyanate, wherein the anhydrosugar alcohol-alkylene glycol composition is more than 50 parts by weight of alkylene oxide per 100 parts by weight of anhydrosugar alcohol composition It is prepared by addition reaction of less than 2,000 parts by weight.

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; dianhydrosugar 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 If it exceeds 1,589, when using the polyurethane-modified epoxy resin composition prepared using the same as a toughening agent 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 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 polyurethane-modified epoxy resin composition prepared using the same as a toughening agent 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, when using the polyurethane-modified epoxy resin composition prepared using the same as a toughening agent for an epoxy resin, there is no additional effect of improving physical properties. 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°C 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 sugar composition is less than 41% by weight, the number average molecular weight (Mn) of the anhydrosugar alcohol composition is too high, and the polyurethane-modified epoxy resin composition prepared using this is used as a toughening agent for an epoxy resin. In the absence of , economic feasibility may be reduced as the material cost increases, and when it exceeds 99.5% by weight, the number average molecular weight of the anhydrosugar alcohol composition becomes too low, resulting in anhydrous sugar alcohol-alkylene glycol composition-derived polyurethane modification. The adhesive properties of the epoxy resin composition may be poor.

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 the polyurethane is modified using this. When an epoxy resin composition is prepared, and when it is used as a toughening agent 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 using it to prepare an isocyanate prepolymer composition or a polyurethane-modified epoxy resin composition.

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 too high, so that a crosslinked polyurethane is formed at the same time as mixing them. If the isocyanate prepolymer composition cannot be prepared, and on the contrary, if the added amount of alkylene oxide is 2,000 parts by weight or more, the polyurethane-modified epoxy resin composition prepared using the prepared anhydrosugar alcohol-alkylene glycol composition is used as a toughening agent for epoxy resins. The impact peel strength becomes poor.

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.

Urethane reaction with polyisocyanate and anhydrosugar alcohol-alkylene glycol composition

According to another aspect of the present invention, it comprises the step of urethane reaction of anhydrosugar alcohol-alkylene glycol composition and polyisocyanate, wherein the anhydrosugar alcohol-alkylene glycol composition is 50 parts by weight of alkylene oxide per 100 parts by weight of anhydrosugar alcohol composition It is prepared by addition reaction of more than part to less than 2,000 parts by weight, and the anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is a monoanhydrosugar alcohol, and the second polyol The component is dianhydrosugar alcohol, the third polyol component is a polysaccharide alcohol represented by the following formula (1), and the fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1), There is provided a method for preparing an isocyanate prepolymer composition, wherein the polyol component of 5 is at least one polymer selected from among the first to fourth polyol components:

[Formula 1]

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

In the preparation method of the isocyanate prepolymer composition according to the present invention, the description of the anhydrosugar alcohol composition, the alkylene oxide and the anhydrosugar alcohol-alkylene glycol composition 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.

According to one embodiment, the urethane reaction may be performed in a ratio of 2 equivalents or more of isocyanate groups in the polyisocyanate with respect to 1 equivalent of the hydroxyl group of the polyol in the anhydrosugar alcohol-alkylene glycol composition.

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, it is not limited thereto.

In one embodiment, the equivalent ratio of NCO groups in the polyisocyanate compound / OH groups in the anhydrosugar alcohol-alkylene glycol 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, or 0.6 or more. and may be less than 8.0, 7.85 or less, 7.8 or less, 7.6 or less, or 7.5 or less, for example, more than 0.1 and less than 8.0, 0.15 to 7.85, 0.5 to 7.6, or 1.0 to 7.5.

The equivalent ratio of the NCO group / OH group is 0.1 or less or 8.0 In this case, when the polyurethane-modified epoxy resin composition prepared by utilizing the prepared isocyanate prepolymer composition is used as a toughening agent for an epoxy resin, the effect of improving the impact strength may be insignificant.

[Polyurethane-modified epoxy resin composition, toughening agent for epoxy resin, epoxy resin composition, and adhesive]

The present invention also provides a polyurethane-modified epoxy resin composition prepared by reacting the isocyanate prepolymer composition of the present invention with an epoxy resin.

The present invention also provides a toughening agent for an epoxy resin comprising the above-described polyurethane-modified epoxy resin composition.

The present invention also provides a toughening agent for the epoxy resin described above; 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.

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, alicyclic diepoxy-adipide, or 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 toughening agent for the epoxy resin of the present invention may be made of only the polyurethane-modified epoxy resin composition of the present invention.

In another embodiment, the toughening agent for an epoxy resin of the present invention may further include an additional toughening agent component in addition to the polyurethane-modified epoxy resin composition of the present invention within the scope capable of achieving the object of the present invention, As this additional toughener component, a toughener component usable for epoxy resins may be used.

Although not limited thereto, in one embodiment, the additional toughener component includes carboxyl-terminated poly(butadiene co-acrylonitrile) (CTBN) modified epoxy, Core-shell rubber modified Epoxy or mixtures thereof may be used.

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 toughening agent for an epoxy resin and 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 accelerating 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. 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 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 a part by weight to 35 parts by weight, 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 120°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 under 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. 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 of isocyanate prepolymer composition>

Example A1: Preparation of an isocyanate prepolymer composition using the anhydrosugar alcohol-alkylene glycol composition of Preparation B1

15 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 145.0 g of isophorone diisocyanate (IPDI, Aldrich Co., Ltd.) and 145.0 g of di-n-butyltin dilaurate (DBTDL, Aldrich Co., Ltd.) 0.08g was placed in a 250ml four-necked glass reactor equipped with a nitrogen gas pipe, a stirrer, a thermometer and a heater, the internal temperature of the reactor was raised to 65°C-70°C, and the urethane reaction was performed while stirring under a nitrogen atmosphere for 1 hour. After completion of the reaction, the reaction product was cooled to room temperature to obtain 157 g of an isocyanate prepolymer composition. At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed as 12.1 ± 0.2 mass% _NCO level.

Example A2: Preparation of an isocyanate prepolymer composition using the anhydrosugar alcohol-alkylene glycol composition of Preparation B2

33.0 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 hexamethylene diisocyanate (HDI) was used instead of isophorone diisocyanate. , Aldrich (manufactured by Aldrich)), 155 g of an isocyanate prepolymer composition was obtained in the same manner as in Example A1, except that 126.0 g was used. At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed as 13.6 ± 0.4 mass% _NCO level.

Example A3: Preparation of isocyanate prepolymer composition using anhydrosugar alcohol-alkylene glycol composition of Preparation B3

45.0 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 4,4'-methylene was replaced with isophorone diisocyanate. 152 g of an isocyanate prepolymer composition was obtained in the same manner as in Example A1, except that 111.3 g of diphenyl diisocyanate (MDI, BASF Co., Ltd., Lupranat MI) was used. At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed as 8.7 ± 0.2 mass% _NCO level.

Example A4: Preparation of an isocyanate prepolymer composition using the anhydrosugar alcohol-alkylene glycol composition of Preparation B4

28.0 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B4 was used in place of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and 128.5 g of hexamethylene diisocyanate in place of isophorone diisocyanate 150 g of an isocyanate prepolymer composition was obtained in the same manner as in Example A1, except that At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed to be 7.9 ± 0.5 mass% _NCO level.

Example A5: Preparation of an isocyanate prepolymer composition using the anhydrosugar alcohol-alkylene glycol composition of Preparation B5

31.0 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 4,4'-methylene was replaced with isophorone diisocyanate. 154 g of an isocyanate prepolymer composition was obtained in the same manner as in Example A1, except that 128.1 g of diphenyl diisocyanate was used. At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed as 13.4 ± 0.1 mass% _NCO level.

Example A6: Preparation of isocyanate prepolymer composition using anhydrosugar alcohol-alkylene glycol composition of Preparation B6

69.0 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 the content of isophorone diisocyanate was changed from 145.0 g to 89.0 g. Except for the changes, 151 g of an isocyanate prepolymer composition was obtained in the same manner as in Example A1. At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed as 9.0 ± 0.4 mass% _NCO level.

Example A7: Preparation of isocyanate prepolymer composition using anhydrosugar alcohol-alkylene glycol composition of Preparation B7

21.0 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B7 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and 4,4'-methylene was replaced with isophorone diisocyanate. 156 g of an isocyanate prepolymer composition was obtained in the same manner as in Example A1, except that 128.1 g of diphenyl diisocyanate was used. At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed as 10.3 ± 0.5 mass% _NCO level.

Example A8: Preparation of isocyanate prepolymer composition using anhydrosugar alcohol-alkylene glycol composition of Preparation B8

50.0 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B8 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and the content of isophorone diisocyanate was changed from 145.0 g to 106.3 g. Except for the changes, 151 g of an isocyanate prepolymer composition was obtained in the same manner as in Example A1. At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed as 9.2 ± 0.2 mass% _NCO level.

Example A9: Preparation of an isocyanate prepolymer composition using the anhydrosugar alcohol-alkylene glycol composition of Preparation B9

80 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 82.2 g of hexamethylene diisocyanate was used instead of isophorone diisocyanate. Except for use, 152 g of an isocyanate prepolymer composition was obtained in the same manner as in Example A1. At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed as 6.8 ± 0.4 mass% _NCO level.

Comparative Example A1: Preparation of an isocyanate prepolymer composition using the anhydrosugar alcohol-alkylene glycol composition of Preparation B10 (preparation impossible)

12 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 the content of isophorone diisocyanate was changed from 145.0 g to 142.7 g Except for that, it was carried out in the same manner as in Example A1, but prepared by addition reaction of 50 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation B10 (Anhydrosugar alcohol-alkylene glycol composition of Preparation Example A1) The reactivity between the anhydrosugar alcohol-alkylene glycol composition) and isophorone diisocyanate is too high, and cross-linked polyurethane is formed at the same time as the mixing of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B10 and isophorone diisocyanate. A prepolymer composition could not be prepared.

Comparative Example A2: Preparation of an isocyanate prepolymer composition using the anhydrosugar alcohol-alkylene glycol composition of Preparation B11

Instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 100.0 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B11 was used, and 52.4 g of hexamethylene diisocyanate in place of isophorone diisocyanate. 141 g of an isocyanate prepolymer composition was obtained in the same manner as in Example A1, except that . At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed as 4.6 ± 0.5 mass% _NCO level.

Comparative Example A3: Preparation of an isocyanate prepolymer composition using the anhydrosugar alcohol-alkylene glycol composition of Preparation B12

100.0 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 4,4'-methylene was replaced with isophorone diisocyanate. 148 g of an isocyanate prepolymer composition was obtained in the same manner as in Example A1, except that 55.3 g of diphenyl diisocyanate was used. At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed as 4.0 ± 0.2 mass% _NCO level.

Comparative Example A4: Preparation of isocyanate prepolymer composition using polytetramethylene ether glycol (PTMEG)

96.0 g of polytetramethylene ether glycol (number average molecular weight of about 2,000 g/mol, Aldrich Co., Ltd.) was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and the content of isophorone diisocyanate 156 g of an isocyanate prepolymer composition was obtained in the same manner as in Example A1 except for changing from 145.0 g to 64.0 g. At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed as 4.7 ± 0.1 mass% _NCO level.

Comparative Example A5: Preparation of isocyanate prepolymer composition using polypropylene glycol (PPG)

In place of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 105 g of polypropylene glycol (number average molecular weight of about 3,000 g/mol, Kumho Petrochemical Co., Ltd., PPG-3022) was used, and isophorone D 149 g of an isocyanate prepolymer composition was obtained in the same manner as in Example A1, except that 64.0 g of hexamethylene diisocyanate was used instead of isocyanate. At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement of ISO 14896, it was confirmed to be 5.8 ± 0.5 mass% _NCO level.

Comparative Example A6: Preparation of isocyanate prepolymer composition using polyethylene glycol (PEG)

In place of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 64.0 g of polyethylene glycol (number average molecular weight about 1,000 g/mol, Aldrich Co., Ltd.) was used, and 4, in place of isophorone diisocyanate 154 g of an isocyanate prepolymer composition was obtained in the same manner as in Example A1, except that 96.1 g of 4'-methylenediphenyl diisocyanate was used. At this time, as a result of confirming the isocyanate content of the obtained isocyanate prepolymer composition through the potentiometric measurement method of ISO 14896, it was confirmed to be 7.1 ± 0.3 mass% _NCO level.

<Production of polyurethane-modified epoxy resin composition>

Example B1: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Example A1

25 g of the isocyanate prepolymer composition obtained in Example A1, diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical (YD-128, Kukdo Chemical) Preparation))) 136.9 g and tetraethylammonium bromide 0.16 g (TEAB, Tokyo Chemical Industry Co., Ltd.) were added and mixed while raising the temperature to 100° C. under a nitrogen atmosphere. Then, the reactants were mixed at 100° C. for 10 to 20 minutes, and the temperature inside the reactor was raised to 140° C. to 160° C. and then the polyurethane-modified epoxy reaction was performed for 30 to 90 minutes, using FT-IR spectrum. Thus, the reaction was terminated when the NCO peak near 2300 cm ^-1 disappeared. After completion of the reaction, 160 g of a polyurethane-modified epoxy resin composition was obtained by cooling the reaction product to room temperature. At this time, as a result of confirming the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed as 319.7 g/epoxy equivalent level.

Example B2: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Example A2

31 g of the isocyanate prepolymer composition obtained in Example A2 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 1,4-butanediol-based epoxy resin in place of the diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A 153 g of a polyurethane-modified epoxy resin composition was obtained in the same manner as in Example B1, except that 130.5 g of a resin (1,4-Butanediol diglycidyl ether, BDGE, Aldrich Co., Ltd.) was used. At this time, as a result of confirming the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed as 253.8 g/epoxy equivalent level.

Example B3: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Example A3

39 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 the diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A was changed from 136.9 g to 122.8 g Except for the above, 153 g of a polyurethane-modified epoxy resin composition was obtained in the same manner as in Example B1. At this time, as a result of checking the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed to be 371.1 g/epoxy equivalent level.

Example B4: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Example A4

55 g of the isocyanate prepolymer composition obtained in Example A4 was used instead of the isocyanate prepolymer composition obtained in Example A1, and a 1,4-butanediol-based epoxy resin in place of the diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A Except that 107.6 g of resin was used, 157 g of a polyurethane-modified epoxy resin composition was obtained in the same manner as in Example B1. At this time, as a result of confirming the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed as 301.6 g/epoxy equivalent level.

Example B5: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Example A5

35 g of the isocyanate prepolymer composition obtained in Example A5 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of the diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A was changed from 136.9 g to 127.3 g Except for the above, 157 g of a polyurethane-modified epoxy resin composition was obtained in the same manner as in Example B1. At this time, as a result of confirming the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed to be 381.8 g/epoxy equivalent level.

Example B6: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Example A6

60 g of the isocyanate prepolymer composition obtained in Example A6 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 1,4-butanediol-based epoxy in place of the diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A Except that 100.3 g of resin was used, 157 g of a polyurethane-modified epoxy resin composition was obtained in the same manner as in Example B1. At this time, as a result of confirming the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed as 320.3 g/epoxy equivalent level.

Example B7: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Example A7

56 g of the isocyanate prepolymer composition obtained in Example A7 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of the diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A was changed from 136.9 g to 104.4 g Except for the above, 155 g of a polyurethane-modified epoxy resin composition was obtained in the same manner as in Example B1. At this time, as a result of confirming the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed to be at a level of 487.3 g/epoxy equivalent.

Example B8: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Example A8

75 g of the isocyanate prepolymer composition obtained in Example A8 was used in place of the isocyanate prepolymer composition obtained in Example A1, and 1,4-butanediol-based epoxy in place of the diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A Except that 85.4 g of resin was used, 157 g of a polyurethane-modified epoxy resin composition was obtained in the same manner as in Example B1. At this time, as a result of confirming the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed as 426.6 g/epoxy equivalent level.

Example B9: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Example A9

39 g of the isocyanate prepolymer composition obtained in Example A9 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of the diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A was changed from 136.9 g to 120.0 g Except for the above, 153 g of a polyurethane-modified epoxy resin composition was obtained in the same manner as in Example B1. At this time, as a result of confirming the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed as 354.7 g/epoxy equivalent level.

Comparative Example B1: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Comparative Example A1 (not manufactured)

In the case of Comparative Example A1, since the isocyanate prepolymer composition was not prepared, a polyurethane-modified epoxy resin composition using the same could not be prepared either.

Comparative Example B2: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Comparative Example A2

74 g of the isocyanate prepolymer composition obtained in Comparative Example A2 was used instead of the isocyanate prepolymer composition obtained in Example A1, and a 1,4-butanediol-based epoxy resin in place of the diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A 157 g of a polyurethane-modified epoxy resin composition was obtained in the same manner as in Example B1, except that 86.1 g of the resin was used. At this time, as a result of confirming the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed as 331.2 g/epoxy equivalent level.

Comparative Example B3: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Comparative Example A3

76 g of the isocyanate prepolymer composition obtained in Comparative Example A3 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of the diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A was changed from 136.9 g to 82.5 g Except for the above, 150 g of a polyurethane-modified epoxy resin composition was obtained in the same manner as in Example B1. At this time, as a result of confirming the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed as 468.0 g/epoxy equivalent level.

Comparative Example B4: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Comparative Example A4

100 g of the isocyanate prepolymer composition obtained in Comparative Example A4 was used in place of the isocyanate prepolymer composition obtained in Example A1, and a 1,4-butanediol-based epoxy resin in place of the diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A 150 g of a polyurethane-modified epoxy resin composition was obtained in the same manner as in Example B1, except that 59.4 g of the resin was used. At this time, as a result of confirming the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed as 544.3 g/epoxy equivalent level.

Comparative Example B5: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Comparative Example A5

44 g of the isocyanate prepolymer composition obtained in Comparative Example A5 was used instead of the isocyanate prepolymer composition obtained in Example A1, and the content of the diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A was changed from 136.9 g to 115.5 g Except for the above, 149 g of a polyurethane-modified epoxy resin composition was obtained in the same manner as in Example B1. At this time, as a result of confirming the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed as 409.6 g/epoxy equivalent level.

Comparative Example B6: Preparation of a polyurethane-modified epoxy resin composition using the isocyanate prepolymer composition of Comparative Example A6

80 g of the isocyanate prepolymer composition obtained in Comparative Example A6 was used in place of the isocyanate prepolymer composition obtained in Example A1, and a 1,4-butanediol-based epoxy resin in place of the diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A 150 g of a polyurethane-modified epoxy resin composition was obtained in the same manner as in Example B1, except that 80.1 g of the resin was used. At this time, as a result of confirming the epoxy equivalent of the obtained polyurethane-modified epoxy resin composition through the epoxy equivalent measurement method of ASTM D 1652, it was confirmed as 431.5 g/epoxy equivalent level.

<Production of epoxy resin composition and cured product thereof>

Examples C1 to C9 and Comparative Examples C1 to C7: Preparation of epoxy resin composition and cured product thereof

As an epoxy resin, 45 parts by weight of a diglycidyl ether (DGEBA)-based epoxy resin of bisphenol A (YD-128, Kukdo Chemical Co., Ltd.), 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 a toughening agent for resin, 15 parts by weight of each of the polyurethane-modified epoxy resin compositions obtained in Examples B1 to B9 and Comparative Examples B2 to B6 or 15 parts by weight of a synthetic urethane resin (Huntsman, Flexibilizer DY 965) were used. did.

Epoxy resin compositions of Examples C1 to C9 and Comparative Examples C1 to C7 were prepared by mixing an epoxy resin, a curing agent, a curing accelerator, a filler, a septum reinforcing agent and a toughening agent 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. Subsequently, 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 C9 and Comparative Examples C1 to C7 as an adhesive, physical properties were measured in the following manner, and the results are shown in Table 2 below.

(1) Evaluation of single lap shear strength (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 C9 and Comparative Examples C1 to C7 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. The shear strength of the adhesive specimen cooled to 23° C. after curing was measured using a universal testing machine. 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) Impact peel strength (N/mm) evaluation

A cold-rolled steel sheet having a size of 90 mm in length × 20 mm in width × 1.6 mm in thickness was washed using ethanol. After applying each of the epoxy resin compositions obtained in Examples C1 to C9 and Comparative Examples C1 to C7 as an adhesive on one surface of the washed cold rolled steel sheet to a surface of 30 mm in length × 20 mm in width, a small amount of microbeads thereon was laminated to maintain a constant adhesive thickness. After that, another cold rolled steel sheet was covered and fixed thereon, and then hardened at 180° C. for 20 minutes. After curing and stabilizing for at least 1 hour at each test temperature condition, the impact peel strength was measured using an impact strength tester in accordance with ISO 11343 standards. At this time, the impact peel strength measurement was performed while applying a load at a speed of 2 m/sec.

[Table 2]

As shown in Table 2, the adhesive specimens of Examples C1 to C9 according to the present invention exhibited a shear strength of 28 MPa or more and an impact peel strength of 35 N/mm or more, and it was confirmed that excellent impact strength properties were realized in various aspects. .

However, the adhesive specimen of Comparative Example C1 in which a toughening agent was not used had poor shear strength and impact peel strength, and Comparative Examples C2 to C3 prepared using an anhydrosugar alcohol-alkylene glycol composition to which alkylene oxide was added in excess. In the case of the adhesive specimen of Even in the case of the adhesive specimen, the shear strength and/or the impact peel strength were relatively poor. In addition, in the case of the adhesive specimen of Comparative Example C7 using a synthetic urethane resin as a toughening agent for an epoxy resin, the impact peel strength was relatively poor.

As described above, it can be confirmed that the adhesive specimen using the toughening agent for an epoxy resin prepared using the isocyanate prepolymer composition according to the present invention greatly improves the impact peel strength while maintaining excellent shear strength.

Claims (17)

As an isocyanate prepolymer composition prepared by urethane reaction of anhydrosugar alcohol-alkylene glycol composition and 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,
Isocyanate prepolymer composition:
[Formula 1]

In Formula 1, n is an integer of 0 to 4. The isocyanate prepolymer composition of claim 1 , wherein the first polyol component is hexitol monohydrate. The isocyanate prepolymer composition of claim 1 , wherein the second polyol component is hexitol dianhydride. The isocyanate prepolymer composition according to claim 1, 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. 8. The isocyanate prepolymer composition of claim 7, 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. Anhydrosugar alcohol- comprising the step of urethane reaction of the alkylene glycol composition and 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,
A method for preparing an isocyanate prepolymer composition:
[Formula 1]

In Formula 1, n is an integer of 0 to 4. The method of claim 9, 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. A polyurethane-modified epoxy resin composition prepared by reacting the isocyanate prepolymer composition of any one of claims 1 to 8 with an epoxy resin. A toughening agent for an epoxy resin comprising the polyurethane-modified epoxy resin composition of claim 11 . The toughening agent 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, novolac type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, bi-cyclic epoxy resin, glycy 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.