KR20230083045A - Curing agent for epoxy resin comprising polyol composition prepared by adding alkylene oxide to anhydrosugar alcohol composition crosslinked with epoxy compound modified with rubber, and epoxy resin composition comprising the same and cured product thereof - Google Patents

Abstract

The present invention relates to a curing agent for an epoxy resin, an epoxy resin composition comprising the same, and a cured product thereof and, more specifically, to a curing agent for an epoxy resin comprising a polyol composition obtained by crosslinking a biomass-derived anhydrous sugar alcohol composition with an epoxy compound modified with rubber, and adding alkylene oxide, thereby being excellent in environmental friendliness, and improving the adhesion of the cured product when used in an epoxy resin composition, an epoxy resin composition comprising the same, and a cured product thereof.

Description

A curing agent for an epoxy resin comprising a polyol composition prepared by adding an alkylene oxide to an anhydrous sugar alcohol composition crosslinked with an epoxy compound modified with rubber, an epoxy resin composition comprising the same, and a cured product thereof polyol composition prepared by adding alkylene oxide to anhydrosugar alcohol composition crosslinked with epoxy compound modified with rubber, and epoxy resin composition comprising the same and cured product thereof}

The present invention relates to a curing agent for an epoxy resin, an epoxy resin composition containing the same, and a cured product thereof, and more specifically, after crosslinking an anhydrous sugar alcohol composition derived from biomass with an epoxy compound modified with rubber, alkylene A curing agent for an epoxy resin comprising a polyol composition obtained by adding an oxide, having excellent eco-friendliness and improving the adhesion of the cured product when used in an epoxy resin composition, and an epoxy resin composition comprising the same and a cured product thereof .

Epoxy resins have excellent heat resistance, mechanical properties, electrical properties and adhesion. Epoxy resins take advantage of this characteristic and are used for sealing materials such as wiring boards, circuit boards, multilayered circuit boards, semiconductor chips, coils, and electric circuits. Alternatively, epoxy resin is also used as a resin for adhesives, paints, and fiber-reinforced resins.

Epoxy resins find widespread use as thermosets in many applications. They are used as a thermosetting matrix in prepregs composed of fibers incorporated in a thermosetting matrix. Also, because of their toughness, flexibility, adhesion and chemical resistance, they can be used as materials for surface coatings, for bonding, molding and laminating, 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 required for a particular application. For example, resins can be solid, liquid or semi-solid, and can have a variety of reactivity depending on the application to which they are applied. The reactivity of epoxy resins is often measured in terms of epoxy equivalent weight, which is the molecular weight of a resin containing a single reactive epoxy group. The lower the epoxy equivalent, the higher the reactivity of the epoxy resin. Different reactivity is required for different epoxy resin applications, depending on whether it is present as a matrix for fiber-reinforced prepregs, adhesive coatings, or structural adhesives.

An epoxy resin is a chemical unit of molecules constituting it, and always has an epoxy bond. It is made by polymerizing epichlorohydrin and bisphenol A. Epoxy resin is not used alone, and it is appropriate to think of it as an intermediate of ordinary resin because it is used by adding a curing agent to change it to a thermoset material. That is, a cured product cannot be obtained with only an epoxy resin, and a thermosetting structure can be obtained only when immovable cross-linking points are formed in combination with an epoxy reactor.

Substances that create such cross-linking points are called curing agents. Curing agents that can be used together with epoxy resins include phenol, acid anhydrides, and amines. Among them, since phenol may have various structures, various physical property changes obtained by changing the epoxy resin can be obtained by changing the structure of the phenolic resin curing agent, and due to these various properties, phenolic resin curing agents are mainly It is being used. However, a problem has been derived due to free phenol present in the phenolic resin. Free phenol disappears after curing, but it poses a problem for its use because it threatens the health of workers during work.

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

Anhydrous sugar alcohol is a substance formed by removing one or more water molecules from the inside of hydrogenated sugar. When one water molecule is removed, it has the form of tetraol with four hydroxyl groups in the molecule, and two water molecules In the case of removal, it has a diol form with two hydroxyl groups in the molecule, and can be prepared using hexitol derived from starch (e.g., Korean Patent Registration No. 10-1079518, Korean Patent Publication No. 10-2012-0066904). Since anhydrosugar alcohol is an environmentally friendly material derived from renewable natural resources, research on its manufacturing method has been conducted with great interest for a long time. Among these anhydrous sugar alcohols, isosorbide prepared from sorbitol currently has the widest range of industrial applications.

The use of anhydrous sugar alcohol is very diverse, such as treatment of heart and blood vessel diseases, patch adhesives, pharmaceuticals such as mouthwashes, 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 the effect of improving the strength of these materials. useful. In addition, it is known that it can be used as an environmentally friendly solvent for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

As such, anhydrous sugar alcohol is receiving a lot of attention due to its various application possibilities, and its use in the actual industry is gradually increasing.

An object of the present invention is to utilize a biomass-derived anhydrous sugar alcohol composition to provide an eco-friendly, curing agent for epoxy resin that can improve the adhesive strength of the cured product when used in an epoxy resin composition, and an epoxy resin composition comprising the same, and It is to provide a cured product thereof.

A first aspect of the present invention, as a curing agent for epoxy resin, includes a polyol composition prepared by an addition reaction of a crosslinked anhydrous sugar alcohol composition and an alkylene oxide, wherein the crosslinked anhydrosugar alcohol composition is an anhydrous sugar alcohol composition and a rubber prepared from a crosslinking reaction of a modified epoxy compound, wherein the anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol; the second polyol component is a dianhydrosugar alcohol; the third polyol component is a polysaccharide alcohol represented by Formula 1 below; a fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from a 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; Provided is a curing agent for an epoxy resin in which the OH equivalent weight (Hydroxyl equivalent weight) of the polyol composition is 251 to 2,035 g / eq:

[Formula 1]

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

A second aspect of the present invention, an epoxy resin; It provides an epoxy resin composition comprising a; and a curing agent for an epoxy resin according to the first aspect of the present invention.

A third aspect of the present invention provides a cured product obtained by curing the epoxy resin composition according to the second aspect of the present invention.

A fourth aspect of the present invention provides an adhesive comprising a cured product according to the third aspect of the present invention.

The curing agent for epoxy resin according to the present invention can improve the adhesive strength of the cured product when used in an epoxy resin composition, and can significantly improve the adhesive strength (in particular, shear strength) of an adhesive using the curing agent.

In addition, since the curing agent for an epoxy resin according to the present invention can be prepared by utilizing an anhydrous sugar alcohol composition, which is a by-product obtained in the process of producing an internal dehydration product of hydrogenated sugar, it enhances economic feasibility and at the same time improves eco-friendliness by solving the by-product disposal problem. can improve

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

[Hardener for Epoxy Resin]

The curing agent for an epoxy resin according to the present invention includes a polyol composition prepared by an addition reaction of an alkylene oxide with a crosslinked anhydrous sugar alcohol composition prepared from a crosslinking reaction of an anhydrous sugar alcohol composition and a rubber-modified epoxy compound, wherein, The OH equivalent weight (Hydroxyl equivalent weight) of the polyol composition is 251 to 2,035 g/eq.

If the OH equivalent of the polyol composition is less than 251 g/eq, when the epoxy resin is cured with such a polyol composition, the reaction activity between the components of the polyol composition and the epoxy resin is lowered, so that the reaction does not sufficiently proceed. As a result, the light Adhesion of the adhesive containing the cargo becomes poor.

On the other hand, when the OH equivalent of the polyol composition exceeds 2,035 g/eq, the chain length per OH becomes excessively long, and tension occurs in the cured epoxy resin product cured with such a polyol composition, and elasticity is reduced (i.e., stretched). It becomes weak and weak), and eventually the adhesive strength (especially shear strength) of the adhesive containing the cured product becomes very poor.

In one embodiment, the OH equivalent (unit: g/eq) of the polyol composition may be 251 or more, 252 or more, or 253 or more, and may be 2,035 or less, 2,030 or less, 2,020 or less, 2,010 or less, 2,000 or less, or 1,995 or less. there is. Also, in one embodiment, the OH equivalent of the polyol composition may be 251 to 2,035 g/eq, more specifically 252 to 2,030 g/eq, and more specifically 253 to 2,010 g/eq. It may be, and more specifically, it may be 253 to 1,995 g / eq.

The anhydrosugar alcohol composition, rubber-modified epoxy compound, and alkylene oxide used in the preparation of the polyol composition will be described in more detail below.

Anhydrous Sugar Alcohol Composition

In the present invention, “anhydrous sugar alcohol” is generally referred to as hydrogenated sugar or sugar alcohol, which is obtained by adding hydrogen to a reducing end group of sugars by removing one or more water molecules from the compound. means any material obtained.

The anhydrosugar-alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component has the formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1), and the fifth polyol component is the first to fourth polyol components It is one or more polymers selected from

[Formula 1]

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

Anhydrous sugar alcohol, which is the first polyol component included in the anhydrous sugar-alcohol composition of the present invention; dianhydrosugar alcohol as a second polyol component; a polysaccharide alcohol as a third polyol component; anhydrous sugar alcohol formed by removing water molecules from polysaccharide alcohol, which is the fourth polyol component; And at least one, preferably two or more, more preferably all of one or more polymers selected from the first to fourth polyol components that are the fifth polyol component, a glucose-containing saccharide composition (e.g., glucose , mannose, fructose, and maltose) by hydrogenation reaction to prepare a hydrogenated sugar composition, dehydration reaction by heating the obtained hydrogenated sugar composition under an acid catalyst, and the resulting dehydration reaction 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 anhydrous sugar alcohol composition of the present invention may be by-products remaining after obtaining a thin film distillate by thin film distillation of the obtained dehydration reaction product.

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

The second polyol component, dianhydrosugar alcohol, is anhydrosugar alcohol formed by removing two water molecules from the inside of hydrogenated sugar, and has a diol form with two hydroxyl groups in the molecule. can be used to manufacture. Since imudang alcohol is an eco-friendly material derived from renewable natural resources, research on its manufacturing method has been conducted with much interest for a long time. Among these dianhydrosugar alcohols, isosorbide prepared from sorbitol currently has the widest range of industrial applications.

In the present invention, the type of dianhydrosugar alcohol is not particularly limited, but may be 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 Chemical Formula 1, which is the third polyol component, may be prepared from a hydrogenation reaction of disaccharides or higher polysaccharides including maltose.

In one embodiment, the anhydrous sugar 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 Formula 2, a compound represented by 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 of 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 condensation polymers 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 between the first polyol component and the second polyol component;

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

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

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

- polycondensation reaction between the second polyol component and the fourth polyol component;

- polycondensation reaction between 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 anhydrous sugar alcohol composition may satisfy the following i) to iii):

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

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

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

In one embodiment, the number average molecular weight (Mn: unit g / mol) of the anhydrous sugar alcohol composition may be 193 or more, 195 or more, 200 or more, 202 or more, 205 or more or 208 or more, and 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. Also, in one embodiment, the number average molecular weight (Mn) of the anhydrous sugar alcohol composition may be 193 to 1,589, specifically 195 to 1,550, more specifically 200 to 1,520, and more specifically As may be 202 to 1,500, more specifically may be 205 to 1,490. If the number average molecular weight of the anhydrous sugar alcohol composition deviates from the above level too much, the adhesive strength of an adhesive comprising a cured epoxy resin cured with a polyol composition prepared using such anhydrous sugar alcohol composition may deteriorate.

In one embodiment, the polydispersity index (PDI) of the anhydrous sugar 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 less, 3.22 or less, or 3.19 or less. In addition, in one embodiment, the polydispersity index (PDI) of the anhydrous sugar alcohol composition may be 1.13 to 3.41, specifically 1.13 to 3.40, more specifically 1.15 to 3.35, and more Specifically, it may be 1.20 to 3.25, and more specifically, it may be 1.23 to 3.22. If the polydispersity index of the anhydrous sugar alcohol composition deviates from the above level, the adhesive strength of an adhesive comprising a cured epoxy resin cured with a polyol composition prepared using such anhydrous sugar alcohol composition may deteriorate.

In one embodiment, the average number of -OH groups per molecule in the anhydrous sugar 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 It may be less than or equal to 21.30, less than or equal to 21.0, less than or equal to 20.5, less than or equal to 20.0, less than or equal to 19.95 or less than or equal to 19.92. Also, in one embodiment, the average number of —OH groups per molecule in the anhydrous sugar alcohol composition may be 2.54 to 21.36, more specifically 2.60 to 21.30, and more specifically 2.65 to 21.30. It may be 21.0. If the average number of -OH groups per molecule in the anhydrous sugar alcohol composition deviates from the above level too much, the adhesive comprising a cured epoxy resin cured with a polyol composition prepared using such anhydrous sugar alcohol composition has poor adhesive strength. it can be done

In one embodiment, in the anhydrous sugar 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 , and the second polyol component may be included in 0.1 to 28% by weight, specifically 1 to 25% by weight, more specifically 3 to 20% by weight, and 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 may be 55 to 90% by weight, specifically 60 to 6.3% by weight 89.9% by weight, more specifically may be included in 70 to 89.9% by weight, but is not particularly limited thereto.

In one embodiment, the anhydrosugar alcohol composition is a glucose-containing saccharide composition (eg, glucose; mannose; fructose; and a saccharide composition comprising disaccharides or higher polysaccharides including maltose) by hydrogenation reaction to prepare a hydrogenated sugar composition , The obtained hydrogenated sugar composition may be dehydrated by heating under an acid catalyst, and the obtained dehydration reaction product may be prepared by thin film distillation, 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, a hydrogenation reaction is performed on the glucose-containing saccharide composition under a hydrogen pressure of 30 to 80 atm and a heating condition of 110° C. to 135° C. to prepare a hydrogenated sugar composition, and the obtained hydrogenated sugar composition is dehydrated. 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 performed under reduced pressure conditions of 2 mbar or less and 150 ° C to 175 ° C It may be performed under 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 wt% or less, 98.5 wt% or less, 98 wt% or less, 97.5 wt% or less, or 97 wt% or less, such as 41 to 99.5 wt%, 45 to 98.5 wt%, or 50 to 98 wt%. may be %.

In one embodiment, the content of the polysaccharide alcohol (disaccharide or higher saccharide alcohol) contained 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 water is removed from the hydrogenated sugar composition) Based on), it may be 0.8% by weight or more, 1% by weight or more, 2% by weight or 3% by weight or more, and 57% by weight or less, 55% by weight or less, 52% by weight or less, 50% by weight or less, or 48% by weight or less It may be, for example, 0.8 to 57% by weight, 1 to 55% by weight, or 3 to 50% by weight.

Rubber Modified Epoxy Compound

The rubber-modified epoxy compound used in the preparation of the crosslinked anhydrosugar alcohol composition is a natural rubber-modified epoxy compound, a carboxyl-terminated butadiene acrylonitrile-modified epoxy compound, a core-shell rubber-modified epoxy compound, a polybutadiene-modified epoxy compound, Acrylonitrile-butadiene-modified epoxy compounds, styrene-butadiene-modified epoxy compounds, epoxy-terminated butadiene acrylonitrile-modified epoxy compounds, amine-terminated butadiene acrylonitrile-modified epoxy compounds, hydroxy-terminated butadiene acrylonitrile-modified epoxy compounds, or these It may be one or more selected from the group consisting of a combination of, but is not limited thereto. In a preferred embodiment, the rubber-modified epoxy compound may be selected from the group consisting of a natural rubber-modified epoxy compound, a carboxyl-terminated butadiene acrylonitrile-modified epoxy compound, or a combination thereof.

In one embodiment, the amount of the rubber-modified epoxy compound cross-linking with the anhydrous sugar alcohol composition may be greater than 5 parts by weight to less than 55 parts by weight based on 100 parts by weight of the anhydrous sugar alcohol composition.

If the amount of the crosslinking rubber-modified epoxy compound per 100 parts by weight of the anhydrous sugar alcohol composition is 5 parts by weight or less, an adhesive comprising a cured epoxy resin cured with a polyol composition prepared using the resulting crosslinked anhydrous sugar alcohol composition adhesion may be poor. On the other hand, even if the amount of the rubber-modified epoxy compound crosslinked per 100 parts by weight of the anhydrous sugar alcohol composition is 55 parts by weight or more, the cured epoxy resin cured with the polyol composition prepared using the resulting crosslinked anhydrous sugar alcohol composition Adhesion of the adhesive containing may be deteriorated.

In one embodiment, the amount of the rubber-modified epoxy compound that reacts with the anhydrous sugar alcohol composition is, for example, greater than 5 parts by weight, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight based on 100 parts by weight of the anhydrous sugar alcohol composition. or more, 9 parts by weight or more, or 10 parts by weight or more, and may also be less than 55 parts by weight, 54 parts by weight or less, 53 parts by weight or less, 52 parts by weight or less, 51 parts by weight or less, or 50 parts by weight or less, but are not limited thereto. don't

In one embodiment, the number average molecular weight of the crosslinked anhydrous sugar alcohol composition prepared from the crosslinking reaction of the above-described anhydrous sugar alcohol composition and a rubber-modified epoxy compound may be, for example, 209 to 5,813 g / mol, and the polydispersity index may be , for example, from 1.65 to 6.11. When the number average molecular weight and polydispersity index of the cross-linked anhydrous sugar-alcohol composition are within the above ranges, the adhesive performance of an adhesive containing a cured epoxy resin cured with a polyol composition prepared using such a cross-linked anhydrous sugar-alcohol composition is improved. can be advantageous for

More specifically, the number average molecular weight (g / mol) of the crosslinked anhydrous sugar alcohol composition may be, for example, 209 or more, 210 or more, 215 or more, 220 or more, 224 or more, 225 or more, 230 or more, or 231 or more, In addition, it may be 5,813 or less, 5,500 or less, 5,207 or less, 5,000 or less, 4,500 or less, 4,000 or less, 3,500 or less, 3,000 or less, or 2,875 or less, but is not limited thereto. Also, more specifically, the polydispersity index of the crosslinked anhydrous sugar alcohol composition may be, for example, 1.65 or more, 1.66 or more, 1.67 or more, 1.68 or more, 1.69 or more or 1.70 or more, and also 6.11 or less, 6.0 or less, 5.9 or less. , 5.8 or less, 5.7 or less, 5.6 or less, 5.5 or less, 5.4 or less, 5.3 or less, 5.2 or less, or 5.18 or less, but is not limited thereto.

In one embodiment, the crosslinking reaction of the anhydrous sugar alcohol composition and the rubber-modified epoxy compound is carried out at an elevated temperature in the presence of a catalyst, such as an organic tin-based catalyst (eg, dibutyltin dilaurate, etc.) For example, it may be performed at 110° C. to 180° C. or 120° C. to 160° C., for example, for 1 to 10 hours or 1 to 8 hours, but is not limited thereto.

alkylene oxide

In the present invention, the “polyol composition” is prepared by an addition reaction of the crosslinked anhydrosugar alcohol composition and alkylene oxide.

That is, in the present invention, the polyol composition includes an adduct obtained by reacting an alkylene oxide with a hydroxyl group of at least one terminal of each of the first to fifth polyol components crosslinked with the rubber-modified epoxy compound, and specifically, An alkylene oxide adduct of a first polyol component crosslinked with a rubber-modified epoxy compound (hereinafter referred to as “first crosslinked anhydrous sugar alcohol-alkylene glycol”), a second polyol component crosslinked with a rubber-modified epoxy compound Alkylene oxide adduct of (hereinafter referred to as “second crosslinked anhydrous sugar alcohol-alkylene glycol”), alkylene oxide adduct of third polyol component crosslinked with rubber-modified epoxy compound (hereinafter referred to as “second crosslinked anhydrous sugar alcohol-alkylene glycol”) 3 crosslinked anhydrous sugar alcohol-alkylene glycol”), an alkylene oxide adduct of a fourth polyol component crosslinked with a rubber-modified epoxy compound (hereinafter referred to as “fourth crosslinked anhydrous sugar alcohol-alkylene glycol”). ”) and an alkylene oxide adduct of a fifth polyol component crosslinked with a rubber-modified epoxy compound (hereinafter referred to as “fifth crosslinked anhydrous sugar alcohol-alkylene glycol”).

In one embodiment, the alkylene oxide may be a C2-C8 linear or C3-C8 branched alkylene oxide, and more specifically, ethylene oxide, propylene oxide, or a combination thereof.

In the present invention, the amount of alkylene oxide added to the crosslinked anhydrous sugar alcohol composition is the OH equivalent (Hydroxyl equivalent weight) of the polyol composition prepared by such addition reaction is in the above-mentioned specific range (eg, 251 to 2,035 g /eq) can be appropriately selected at a level that satisfies.

According to one embodiment, the alkylene oxide may be added in an amount exceeding 50 parts by weight per 100 parts by weight of the crosslinked anhydrous sugar alcohol composition.

More specifically, more than 50 parts by weight and less than 4,300 parts by weight of alkylene oxide per 100 parts by weight of the crosslinked anhydrous sugar alcohol composition may be added, for example, more than 50 parts by weight, 51 parts by weight or more, 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 100 parts by weight or more, and may be less than 4,300 parts by weight, 4,290 parts by weight or less, 4,270 parts by weight or less, 4,250 parts by weight or less, 4,230 parts by weight or less, 4,210 It may be less than or equal to 4,200 parts by weight, but is not limited thereto.

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

In one embodiment, the curing agent for an epoxy resin of the present invention may further include a curing agent component for an epoxy resin other than the polyol composition described above.

In one embodiment, a phenol-based compound, an acid anhydride-based compound, an amine-based compound, or a combination thereof may be used as the additional curing agent component for an epoxy resin, but is not limited thereto.

[Epoxy resin composition, cured product thereof, and adhesive containing the cured product]

According to another aspect of the present invention, an epoxy resin; And the curing agent for the epoxy resin of the present invention; containing, an epoxy resin composition is provided.

A wide range of epoxy resins can be used in the epoxy resin composition of the present invention. Epoxy resins can be solid, liquid or semi-solid, and can have a variety of reactivity depending on the application to which they are applied. The reactivity of epoxy resins is often measured in terms of epoxy equivalent weight, which is the molecular weight of a resin containing a single reactive epoxy group. The lower the epoxy equivalent, the higher the reactivity of the epoxy resin.

In one embodiment, the epoxy resins include bisphenol A-epichlorohydrin resins, epoxy novolac resins, alicyclic epoxy resins, aliphatic epoxy resins, bi-switched epoxy resins, glycidyl ester type epoxy resins, brominated epoxy resins, and those selected from the group consisting of bio-derived epoxy resins, epoxidized soybean oil, and combinations thereof, but are not limited thereto.

In another specific embodiment, the epoxy resin is a novolac-type epoxy resin such as a phenol novolac-type epoxy resin or a cresol novolak-type epoxy resin, a bisphenol-type epoxy resin such as a bisphenol A-type epoxy resin or a bisphenol F-type epoxy resin, N , Aromatic glycidylamine type epoxy resins such as N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane type glycidylamine, aminophenol type glycidylamine, hydroquinone Paddy 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. Aralkyl-type epoxy resins, vinylcyclohexene dioxide, dicyclopentadiene oxide, aliphatic epoxy resins such as alicyclic epoxies such as alicyclic diepoxy-adipade, and combinations thereof may be used. Not limited.

In another embodiment, the epoxy resin is a bisphenol F type epoxy resin, a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, a biphenyl type epoxy resin, a stilbene type epoxy resin, a hydroquinone type epoxy resin, a naphthalene skeleton type epoxy resin, tetraphenylolethane type epoxy resin, diphenylphosphate (DPP) type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadienephenol type epoxy resin, diglycidyl of bisphenol A ethylene oxide adduct Glycidyl ether having one epoxy group, such as ether, diglycidyl ether of bisphenol A propylene oxide adduct, phenyl glycidyl ether, cresyl glycidyl ether, etc. Nuclear hydrogenated epoxy that is a nuclear hydrogenation product of these epoxy resins Resins and those selected from the group consisting of combinations thereof, but are not limited thereto.

In one embodiment of the epoxy resin composition of the present invention, the epoxy resin is a natural rubber-modified epoxy resin, a carboxyl-terminated butadiene acrylonitrile-modified epoxy resin, a core-shell rubber-modified epoxy resin, a polybutadiene-modified epoxy resin, an acrylic Ronitrile-butadiene-modified epoxy resin, styrene-butadiene-modified epoxy resin, epoxy-terminated butadiene acrylonitrile-modified epoxy resin, amine-terminated butadiene acrylonitrile-modified epoxy resin, hydroxy-terminated butadiene acrylonitrile-modified epoxy resin, bisphenol A -Epichlorohydrin resin, epoxy novolac resin, alicyclic (cycloaliphatic) epoxy resin, aliphatic epoxy resin, bi-switched epoxy resin, glycidyl ester type epoxy resin, brominated epoxy resin, bio-derived epoxy resin, epoxidized soybean oil Resin, novolac type epoxy resin, bisphenol type epoxy resin, aromatic glycidylamine type epoxy resin, hydroquinone type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin, triphenol propane type Epoxy resins, alkyl-modified triphenolmethane-type epoxy resins, triazine nucleus-containing epoxy resins, dicyclopentadiene-modified phenol-type epoxy resins, naphthol-type epoxy resins, naphthalene-type epoxy resins, aralkyl-type epoxy resins, bisphenol F-type epoxy resins, Cresol novolak type epoxy resin, phenol novolak type epoxy resin, hydroquinone type epoxy resin, naphthalene skeleton type epoxy resin, tetraphenylolethane type epoxy resin, diphenyl phosphate type epoxy resin, trishydroxyphenylmethane type epoxy resin, Dicyclopentadienephenol type epoxy resin, diglycidyl ether of bisphenol A ethylene oxide adduct, diglycidyl ether of bisphenol A propylene oxide adduct, diglycidyl ether of bisphenol A, phenyl glycidyl ether, cresyl It may be at least one selected from the group consisting of glycidyl ether, nuclear hydrogenation epoxy resins that are nuclear hydrogenation products of these epoxy resins, and combinations thereof.

In one embodiment, the equivalent ratio of the curing agent for epoxy resin of the present invention to the epoxy resin in the epoxy resin composition (equivalent of the curing agent for epoxy resin / equivalent of the epoxy resin) may be, for example, 0.9 to 1.1, and more specifically may be 0.92 to 1.08, and more specifically may be 0.95 to 1.05. If the equivalent of the curing agent for epoxy resin is too small with respect to the equivalent of the epoxy resin, there may be a problem in that the mechanical strength is lowered and the physical properties in terms of adhesive strength are lowered. In many cases, there may be a problem in that physical properties are deteriorated in terms of mechanical strength, thermal and adhesive strength.

Room temperature curing of epoxy resin usually requires a temperature of 15 ° C or higher and a curing time of 24 hours or more, so fast curing and low-temperature curing are sometimes necessary.

Therefore, for the curing accelerating effect, the epoxy resin composition of the present invention may further include a curing catalyst.

Curing catalysts usable in the present invention include, for example, amine-based compounds (eg, tertiary amines) such as benzyldimethylamine, tris(dimethylaminomethyl)phenol, and dimethylcyclohexylamine; imidazole compounds such as 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-methylimidazole; organophosphorus compounds such as triphenylphosphine and triphenyl phosphite; quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide; diazabicycloalkenes such as 1,8-diazabicyclo[5.4.0]undecene-7 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 triphenylborate; metal halides such as zinc chloride and stannous chloride; Latent curing catalysts (e.g., dicyandiamide, high melting point dispersed latent amine adducts obtained by adding amines to epoxy resins, etc.; microcapsule type latent catalysts in which the surface of an imidazole-based, phosphorus-based, or phosphine-based accelerator is coated with a polymer) amine salt-type latent catalysts; high-temperature dissociation-type thermal cation polymerization-type latent catalysts such as Lewis acid salts and Bronsted acid salts, etc.), and those selected from the group consisting of combinations thereof, but are not limited thereto.

In one embodiment, the curing catalyst may be at least one selected from the group consisting of an amine-based compound, an imidazole-based compound, an organophosphorus compound, or a combination thereof.

When the curing catalyst is included in the epoxy resin composition of the present invention, the amount used may be 0.01 part by weight to 1.0 part by weight, more specifically, 0.05 part by weight to 100 parts by weight of the total of the epoxy resin and the curing agent for the epoxy resin. It may be 0.5 parts by weight, and more specifically, it may be 0.08 parts by weight to 0.2 parts by weight, but is not limited thereto. If the amount of the curing catalyst is too small, the curing reaction of the epoxy resin may not sufficiently proceed, resulting in deterioration of mechanical and thermal properties. Since this progresses slowly, there may be a problem of increasing the viscosity.

The epoxy resin composition of the present invention, if necessary, additives commonly used in epoxy resin compositions, such as antioxidants, UV absorbers, fillers, resin modifiers, silane coupling agents, diluents, colorants, antifoaming agents, defoaming agents, dispersing agents, viscosity It may further include one or more additives selected from the group consisting of modifiers, gloss modifiers, wetting agents, conductivity imparting agents, and combinations thereof.

The antioxidant may be used to further improve heat resistance stability of the cured product obtained, and is not particularly limited, but examples thereof include phenolic antioxidants (dibutylhydroxytoluene, etc.), sulfur-based antioxidants (mercaptopropionic acid derivatives, etc.) , phosphorus antioxidants (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.) and combinations thereof. 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 the total of 100 parts by weight of the epoxy resin and the curing agent for the epoxy resin.

Although it does not specifically limit as said UV absorber, For example, the benzotriazole type UV absorber represented by BASF Japan Ltd. TINUBIN P and TINUVIN 234; triazine-based UV absorbers such as TINUVIN 1577ED; A hindered amine-based UV absorber such as CHIMASSOLV 2020FDL and a combination thereof may be used. The content of the UV absorber in the composition may be 0.01 to 10 parts by weight, 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 for the epoxy resin.

The filler is used for the main purpose of improving the mechanical properties of a cured product by mixing it with an epoxy resin or a curing agent for epoxy resin. In general, mechanical properties are improved when the amount of the filler is increased. Inorganic fillers include extenders such as talc, sand, silica, talc, calcium carbonate, and the like; reinforcing fillers such as mica, quartz, and glass fibers; There are those with special uses such as quartz powder, graphite, alumina, and aerosil (for the purpose of imparting thixotropic properties). Metals include aluminum, aluminum oxide, iron, iron oxide, and copper, which contribute to thermal expansion coefficient, abrasion resistance, thermal conductivity, and adhesion. There are things that impart flame retardancy, such as antimony oxide (SB2O3), barium titanate, and fillers for weight reduction such as fine plastic spheres (phenol resin, urea resin, etc.) as organic materials. In addition, as fillers with reinforcing properties, various glass fibers or chemical fiber fabrics can be treated as fillers in a broad sense in the manufacture of laminated products. Thixotropic (thixotropic or thixotropic) refers to the property of a liquid state when flowing and a solid state when stationary so that resin impregnated into a laminate or attached to a vertical plane or immersion method does not flow or lose during curing. refers to having), fine particles with a large unit surface area are used. For example, colloidal silica (Aerosil) or bentonite-based clay is used. In one embodiment, the filler is not particularly limited, but for example, one selected from the group consisting of glass fiber, carbon fiber, titanium oxide, alumina, talc, mica, aluminum hydroxide, and combinations thereof may be used. The content of the filler 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 the total of 100 parts by weight of the epoxy resin and the curing agent for the epoxy resin.

Examples of the resin modifier include, but are not particularly limited to, flexibility imparting agents such as polypropylene glycidyl ether, polymerized fatty acid polyglycidyl ether, polypropylene glycol, and urethane prepolymer. The content of the resin modifier in the composition may be 0.01 to 80 parts by weight, or 0.01 to 50 parts by weight, or 0.1 to 20 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent for epoxy resin.

The silane coupling agent is not particularly limited, and examples thereof include chloropropyltrimethoxysilane, vinyltrichlorosilane, γmethacryloxypropyltrimethoxysilane, and γaminopropyltriethoxysilane. . 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 the total of 100 parts by weight of the epoxy resin and the curing agent for epoxy resin.

The diluent is used for the main purpose of reducing the viscosity by adding it to an epoxy resin or a curing agent for epoxy resin, and when used, it is used to improve flowability, defoaming property, improve penetration in details of parts, etc. or to effectively add fillers play a role Diluents generally do not volatilize unlike solvents and remain in the cured product during resin curing, 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 form a cross-linked structure in the cured product, and the non-reactive diluent remains 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, etc. Commonly used non-reactive diluents include dibutyl phthalate (DBP), dioctyl phthalate (DOP), nonyl-phenol, hysol, and the like. In one embodiment, the diluent is not particularly limited, but examples include n-butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, vinylcyclohexene dioxide, diglycidyl aniline, What is selected from the group consisting of glycerin triglycidyl ether and combinations 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 the total of 100 parts by weight of the epoxy resin and the curing agent for the epoxy resin.

A pigment or dye is used as a colorant for adding color to the resin. Commonly used pigments include colorants such as titanium dioxide, cadmium red, channing green, carbon black, chrome green, chrome yellow, navy blue, and channing blue.

In addition, antifoaming and defoaming agents used for the purpose of removing air bubbles in resins, dispersing agents for increasing the dispersion effect of resins and pigments, wetting agents for improving adhesion between epoxy resins and materials, and viscosity modifiers , gloss control agents for adjusting the glossiness of resin, additives for improving adhesion, additives 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 a conventionally known curing apparatus such as a closed curing furnace or a tunnel furnace capable of continuous curing can be used. The heating method used for the curing is not particularly limited, but conventionally known methods such as hot air circulation, infrared heating, and high frequency heating can be used.

The curing temperature and curing time may be in the range of 30 seconds to 10 hours at 50°C to 250°C. In one embodiment, after fore-curing under the conditions of 50 ℃ ~ 120 ℃, 0.5 hours to 5 hours, it may be post-cured under the conditions of 120 ℃ ~ 180 ℃, 0.1 hours to 5 hours. In another embodiment, primary curing under conditions of 50 ° C to 85 ° C, 0.5 hours to 5 hours, secondary curing under conditions of 85 ° C to 105 ° C, 0.5 hours to 5 hours, 105 ° C to 145 ° C, 0.5 Third curing under conditions of time to 5 hours, and fourth curing under conditions of 145 ° C to 180 ° C and 0.5 hours to 5 hours can be performed. In another embodiment, it may be cured under conditions of 150 ° C. to 250 ° C. for 30 seconds to 30 minutes for short-time curing.

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

Therefore, according to another aspect of the present invention, a cured product obtained by curing the epoxy resin composition of the present invention is provided.

In addition, according to another aspect of the present invention, an adhesive comprising the cured product is provided.

The adhesive of the present invention may additionally include additives commonly used in epoxy-based adhesives.

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 by these examples.

[Example]

<Preparation of anhydrous sugar-alcohol composition containing the first to fifth polyol components>

Preparation Example A1: Preparation of anhydrous sugar alcohol composition using 97% by weight of glucose

A liquid hydrogenated sugar composition having a concentration of 55% by weight (sorbitol 96% by weight, mannitol 0.9% by weight based on solid content) by hydrogenating a glucose product having a purity of 97% in the presence of a nickel catalyst and under a temperature of 125 ° C. and a hydrogen pressure of 60 atm. % and disaccharide or higher polysaccharide alcohol 3.1% by weight) was obtained, which was put into a batch reactor equipped with a stirrer and concentrated by heating at 100 ° C., thereby obtaining 1,000 g of a concentrated hydrogenated sugar composition.

A reactor was charged with 1,000 g of the concentrated hydrogenated sugar composition and 9.6 g of sulfuric acid. 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 anhydrous sugar 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% sodium hydroxide aqueous solution was added to neutralize the reaction product. Thereafter, the temperature was cooled to 100° C. or less, and concentrated for 1 hour or more under a reduced pressure of 45 mmHg to remove residual moisture and low-boiling substances to obtain about 831 g of anhydrous sugar 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 through this, the molar conversion from sorbitol to isosorbide was calculated as 77.6%.

831 g of the obtained anhydrous sugar alcohol conversion solution was put into a thin film distiller (SPD) to proceed with distillation. At this time, distillation was performed at a temperature of 160° C. and a vacuum pressure of 1 mbar, and about 589 g of distillate was obtained (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 separating the distillate, isosorbide (dianhydrosugar alcohol) [second polyol component] 11.5% by weight, isomannide (dianhydrosugar alcohol) [second polyol component] 0.4% by weight, sorbitan (anhydrous sugar alcohol) 0.4% by weight alcohol) [first polyol component] 7.4% by weight, polysaccharide alcohol represented by Formula 1 [third polyol component] and anhydrosugar alcohol derived therefrom (ie, formed by removing water molecules from polysaccharide alcohol) [agent 4 polyol component] 2.5% by weight and their polymer [fifth polyol component] 78.2% by weight, the number average molecular weight of the composition is 208 g / mol, the polydispersity index of the composition is 1.25, and the hydroxyl group of the composition is About 242 g of an anhydrous sugar alcohol composition having a value of 751 mg KOH/g and an average number of -OH groups per molecule in the composition of 2.78 was obtained.

Preparation Example A2: Preparation of anhydrous sugar alcohol composition using a saccharide composition containing 50.2% by weight of glucose

Except for using 50.2% by weight of a glucose-containing saccharide composition (50.2% by weight of glucose and 49.8% by weight of mannose, fructose and polysaccharides (disaccharide or higher saccharide such as maltose)) instead of a glucose product with a purity of 97%, Preparation Example A 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% by weight (based on solid content, 48.5% by weight of sorbitol, 3.6% by weight of mannitol, and 47.9% by weight of disaccharide or higher polysaccharide alcohol). 1,000 g of a concentrated hydrogenated sugar composition was obtained by heating to 100° C. and concentrating in a batch reactor equipped with .

The concentrated hydrogenated sugar composition 1,000 For g, a dehydration reaction was performed in the same manner as in Preparation Example A1 to convert it into anhydrous sugar alcohol. 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 anhydrosugar-alcohol conversion solution by gas chromatography, the conversion content of isosorbide was 33.7% by weight, through which isosorb from sorbitol The molar conversion of the beads was calculated to be 77.1%.

Thin-film distillation was performed on 890 g of the obtained anhydrous sugar 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 (monuhydrosugar alcohol) 0.9% by weight, disaccharide or higher polysaccharide alcohols and derived therefrom 6.2% by weight of anhydrous sugar alcohol and 89.9% by weight of polymers thereof, the number average molecular weight of the composition is 1,480 g / mol, the polydispersity index of the composition is 3.19, the hydroxyl value of the composition is 755 mg KOH / g, , to obtain about 586 g of anhydrosugar alcohol composition having an average number of -OH groups per molecule in the composition of 19.92.

<Preparation of anhydrous sugar-alcohol composition crosslinked with rubber-modified epoxy compound>

Preparation Example B1: Preparation of anhydrosugar alcohol composition crosslinked with natural rubber (NR)-modified epoxy compound (using 10 parts by weight of natural rubber-modified epoxy compound per 100 parts by weight of anhydrous sugar alcohol composition)

100.0 g of the anhydrous sugar alcohol composition obtained in Preparation Example A1, 10.0 g of a natural rubber-modified epoxy compound (KR-909, Kukdo Chemical Co., Ltd.) and dibutyltin dilaurate as a reaction catalyst in a three-necked glass reactor equipped with an agitator. After adding 0.1 g of (Aldrich (product)) and raising the internal temperature of the reactor to 150° C., a crosslinking reaction was performed while stirring for 2 hours. After completion of the crosslinking reaction, the reaction product was cooled to room temperature to obtain 95 g of a crosslinked anhydrous sugar alcohol composition. The obtained crosslinked anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

Preparation Example B2: Preparation of anhydrosugar-alcohol composition crosslinked with natural rubber-modified epoxy compound (using 50 parts by weight of natural rubber-modified epoxy compound per 100 parts by weight of anhydrous sugar-alcohol composition)

144 g of the crosslinked anhydrous sugar alcohol composition was prepared in the same manner as in Preparation Example B1, except that the content of the natural rubber-modified epoxy compound (KR-909, Kukdo Chemical Co., Ltd.) was changed from 10.0 g to 50.0 g. obtained. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

Preparation Example B3: Preparation of anhydrosugar-alcohol composition crosslinked with natural rubber-modified epoxy compound (using 10 parts by weight of natural rubber-modified epoxy compound per 100 parts by weight of anhydrous sugar-alcohol composition)

Except for using 100.0 g of the anhydrous sugar-alcohol composition obtained in Preparation Example A2 instead of the anhydrous sugar-alcohol composition obtained in Preparation Example A1, 104 g of the cross-linked anhydrous sugar-alcohol composition was prepared in the same manner as in Preparation Example B1. obtained. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

Preparation Example B4: Preparation of anhydrosugar-alcohol composition crosslinked with natural rubber-modified epoxy compound (using 50 parts by weight of natural rubber-modified epoxy compound per 100 parts by weight of anhydrous sugar-alcohol composition)

Instead of the anhydrous sugar alcohol composition obtained in Preparation Example A1, 100.0 g of the anhydrous sugar alcohol composition obtained in Preparation Example A2 was used, and the content of a natural rubber-modified epoxy compound (KR-909, Kukdo Chemical Co., Ltd.) was 10.0 g. 141 g of a crosslinked anhydrous sugar alcohol composition was obtained in the same manner as in Preparation Example B1, except that the amount was changed to 50.0 g. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

Preparation Example B5: Preparation of anhydrosugar alcohol composition crosslinked with CTBN (Carboxyl-Terminated Butadiene-Acrylonitrile) modified epoxy compound (using 25 parts by weight of CTBN-modified epoxy compound per 100 parts by weight of anhydrosugar alcohol composition)

Except for the use of 25.0 g of CTBN (Carboxyl-Terminated Butadiene-Acrylonitrile) modified epoxy compound (KR-818, Kukdo Chemical Co., Ltd.) instead of natural rubber-modified epoxy compound (KR-909, Kukdo Chemical Co., Ltd.) , In the same manner as in Preparation Example B1, 118 g of a crosslinked anhydrous sugar alcohol composition was obtained. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

Preparation Example B6: Preparation of anhydrosugar-alcohol composition crosslinked with natural rubber-modified epoxy compound (using 5 parts by weight of natural rubber-modified epoxy compound per 100 parts by weight of anhydrous sugar-alcohol composition)

101 g of the cross-linked anhydrous sugar alcohol composition was prepared in the same manner as in Preparation Example B1, except that the amount of the natural rubber-modified epoxy compound (KR-909, Kukdo Chemical Co., Ltd.) was changed from 10.0 g to 5.0 g. obtained. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

Preparation Example B7: Preparation of anhydrosugar-alcohol composition crosslinked with natural rubber-modified epoxy compound (using 55 parts by weight of natural rubber-modified epoxy compound per 100 parts by weight of anhydrous sugar-alcohol composition)

141 g of the crosslinked anhydrous sugar alcohol composition was prepared in the same manner as in Preparation Example B1, except that the content of the natural rubber-modified epoxy compound (KR-909, Kukdo Chemical Co., Ltd.) was changed from 10.0 g to 55.0 g. obtained. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

The components used in the preparation of the crosslinked anhydrosugar alcohol compositions obtained in Preparation Examples B1 to B7 and their amounts are shown in Table 1 below.

[Table 1]

<Preparation of polyol composition by addition reaction of crosslinked anhydrous sugar alcohol composition and alkylene oxide>

Example A1: Preparation of a polyol composition having an added content of 100 parts by weight of ethylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

100 g of the crosslinked anhydrous sugar alcohol composition obtained in Preparation Example B1 and 0.1 g of potassium hydroxide (KOH) were placed in a high-pressure reactor equipped with a stirrer, the temperature inside the reactor was raised to 120 ° C, and then 100 g of ethylene oxide was added. Then, by reacting at 120° C. for 3 hours, 195 g of a polyol composition was obtained.

Example A2: Preparation of a polyol composition having an added content of ethylene oxide of 4,200 parts by weight per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

Except for changing the ethylene oxide content from 100 g to 4,200 g, a polyol composition of 4,090 g was obtained in the same manner as in Example A1.

Example A3: Preparation of a polyol composition having an added content of 100 parts by weight of propylene oxide per 100 parts by weight of an anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

195 g of a polyol composition was obtained in the same manner as in Example A1, except that 100 g of propylene oxide was used instead of ethylene oxide.

Example A4: Preparation of a polyol composition having an added content of 3,600 parts by weight of propylene oxide per 100 parts by weight of an anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

3,520 g of a polyol composition was obtained in the same manner as in Example A1, except that 3,600 g of propylene oxide was used instead of ethylene oxide.

Example A5: Preparation of a polyol composition having an added content of 100 parts by weight of ethylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound

195 g of a polyol composition was obtained by carrying out in the same manner as in Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B2 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1. did

Example A6: Preparation of a polyol composition having an added content of 2,700 parts by weight of ethylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound

Example, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B2 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and the ethylene oxide content was changed from 100 g to 2,700 g. By carrying out in the same manner as in A1, 2,745 g of a polyol composition was obtained.

Example A7: Preparation of a polyol composition having an added content of 100 parts by weight of propylene oxide per 100 parts by weight of an anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound

Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B2 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used instead of ethylene oxide. By carrying out in the same manner as above, 186 g of a polyol composition was obtained.

Example A8: Preparation of a polyol composition having an added content of 2,300 parts by weight of propylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound

Example, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B2 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and 2,300 g of propylene oxide was used instead of ethylene oxide. By carrying out in the same manner as in A1, 2,370 g of a polyol composition was obtained.

Example A9: Preparation of a polyol composition having an added content of 100 parts by weight of ethylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

180 g of a polyol composition was obtained by carrying out in the same manner as in Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B3 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1. did

Example A10: Preparation of a polyol composition having an added content of ethylene oxide of 560 parts by weight per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B3 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and the ethylene oxide content was changed from 100 g to 560 g. By carrying out in the same way as above, 602 g of a polyol composition was obtained.

Example A11: Preparation of a polyol composition having an added content of propylene oxide of 100 parts by weight per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B3 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used instead of ethylene oxide. By carrying out in the same way as above, 185 g of a polyol composition was obtained.

Example A12: Preparation of a polyol composition having an added content of propylene oxide of 480 parts by weight per 100 parts by weight of an anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B3 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and 480 g of propylene oxide was used instead of ethylene oxide. By carrying out in the same way as above, 507 g of a polyol composition was obtained.

Example A13: Preparation of a polyol composition having an added content of 100 parts by weight of ethylene oxide per 100 parts by weight of an anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound

Except for using 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B4 instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, 176 g of a polyol composition was obtained in the same manner as in Example A1. did

Example A14: Preparation of a polyol composition having an added content of ethylene oxide of 550 parts by weight per 100 parts by weight of an anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound

Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B4 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and the ethylene oxide content was changed from 100 g to 550 g. By carrying out in the same manner as above, 570 g of a polyol composition was obtained.

Example A15: Preparation of a polyol composition having an added content of 100 parts by weight of propylene oxide per 100 parts by weight of an anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound

Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B4 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used instead of ethylene oxide. By carrying out in the same manner as in, 181 g of a polyol composition was obtained.

Example A16: Preparation of a polyol composition having an additional content of propylene oxide of 750 parts by weight per 100 parts by weight of an anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound

Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B4 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and 750 g of propylene oxide was used instead of ethylene oxide. By carrying out in the same way as above, 822 g of a polyol composition was obtained.

Example A17: Preparation of a polyol composition having an added content of propylene oxide of 100 parts by weight per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 25 parts by weight of a CTBN-modified epoxy compound

Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B5 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used instead of ethylene oxide. By carrying out in the same manner as in, 190 g of a polyol composition was obtained.

Comparative Example A1: Preparation of a polyol composition having an added content of ethylene oxide of 50 parts by weight per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

Except for changing the ethylene oxide content from 100 g to 50 g, 144 g of a polyol composition was obtained by carrying out in the same manner as in Example A1.

Comparative Example A2: Preparation of a polyol composition having an added content of 4,300 parts by weight of ethylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

4,220 g of a polyol composition was obtained in the same manner as in Example A1, except that the ethylene oxide content was changed from 100 g to 4,300 g.

Comparative Example A3: Preparation of a polyol composition having an added content of 50 parts by weight of propylene oxide per 100 parts by weight of an anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

140 g of a polyol composition was obtained in the same manner as in Example A1, except that 50 g of propylene oxide was used instead of ethylene oxide.

Comparative Example A4: Preparation of a polyol composition having an added content of propylene oxide of 3,700 parts by weight per 100 parts by weight of an anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

3,210 g of a polyol composition was obtained in the same manner as in Example A1, except that 3,700 g of propylene oxide was used instead of ethylene oxide.

Comparative Example A5: Preparation of a polyol composition having an added content of ethylene oxide of 50 parts by weight per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound

Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B2 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and the ethylene oxide content was changed from 100 g to 50 g. By carrying out in the same manner as in, 125 g of a polyol composition was obtained.

Comparative Example A6: Preparation of a polyol composition having an added content of 2,800 parts by weight of ethylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound

Example, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B2 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and the ethylene oxide content was changed from 100 g to 2,800 g. By carrying out in the same manner as in A1, 2,150 g of a polyol composition was obtained.

Comparative Example A7: Preparation of a polyol composition having an added content of propylene oxide of 50 parts by weight per 100 parts by weight of an anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound

Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B2 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and 50 g of propylene oxide was used instead of ethylene oxide. By carrying out in the same manner as in, 130 g of a polyol composition was obtained.

Comparative Example A8: Preparation of a polyol composition having an added content of 2,400 parts by weight of propylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound

Examples, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B2 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and 2,400 g of propylene oxide was used instead of ethylene oxide. By carrying out in the same manner as in A1, 2,150 g of a polyol composition was obtained.

Comparative Example A9: Preparation of a polyol composition having an added content of 100 parts by weight of ethylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 5 parts by weight of a natural rubber-modified epoxy compound

180 g of a polyol composition was obtained by carrying out in the same manner as in Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B6 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1. did

Comparative Example A10: Preparation of a polyol composition having an added content of 4,200 parts by weight of ethylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 5 parts by weight of a natural rubber-modified epoxy compound

Example, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B6 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and the ethylene oxide content was changed from 100 g to 4,200 g. By carrying out in the same manner as in A1, 4,015 g of a polyol composition was obtained.

Comparative Example A11: Preparation of a polyol composition having an added content of 100 parts by weight of propylene oxide per 100 parts by weight of an anhydrous sugar alcohol composition crosslinked with 5 parts by weight of a natural rubber-modified epoxy compound

Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B6 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used instead of ethylene oxide. By carrying out in the same manner as in, 180 g of a polyol composition was obtained.

Comparative Example A12: Preparation of a polyol composition having an added content of 3,600 parts by weight of propylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 5 parts by weight of a natural rubber-modified epoxy compound

Example, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B6 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and 3,600 g of propylene oxide was used instead of ethylene oxide. By carrying out in the same manner as in A1, 3,480 g of a polyol composition was obtained.

Comparative Example A13: Preparation of a polyol composition having an added content of 100 parts by weight of ethylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 55 parts by weight of a natural rubber-modified epoxy compound

175 g of a polyol composition was obtained in the same manner as in Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B7 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1. did

Comparative Example A14: Preparation of a polyol composition having an added content of 2,700 parts by weight of ethylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 55 parts by weight of a natural rubber-modified epoxy compound

Example, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B7 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and the ethylene oxide content was changed from 100 g to 2,700 g. By carrying out in the same manner as in A1, 2,540 g of a polyol composition was obtained.

Comparative Example A15: Preparation of a polyol composition having an added content of 100 parts by weight of propylene oxide per 100 parts by weight of an anhydrous sugar alcohol composition crosslinked with 55 parts by weight of a natural rubber-modified epoxy compound

Example A1, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B7 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used instead of ethylene oxide. By carrying out in the same manner as in, 180 g of a polyol composition was obtained.

Comparative Example A16: Preparation of a polyol composition having an added content of 2,300 parts by weight of propylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 55 parts by weight of a natural rubber-modified epoxy compound

Examples, except that 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B7 was used instead of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1, and 2,300 g of propylene oxide was used instead of ethylene oxide. By carrying out in the same manner as in A1, 2,200 g of a polyol composition was obtained.

Ingredients used in the preparation of the polyol compositions obtained in Examples A1 to A17 and Comparative Examples A1 to A16, the amounts thereof, and the physical properties of the obtained polyol compositions are shown in Table 2 below.

[How to measure physical properties]

1. OH equivalent weight (Hydroxyl equivalent weight (HEW), unit: g/eq)

(1) After dissolving 5 g of each of the polyol compositions obtained in Examples A1 to A17 and Comparative Examples A1 to A16 in 100 ml of chloroform, it was added to a 500 ml round flask containing 100 ml of acetic anhydride and 100 ml of pyridine, followed by stirring for 3 days. , the polyol compositions obtained in Examples A1 to A17 and Comparative Examples A1 to A16 above were acetylated. Then, after washing the acetylated polyol compositions with water, the number average molecular weight of the polyol compositions was measured through gel permeation chromatography (GPC).

Specifically, after dissolving 1 to 3 parts by weight of each of the acetylated polyol compositions in tetrahydrofuran (THF), the number average molecular weight (Mn) was measured using a gel permeation chromatography apparatus (Agilent Co.). At this time, the column used was GPC KF-802.5 (Shodex Co.), the column temperature was 40 ° C, the developing solvent used was tetrahydrofuran, which was flowed at a rate of 0.5 ml / min, and polystyrene ( Aldrich Co.) was used.

(2) Esterification reaction of each of the polyol compositions prepared in Examples A1 to A17 and Comparative Examples A1 to A16 with an excess of phthalic anhydride under an imidazole catalyst according to ASTM D-4274D, a hydroxyl value test standard After that, the remaining phthalic anhydride was titrated with 0.5N sodium hydroxide (NaOH) to measure the hydroxyl value (unit: mg KOH/g) of each polyol composition.

(3) The OH equivalent of the polyol compositions obtained in Examples A1 to A17 and Comparative Examples A1 to A16 was measured through the following formula using the number average molecular weight and hydroxyl value of each polyol composition measured above.

[OH equivalent] = (number average molecular weight of the measured polyol composition) / (number of OH functional groups calculated from the hydroxyl value and number average molecular weight of the measured polyol composition)

[Table 2]

<Preparation of Epoxy Resin Composition>

Example B1: Preparation of an epoxy resin composition using the polyol composition of Example A1 as a curing agent

Diglycidyl ether of bisphenol A (DGEBA)-based bifunctional epoxy resin (YD-128, Kukdo Chemical Co., Ltd., Epoxy equivalent weight (EEW): 187 g/eq, 1 equivalent) and the polyol composition of Example A1 (HEW: 278 g/eq, 1 equivalent), based on 100 parts by weight of the mixture, N, N-dimethylbutylamine (DMBA, Sigma aldrich) as a catalyst An epoxy resin composition was prepared by adding 0.1 part by weight.

Example B2: Preparation of an epoxy resin composition using the polyol composition of Example A2 as a curing agent

An epoxy resin composition was prepared in the same manner as in Example B1, except that the polyol composition of Example A2 (HEW: 1,990 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent.

Example B3: Preparation of an epoxy resin composition using the polyol composition of Example A3 as a curing agent

As an epoxy resin, cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin ) was used, the polyol composition of Example A3 (HEW: 296 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and 2- An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of ethyl-4-methylimidazole (2-ethyl-4-methylimidazole, 2E4M, Sigma Aldrich) was used.

Example B4: Preparation of an epoxy resin composition using the polyol composition of Example A4 as a curing agent

As an epoxy resin, cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin ) was used, the polyol composition of Example A4 (HEW: 1,990 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and 2 was used instead of N,N-dimethylbutylamine as a catalyst. An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of -ethyl-4-methylimidazole was used.

Example B5: Preparation of an epoxy resin composition using the polyol composition of Example A5 as a curing agent

As an epoxy resin, O-cresol novolac epoxy resin (YDCN-500-90P) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin, Kukdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent), the polyol composition of Example A5 (HEW: 253 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and N,N-dimethyl as a catalyst. An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of triphenylphosphine (TPP, Sigma Aldrich) was used instead of butylamine.

Example B6: Preparation of an epoxy resin composition using the polyol composition of Example A6 as a curing agent

As an epoxy resin, O-cresol novolac epoxy resin (YDCN-500-90P) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin, Kukdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent), the polyol composition of Example A6 (HEW: 1,967 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and N,N- An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of triphenylphosphine was used instead of dimethylbutylamine.

Example B7: Preparation of an epoxy resin composition using the polyol composition of Example A7 as a curing agent

An epoxy resin composition was prepared in the same manner as in Example B1, except that the polyol composition of Example A7 (HEW: 258 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent.

Example B8: Preparation of an epoxy resin composition using the polyol composition of Example A8 as a curing agent

An epoxy resin composition was prepared in the same manner as in Example B1, except that the polyol composition of Example A8 (HEW: 1,956 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent.

Example B9: Preparation of an epoxy resin composition using the polyol composition of Example A9 as a curing agent

As an epoxy resin, cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin ) was used, the polyol composition of Example A9 (HEW: 736 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and 2- An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of ethyl-4-methylimidazole was used.

Example B10: Preparation of an epoxy resin composition using the polyol composition of Example A10 as a curing agent

As an epoxy resin, cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin ), using the polyol composition of Example A10 (HEW: 1,995 g / eq, 1 equivalent) instead of the polyol composition of Example A1 as a curing agent, and using 2 instead of N, N-dimethylbutylamine as a catalyst An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of -ethyl-4-methylimidazole was used.

Example B11: Preparation of an epoxy resin composition using the polyol composition of Example A11 as a curing agent

As an epoxy resin, O-cresol novolac epoxy resin (YDCN-500-90P) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin, Kukdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent), the polyol composition of Example A11 (HEW: 782 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and N,N-dimethyl as a catalyst. An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of triphenylphosphine was used instead of butylamine.

Example B12: Preparation of an epoxy resin composition using the polyol composition of Example A12 as a curing agent

As an epoxy resin, O-cresol novolac epoxy resin (YDCN-500-90P) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin, Kukdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent), the polyol composition of Example A12 (HEW: 1,995 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and N,N- An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of triphenylphosphine was used instead of dimethylbutylamine.

Example B13: Preparation of an epoxy resin composition using the polyol composition of Example A13 as a curing agent

An epoxy resin composition was prepared in the same manner as in Example B1, except that the polyol composition of Example A13 (HEW: 747 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent.

Example B14: Preparation of an epoxy resin composition using the polyol composition of Example A14 as a curing agent

An epoxy resin composition was prepared in the same manner as in Example B1, except that the polyol composition of Example A14 (HEW: 1,995 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent.

Example B15: Preparation of an epoxy resin composition using the polyol composition of Example A15 as a curing agent

As an epoxy resin, cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin ) was used, the polyol composition of Example A15 (HEW: 793 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and 2- An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of ethyl-4-methylimidazole was used.

Example B16: Preparation of an epoxy resin composition using the polyol composition of Example A16 as a curing agent

As an epoxy resin, cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin ), using the polyol composition of Example A16 (HEW: 1,943 g/eq, 1 equivalent) instead of the polyol composition of Example A1 as a curing agent, and using 2 instead of N,N-dimethylbutylamine as a catalyst An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of -ethyl-4-methylimidazole was used.

Example B17: Preparation of an epoxy resin composition using the polyol composition of Example A17 as a curing agent

As an epoxy resin, cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin ) was used, the polyol composition of Example A17 (HEW: 530 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and 2- An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of ethyl-4-methylimidazole was used.

Comparative Example B1: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A1 as a curing agent

As an epoxy resin, cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin ) was used, the polyol composition of Comparative Example A1 (HEW: 247 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and 2- An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of ethyl-4-methylimidazole was used.

Comparative Example B2: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A2 as a curing agent

As an epoxy resin, cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin ) was used, the polyol composition of Comparative Example A2 (HEW: 4,625 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and N, N-dimethylbutylamine was used as a catalyst instead of 2 An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of -ethyl-4-methylimidazole was used.

Comparative Example B3: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A3 as a curing agent

As an epoxy resin, O-cresol novolac epoxy resin (YDCN-500-90P) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin, Kukdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent), the polyol composition of Comparative Example A3 (HEW: 248 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and N,N-dimethyl as a catalyst. An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of triphenylphosphine was used instead of butylamine.

Comparative Example B4: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A4 as a curing agent

As an epoxy resin, O-cresol novolac epoxy resin (YDCN-500-90P) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin, Kukdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent), the polyol composition of Comparative Example A4 (HEW: 4,643 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and N,N- An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of triphenylphosphine was used instead of dimethylbutylamine.

Comparative Example B5: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A5 as a curing agent

An epoxy resin composition was prepared in the same manner as in Example B1, except that the polyol composition of Comparative Example A5 (HEW: 117 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent.

Comparative Example B6: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A6 as a curing agent

An epoxy resin composition was prepared in the same manner as in Example B1, except that the polyol composition of Comparative Example A6 (HEW: 2,036 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent.

Comparative Example B7: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A7 as a curing agent

As an epoxy resin, cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin ) was used, the polyol composition of Comparative Example A7 (HEW: 118 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and 2- An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of ethyl-4-methylimidazole was used.

Comparative Example B8: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A8 as a curing agent

As an epoxy resin, cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin ), using the polyol composition of Comparative Example A8 (HEW: 2,036 g/eq, 1 equivalent) instead of the polyol composition of Example A1 as a curing agent, and using 2 instead of N,N-dimethylbutylamine as a catalyst An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of -ethyl-4-methylimidazole was used.

Comparative Example B9: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A9 as a curing agent

As an epoxy resin, O-cresol novolac epoxy resin (YDCN-500-90P) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin, Kukdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent), the polyol composition of Comparative Example A9 (HEW: 250 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and N,N-dimethyl as a catalyst. An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of triphenylphosphine was used instead of butylamine.

Comparative Example B10: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A10 as a curing agent

As an epoxy resin, O-cresol novolac epoxy resin (YDCN-500-90P) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin, Kukdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent), the polyol composition of Comparative Example A10 (HEW: 4,241 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and N,N- An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of triphenylphosphine was used instead of dimethylbutylamine.

Comparative Example B11: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A11 as a curing agent

An epoxy resin composition was prepared in the same manner as in Example B1, except that the polyol composition of Comparative Example A11 (HEW: 247 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent.

Comparative Example B12: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A12 as a curing agent

An epoxy resin composition was prepared in the same manner as in Example B1, except that the polyol composition of Comparative Example A12 (HEW: 4,241 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent.

Comparative Example B13: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A13 as a curing agent

As an epoxy resin, cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin ) was used, the polyol composition of Comparative Example A13 (HEW: 104 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and 2- An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of ethyl-4-methylimidazole was used.

Comparative Example B14: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A14 as a curing agent

As an epoxy resin, cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin ) was used, the polyol composition of Comparative Example A14 (HEW: 2,136 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and N, N-dimethylbutylamine was used as a catalyst instead of 2 An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of -ethyl-4-methylimidazole was used.

Comparative Example B15: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A15 as a curing agent

As an epoxy resin, O-cresol novolac epoxy resin (YDCN-500-90P) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin, Kukdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent), the polyol composition of Comparative Example A15 (HEW: 104 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and N,N-dimethyl as a catalyst. An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of triphenylphosphine was used instead of butylamine.

Comparative Example B16: Preparation of an epoxy resin composition using the polyol composition of Comparative Example A16 as a curing agent

As an epoxy resin, O-cresol novolac epoxy resin (YDCN-500-90P) instead of diglycidyl ether of bisphenol A (DGEBA)-based difunctional epoxy resin, Kukdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent), the polyol composition of Comparative Example A16 (HEW: 2,126 g/eq, 1 equivalent) was used instead of the polyol composition of Example A1 as a curing agent, and N,N- An epoxy resin composition was prepared in the same manner as in Example B1, except that 0.1 part by weight of triphenylphosphine was used instead of dimethylbutylamine.

<Preparation of adhesive specimen>

Using the polyol compositions prepared in Examples B1 to B17 and Comparative Examples B1 to B16 as adhesives, physical properties of the adhesive specimens were measured in the following manner, and the results are shown in Table 3 below.

<Measurement of physical properties>

(1) Shear strength (Unit: MPa)

Stainless steel with a size of 100 mm in length x 20 mm in width x 1 mm in thickness was cleaned using ethanol. Each of the epoxy resin compositions obtained in Examples B1 to B17 and Comparative Examples B1 to B16 as an adhesive was applied to one surface of the cleaned stainless steel with a length of 20 mm × width of 20 mm, and then a constant adhesive thickness was maintained thereon. To do this, a small amount of microbeads were laminated. After that, another stainless steel was covered and fixed thereon, followed by primary hardening at 50°C for 30 minutes, secondary hardening at 90°C for 30 minutes, third hardening at 110°C for 30 minutes, and 150°C for 30 minutes. It was cured 4 times. Shear strength was measured using a universal testing machine (Instron 5967, manufactured by Instron Co., Ltd.) for the adhesive specimens cooled to 23° C. after curing. At this time, the shear strength was measured while applying a load in the direction of 180 degrees at a tensile rate of 5 mm/min. Specifically, after measuring the shear strength of a total of 5 times for each adhesive specimen, their average value was calculated.

[Table 3]

As shown in Table 3, in the case of the epoxy bonded specimens of Examples B1 to B17 according to the present invention, it was confirmed that they exhibited excellent adhesive strength by exhibiting a shear strength of 23 MPa or more.

On the other hand, in the case of the epoxy adhesive specimens of Comparative Examples B1, B3, B5, B7, B9, B11, B13, and B15, the reaction activity of the polyol composition used as the curing agent was low, indicating poor adhesive strength, and Comparative Examples B2, B4, and B6 , B8, B10, B12, B14, and B16 epoxy bonded specimens, when shear strength was measured, sagging occurred at the bonding interface of the epoxy bonded specimens, and the shear strength was less than 12 MPa, showing poor adhesive strength.

Claims (19)

As a curing agent for epoxy resins,
Including a polyol composition prepared by an addition reaction of a crosslinked anhydrous sugar alcohol composition and an alkylene oxide,
The crosslinked anhydrous sugar alcohol composition is prepared from a crosslinking reaction between an anhydrous sugar alcohol composition and a rubber-modified epoxy compound,
The anhydrosugar-alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol; the second polyol component is a dianhydrosugar alcohol; the third polyol component is a polysaccharide alcohol represented by Formula 1 below; a fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from a polysaccharide alcohol represented by the following formula (1); the fifth polyol component is at least one polymer selected from the first to fourth polyol components;
The OH equivalent weight (Hydroxyl equivalent weight) of the polyol composition is 251 to 2,035 g / eq,
Hardeners for Epoxy Resins:
[Formula 1]

In Formula 1, n is an integer from 0 to 4. According to claim 1,
the first polyol component is monohydrosugar hexitol;
the second polyol component is dianhydrosugar hexitol;
A curing agent for an epoxy resin, 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 of 0 to 4. The curing agent for an epoxy resin according to claim 1, wherein the fifth polyol component comprises at least one selected from the group consisting of condensation polymers prepared from the following condensation polymerization 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 between the first polyol component and the second polyol component;
- polycondensation reaction between the first polyol component and the third polyol component;
- polycondensation reaction between the first polyol component and the fourth polyol component;
- polycondensation reaction between the second polyol component and the third polyol component;
- polycondensation reaction between the second polyol component and the fourth polyol component;
- polycondensation reaction between 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 curing agent for an epoxy resin according to claim 1, wherein the anhydrous sugar alcohol composition satisfies the following i) to iii):
i) the number average molecular weight (Mn) of the anhydrous sugar alcohol composition is 193 to 1,589 g/mol;
ii) the polydispersity index (PDI) of the anhydrous sugar alcohol composition is 1.13 to 3.41;
iii) The average number of -OH groups per molecule in the anhydrous sugar alcohol composition is 2.54 to 21.36. The method of claim 1, wherein the anhydrous sugar alcohol composition hydrogenates a glucose-containing saccharide composition to prepare a hydrogenated sugar composition, heats the obtained hydrogenated sugar composition under an acid catalyst for a dehydration reaction, and the obtained dehydration reaction product A curing agent for epoxy resins prepared by thin-film distillation. The curing agent for an epoxy resin according to claim 5, wherein the glucose-containing saccharide composition contains 41% to 99.5% by weight of glucose based on the total weight of the saccharide composition. The method of claim 1, wherein the rubber-modified epoxy compound is a natural rubber-modified epoxy compound, a carboxyl-terminated butadiene acrylonitrile-modified epoxy compound, a core-shell rubber-modified epoxy compound, a polybutadiene-modified epoxy compound, or an acrylonitrile-butadiene-modified epoxy compound. Selected from the group consisting of a styrene-butadiene-modified epoxy compound, an epoxy-terminated butadiene acrylonitrile-modified epoxy compound, an amine-terminated butadiene acrylonitrile-modified epoxy compound, a hydroxy-terminated butadiene acrylonitrile-modified epoxy compound, or a combination thereof At least one of which is, a curing agent for an epoxy resin. The curing agent for an epoxy resin according to claim 1, wherein the amount of the rubber-modified epoxy compound crosslinking with the anhydrous sugar alcohol composition is greater than 5 parts by weight and less than 55 parts by weight based on 100 parts by weight of the anhydrous sugar alcohol composition. The curing agent for an epoxy resin according to claim 1, wherein the amount of the alkylene oxide added to the crosslinked anhydrous sugar alcohol composition is greater than 50 parts by weight based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition. The curing agent for an epoxy resin according to claim 1, wherein the alkylene oxide is a linear or branched alkylene oxide having 2 to 8 carbon atoms. The curing agent for an epoxy resin according to claim 1, further comprising a curing agent component for an epoxy resin other than the polyol composition. epoxy resin; and
A curing agent for an epoxy resin according to any one of claims 1 to 11;
Epoxy resin composition. The method of claim 12, wherein the epoxy resin is a natural rubber-modified epoxy resin, a carboxyl-terminated butadiene acrylonitrile-modified epoxy resin, a core-shell rubber-modified epoxy resin, a polybutadiene-modified epoxy resin, an acrylonitrile-butadiene-modified epoxy resin, or styrene. -Butadiene-modified epoxy resin, epoxy-terminated butadiene acrylonitrile-modified epoxy resin, amine-terminated butadiene acrylonitrile-modified epoxy resin, hydroxy-terminated butadiene acrylonitrile-modified epoxy resin, bisphenol A-epichlorohydrin resin, epoxy Novolak resins, alicyclic (cycloaliphatic) epoxy resins, aliphatic epoxy resins, bi-dicyclic epoxy resins, glycidyl ester type epoxy resins, brominated epoxy resins, bio-derived epoxy resins, epoxidized soybean oil resins, novolak type epoxy resins, Bisphenol type epoxy resin, aromatic glycidylamine type epoxy resin, hydroquinone 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, aralkyl type epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin, phenol Novolak type epoxy resin, hydroquinone type epoxy resin, naphthalene skeleton type epoxy resin, tetraphenylolethane type epoxy resin, diphenyl phosphate type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadienephenol type epoxy resin , diglycidyl ether of bisphenol A ethylene oxide adduct, diglycidyl ether of bisphenol A propylene oxide adduct, diglycidyl ether of bisphenol A, phenyl glycidyl ether, cresyl glycidyl ether, these epoxy resins At least one selected from the group consisting of a nuclear hydrogenated epoxy resin or a combination thereof, which is a nuclear hydrogenation product, an epoxy resin composition. The epoxy resin composition according to claim 12, wherein the equivalent ratio of the curing agent for epoxy resin to the epoxy resin (equivalent of the curing agent for epoxy resin/equivalent of the epoxy resin) is 0.9 to 1.1. 13. The epoxy resin composition according to claim 12, further comprising a curing catalyst. The epoxy resin composition according to claim 15, wherein the curing catalyst is at least one selected from the group consisting of an amine-based compound, an imidazole-based compound, an organophosphorus compound, or a combination thereof. 13. The group of claim 12, consisting of an antioxidant, a UV absorber, a filler, a resin modifier, a silane coupling agent, a diluent, a colorant, an antifoaming agent, a defoaming agent, a dispersing agent, a viscosity modifier, a gloss modifier, a wetting agent, a conductivity imparting agent, or a combination thereof. Further comprising one or more additives selected from, the epoxy resin composition. A cured product obtained by curing the epoxy resin composition of claim 12. An adhesive comprising the cured product of claim 18.