KR102704049B1 - Curing agent for epoxy resin comprising anhydrosugar alcohol-alkylene glycol composition, 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, and an epoxy resin composition containing the same, and a cured product thereof, and more specifically, to an epoxy resin curing agent comprising an anhydrous sugar alcohol-alkylene glycol composition obtained by addition reacting an anhydrous sugar alcohol composition derived from biomass with an alkylene oxide, which is excellent in environmental friendliness and can improve the adhesiveness of the cured product when used in an epoxy resin composition, and an epoxy resin composition containing the same, and a cured product thereof.

Description

Curing agent for epoxy resin comprising anhydrosugar alcohol-alkylene glycol composition, and epoxy resin composition comprising the same and cured product thereof

The present invention relates to a curing agent for an epoxy resin, and an epoxy resin composition containing the same, and a cured product thereof, and more specifically, to an epoxy resin curing agent comprising an anhydrous sugar alcohol-alkylene glycol composition obtained by addition reacting an anhydrous sugar alcohol composition derived from biomass with an alkylene oxide, which is excellent in environmental friendliness and can improve the adhesiveness of the cured product when used in an epoxy resin composition, and an epoxy resin composition containing the same, and a cured product thereof.

Epoxy resins have excellent heat resistance, mechanical properties, electrical properties, and adhesive properties. By taking advantage of these properties, epoxy resins are used as sealing materials for wiring boards, circuit boards, multilayer circuit boards, semiconductor chips, coils, and electric circuits. Epoxy resins are also used as resins for adhesives, paints, and fiber-reinforced resins.

Epoxy resins find wide application as thermosetting resins in many applications. They are used as a thermosetting matrix in prepregs consisting of fibers embedded in a thermosetting matrix. They can also be used as surface coating materials, for bonding, molding and laminating due to their toughness, flexibility, adhesion and chemical resistance, all of which find diverse applications in a wide variety of industries such as aerospace, automotive, electronics, construction, furniture, green energy and sporting goods industries.

A wide range of epoxy resins are readily available and can be used depending on their reactivity required for a particular application. For example, the resins may be solid, liquid, or semi-solid, and may have varying reactivity depending on the application to which they are to be applied. The reactivity of an epoxy resin is often measured in terms of its epoxy equivalent weight, which is the molecular weight of the resin containing a single reactive epoxy group. The lower the epoxy equivalent weight, the higher the reactivity of the epoxy resin. Different epoxy resin applications require different reactivity, but this depends on whether the resin is present as a matrix in a fiber-reinforced prepreg, an adhesive coating, or a structural adhesive.

Epoxy resins are chemical units of molecules that compose them, and they must have epoxy bonds. A typical example is the one made by polymerizing epichlorohydrin and bisphenol A. Epoxy resins are never used alone, and are used by adding a hardener to change them into thermoset materials, so it would be appropriate to think of them as intermediates for regular resins. In other words, you cannot obtain a cured product with just an epoxy resin, and you must combine it with an epoxy reactor to form immovable cross-linking points to obtain a thermosetting structure.

The substances that create these cross-linking points are called hardeners. Hardeners that can be used with epoxy resins include phenol, acid anhydrides, and amines. Among them, since phenol can have various structures, the various changes in physical properties obtained by changing epoxy resins can also be obtained by changing the structure of phenol-based resin hardeners, and due to these various properties, phenol-based resin hardeners are currently mainly used. However, problems are being raised due to free phenol existing in phenol resins. Free phenol disappears after curing, but it poses a problem in use because it threatens the health of workers during work.

Hydrogenated sugars (also called “sugar alcohols”) are compounds obtained by adding hydrogen to the reducing terminal group of a sugar, and generally have the chemical formula HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer from 2 to 5), and are classified into tetrintol, pentitol, hexitol, and heptitol (having 4, 5, 6, and 7 carbon atoms, respectively) depending on the number of carbon atoms. Among them, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

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

The uses of anhydrous alcohol are very diverse, such as treatment of heart and blood vessel diseases, adhesives for patches, medicines such as mouthwashes, solvents for compositions in the cosmetics 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. Since it is an eco-friendly material derived from natural products, it is also very useful in the plastics industry such as bioplastics. In addition, it is known that it can be used as an eco-friendly solvent for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

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

The purpose of the present invention is to provide an epoxy resin curing agent which utilizes an anhydrous sugar alcohol composition derived from biomass and is excellent in environmental friendliness, and which can improve the adhesiveness of the cured product when used in an epoxy resin composition, and an epoxy resin composition containing the same and a cured product thereof.

The first aspect of the present invention provides an epoxy resin curing agent, which comprises an anhydrous sugar alcohol-alkylene glycol composition prepared by addition reacting an anhydrous sugar alcohol composition with an alkylene oxide, wherein the anhydrous sugar alcohol composition comprises first to fifth polyol components, wherein the first polyol component is a monoanhydrous sugar alcohol; the second polyol component is a dianhydrous sugar alcohol; the third polyol component is a polysaccharide alcohol represented by the following chemical formula 1; the fourth polyol component is an anhydrous sugar alcohol formed by removing a water molecule from a polysaccharide alcohol represented by the following chemical formula 1; the fifth polyol component is at least one polymer selected from among the first to fourth polyol components; and the anhydrous sugar alcohol-alkylene glycol composition has an OH equivalent (Hydroxyl equivalent weight) of 225 to 2,133 g/eq:

[Chemical Formula 1]

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

A second aspect of the present invention provides an epoxy resin composition comprising: an epoxy resin; 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 an 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, thereby significantly improving the adhesive strength (particularly, shear strength) of an adhesive utilizing the curing agent.

In addition, since the curing agent for epoxy resin according to the present invention can be manufactured by utilizing an anhydrous sugar alcohol composition, which is a by-product obtained in the process of manufacturing an internal dehydration product of hydrogenated sugar, it is possible to improve cost-effectiveness and environmental friendliness by solving the problem of by-product disposal.

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 comprises an anhydrous sugar alcohol-alkylene glycol composition prepared by addition reacting an anhydrous sugar alcohol composition and an alkylene oxide, wherein the OH equivalent (Hydroxyl equivalent weight) of the anhydrous sugar alcohol-alkylene glycol composition is 225 to 2,133 g/eq.

When the OH equivalent of the above anhydrous alcohol-alkylene glycol composition is less than 225 g/eq, when curing an epoxy resin with the anhydrous alcohol-alkylene glycol composition, the reaction activity between the components of the anhydrous alcohol-alkylene glycol composition and the epoxy resin is low, so that the reaction does not proceed sufficiently, and as a result, the adhesive strength of the adhesive including the cured product is poor.

On the other hand, when the OH equivalent of the anhydrous alcohol-alkylene glycol composition exceeds 2,133 g/eq, the length of the chain per OH becomes excessively long, and the epoxy resin cured with such anhydrous alcohol-alkylene glycol composition experiences tension and has a reduced elasticity (i.e., it only stretches and has no strength), so that the adhesive strength (especially, shear strength) of the adhesive including the cured product becomes very poor.

In one specific embodiment, the OH equivalent (unit: g/eq) of the anhydrous alcohol-alkylene glycol composition can be 225 or more, 230 or more, 240 or more, 250 or more, 260 or more, or 265 or more, and further can be 2,133 or less, 2,100 or less, 2,050 or less, or 2,000 or less. Further, in one specific embodiment, the OH equivalent of the anhydrous alcohol-alkylene glycol composition can be 225 to 2,133 g/eq, more specifically 230 to 2,100 g/eq, still more specifically 250 to 2,050 g/eq, and still more specifically 265 to 2,000 g/eq.

The anhydrous sugar alcohol composition and alkylene oxide used in the production of the above anhydrous sugar alcohol-alkylene glycol composition are described in more detail below.

Anhydrous alcohol composition

In the present invention, “anhydrous sugar alcohol” means any substance obtained by removing one or more water molecules from a compound obtained by adding hydrogen to a reducing terminal group of a sugar, commonly called hydrogenated sugar or sugar alcohol.

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

[Chemical Formula 1]

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

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

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

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

In the present invention, the type of the dihydric alcohol is not particularly limited, but is preferably a dihydric alcohol hexitol, and more specifically, is 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 specific example, the polysaccharide alcohol represented by the chemical formula 1, which is the third polyol component, can be produced by the hydrogenation reaction of a polysaccharide higher than a disaccharide, including maltose.

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

[Chemical formula 2]

[Chemical Formula 3]

In the above chemical formulas 2 and 3, n is each independently an integer from 0 to 4.

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

- Condensation polymerization reaction of the first polyol component,

- Condensation polymerization reaction of the second polyol component,

- Condensation polymerization reaction of the third polyol component,

- Condensation polymerization reaction of the fourth polyol component,

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

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

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

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

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

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

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

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

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

- A condensation polymerization reaction of a second polyol component, a third polyol component and a fourth polyol component, or

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

In one specific embodiment, the anhydrous alcohol composition may satisfy the following i) to iii):

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

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

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

In one specific 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 further may be 1,589 or less, 1,560 or less, 1,550 or less, 1,520 or less, 1,500 or less, 1,490 or less, or 1,480 or less. Furthermore, in one specific 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, even more specifically 202 to 1,500, and even more specifically 205 to 1,490. If the number average molecular weight of the anhydrous sugar alcohol composition exceeds the above-mentioned level, the adhesive strength of an adhesive including an epoxy resin cured product prepared by using the anhydrous sugar alcohol-alkylene glycol composition may deteriorate.

In one specific embodiment, the polydispersity index (PDI) of the anhydrous sugar alcohol composition can be 1.13 or more, 1.15 or more, 1.20 or more, 1.23 or more, or 1.25 or more, and further can be 3.41 or less, 3.40 or less, 3.35 or less, 3.30 or less, 3.25 or less, 3.22 or less, or 3.19 or less. Further, in one specific embodiment, the polydispersity index (PDI) of the anhydrous sugar alcohol composition can be 1.13 to 3.41, specifically 1.13 to 3.40, more specifically 1.15 to 3.35, even more specifically 1.20 to 3.25, and even more specifically 1.23 to 3.22. If the polydispersity index of the above anhydrous alcohol composition exceeds the above level, the adhesive strength of an adhesive including an epoxy resin cured product prepared by using the anhydrous alcohol-alkylene glycol composition may deteriorate.

In one specific embodiment, the average number of -OH groups per molecule in the anhydrous sugar alcohol composition can be at least 2.54, at least 2.60, at least 2.65, at least 2.70, at least 2.75, or at least 2.78, and further can be at most 21.36, at most 21.30, at most 21.0, at most 20.5, at most 20.0, at most 19.95, or at most 19.92. Further, in one specific embodiment, the average number of -OH groups per molecule in the anhydrous sugar alcohol composition can be from 2.54 to 21.36, more specifically from 2.60 to 21.30, and even more specifically from 2.65 to 21.0. If the average number of -OH groups per molecule in the anhydrous sugar alcohol composition exceeds the above-mentioned level, the adhesive strength of an adhesive including an epoxy resin cured product prepared using the anhydrous sugar alcohol-alkylene glycol composition may deteriorate.

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

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

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

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

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

Alkylene oxide

In the present invention, the “anhydrous alcohol-alkylene glycol composition” is prepared by addition reacting the anhydrous alcohol composition of the present invention with an alkylene oxide.

That is, in the present invention, the anhydrous alcohol-alkylene glycol composition includes an adduct obtained by reacting an alkylene oxide with a hydroxyl group at one or more terminals of each of the first to fifth polyol components, and specifically, includes an alkylene oxide adduct of the first polyol component (hereinafter referred to as the “first anhydrous alcohol-alkylene glycol”), an alkylene oxide adduct of the second polyol component (hereinafter referred to as the “second anhydrous alcohol-alkylene glycol”), an alkylene oxide adduct of the third polyol component (hereinafter referred to as the “third anhydrous alcohol-alkylene glycol”), an alkylene oxide adduct of the fourth polyol component (hereinafter referred to as the “fourth anhydrous alcohol-alkylene glycol”), and an alkylene oxide adduct of the fifth polyol component (hereinafter referred to as the “fifth anhydrous alcohol-alkylene glycol”).

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

According to one specific example, more than 50 parts by weight and less than 2,000 parts by weight of alkylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition can be additionally reacted.

If the amount of the alkylene oxide to be added is 50 parts by weight or less per 100 parts by weight of the anhydrous sugar alcohol composition, when the epoxy resin is cured with such an anhydrous sugar alcohol-alkylene glycol composition, the reaction activity between the components of the anhydrous sugar alcohol-alkylene glycol composition and the epoxy resin is lowered, so that the reaction does not proceed sufficiently, and as a result, the adhesive strength of the adhesive including the cured product may become poor. On the other hand, if the amount of the alkylene oxide to be added is 2,000 parts by weight or more per 100 parts by weight of the anhydrous sugar alcohol composition, the length of the chain per OH becomes excessively long, and the epoxy resin cured with such an anhydrous sugar alcohol-alkylene glycol composition experiences tension and has a reduced elasticity (i.e., it only stretches and becomes weak), so that the adhesive strength (particularly, shear strength) of the adhesive including the cured product may become very poor.

In one specific embodiment, the amount of alkylene oxide added to 100 parts by weight of the anhydrous sugar alcohol composition may be, for example, greater than 50 parts by weight, at least 51 parts by weight, at least 60 parts by weight, at least 70 parts by weight, at least 80 parts by weight, at least 90 parts by weight, or at least 100 parts by weight, and may also be, but is not limited to, less than 2,000 parts by weight, at most 1,990 parts by weight, at most 1,950 parts by weight, at most 1,900 parts by weight, at most 1,850 parts by weight, or at most 1,800 parts by weight.

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

In one specific embodiment, the curing agent for epoxy resin of the present invention may additionally include an epoxy resin curing agent component other than the anhydrous sugar alcohol-alkylene glycol composition described above.

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

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

According to another aspect of the present invention, an epoxy resin composition is provided, comprising: an epoxy resin; and a curing agent for the epoxy resin of the present invention described above.

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

In one specific example, the epoxy resin may be selected from the group consisting of, but is not limited to, bisphenol A-epichlorohydrin resin, epoxy novolac resin, cycloaliphatic epoxy resin, aliphatic epoxy resin, heterocyclic epoxy resin, glycidyl ester type epoxy resin, brominated epoxy resin, bio-derived epoxy resin, epoxidized soybean oil, and combinations thereof.

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

In another specific example, the epoxy resin may be selected from the group consisting of, but is not limited to, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin, naphthalene skeleton type epoxy resin, tetraphenylolethane type epoxy resin, diphenyl phosphate (DPP) type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, glycidyl ethers having one epoxy group such as diglycidyl ether of bisphenol A ethylene oxide adduct, diglycidyl ether of bisphenol A propylene oxide adduct, phenyl glycidyl ether, cresyl glycidyl ether, nuclear hydrogenated epoxy resins which are nuclear hydrogenated products of these epoxy resins, and combinations thereof.

In one specific example of the epoxy resin composition of the present invention, the epoxy resin is selected from the group consisting of bisphenol A-epichlorohydrin resin, epoxy novolac resin, cycloaliphatic (cycloaliphatic) epoxy resin, aliphatic epoxy resin, disubstituted 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, 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 novolac type epoxy resin, phenol novolac type epoxy resin, hydroquinone type epoxy resin, It may be at least one selected from the group consisting of naphthalene skeleton epoxy resin, tetraphenylolethane type epoxy resin, diphenyl phosphate type epoxy resin, trishydroxyphenylmethane type epoxy resin, diphenyl phosphate type epoxy resin, dicyclopentadiene phenol 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, nuclear hydrogenated epoxy resin which is a nuclear hydrogenation product of these epoxy resins, or a combination thereof.

In one specific example, the equivalent ratio of the epoxy resin curing agent of the present invention to the epoxy resin in the epoxy resin composition (equivalent weight of the epoxy resin curing agent/equivalent weight of the epoxy resin) may be, for example, 0.9 to 1.1, more specifically 0.92 to 1.08, and even more specifically 0.95 to 1.05. If the equivalent weight of the epoxy resin curing agent to the equivalent weight of the epoxy resin is too low, there may be a problem that the mechanical strength is lowered and the physical properties in terms of adhesive strength are lowered, and conversely, if the equivalent weight of the epoxy resin curing agent to the equivalent weight of the epoxy resin is too high, there may be a problem that the physical properties in terms of mechanical strength, thermal strength, and adhesive strength are lowered.

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

Therefore, for the purpose of promoting curing, the epoxy resin composition of the present invention may additionally contain a curing catalyst.

Examples of the curing catalyst that can be used in the present invention include amine compounds (e.g., tertiary amines) such as benzyldimethylamine, tris(dimethylaminomethyl)phenol, and dimethylcyclohexylamine; imidazole compounds such as 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-methylimidazole; organophosphorus compounds such as triphenylphosphine and triphenyl phosphite; quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide; diazabicycloalkenes such as 1,8-diazabicyclo[5.4.0]undecene-7 or organic acid salts thereof; organometallic compounds such as zinc octylate, tin octylate, and aluminum acetylacetone complex; Examples of the polymerizable ...

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

When the epoxy resin composition of the present invention contains a curing catalyst, the amount thereof may be 0.01 to 1.0 parts by weight, more specifically 0.05 to 0.5 parts by weight, and even more specifically 0.08 to 0.2 parts by weight, relative to 100 parts by weight of the total of the epoxy resin and the curing agent for the epoxy resin, but is not limited thereto. If the amount of the curing catalyst used is too small, the curing reaction of the epoxy resin may not progress sufficiently, which may cause a problem in that the mechanical properties and thermal properties may deteriorate, and conversely, if the amount of the curing catalyst used is too large, the curing reaction may progress slowly even during storage of the epoxy resin composition, which may cause a problem in that the viscosity may increase.

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

The above antioxidant can be used to further improve the heat resistance stability of the obtained cured product, and is not particularly limited, but for example, one selected from the group consisting of phenol-based antioxidants (e.g., dibutylhydroxytoluene), sulfur-based antioxidants (e.g., mercaptopropionic acid derivatives), phosphorus-based antioxidants (e.g., 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), and combinations thereof can be used. The content of the antioxidant in the composition can be 0.01 to 10 parts by weight, or 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight, relative to 100 parts by weight of the total of the epoxy resin and the curing agent for the epoxy resin.

The UV absorbent is not particularly limited, but may be selected from the group consisting of, for example, benzotriazole-based UV absorbers such as TINUBIN P or TINUVIN 234 manufactured by BASF Japan Ltd.; triazine-based UV absorbers such as TINUVIN 1577ED; hindered amine-based UV absorbers such as CHIMASSOLV 2020FDL, and combinations thereof. The content of the UV absorbent in the composition may be 0.01 to 10 parts by weight, or 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight, relative to 100 parts by weight of the total of the epoxy resin and the curing agent for the epoxy resin.

The above fillers are mainly used for the purpose of improving the mechanical properties of the cured product by mixing them with epoxy resin or an epoxy resin curing agent, and generally, the mechanical properties improve as the amount added increases. Inorganic fillers include extenders such as talc, sand, silica, talc, and calcium carbonate; reinforcing fillers such as mica, quartz, and glass fiber; and those with special 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 the coefficient of thermal expansion, wear resistance, thermal conductivity, and adhesiveness; antimony oxide (SB2O3), which imparts flame retardancy; barium titanate, and organic fillers such as fine plastic balls (phenol resin, urea resin, etc.) for weight reduction. In addition, various glass fibers or chemical fiber cloths as fillers with reinforcing properties can be treated as fillers in a broad sense in the manufacture of laminated products. In order to impart thixotropy to the resin (thixotropy or thixotropy refers to the property of having a liquid state when flowing and a solid state when stationary so that the resin attached to a vertical plane or by the immersion method or impregnated into the laminated material does not flow down or get lost during curing), fine particles with a large unit surface area are used. For example, colloidal silica (Aerosil) or bentonite-based clay is used. In one specific example, the filler is not particularly limited, but may be selected from the group consisting of glass fiber, carbon fiber, titanium oxide, alumina, talc, mica, aluminum hydroxide, and combinations thereof. 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, relative to 100 parts by weight of the total of the epoxy resin and the curing agent for the epoxy resin.

The resin modifier is not particularly limited, and examples thereof include, but are not limited to, a flexibility-imparting agent 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, relative to 100 parts by weight of the total of the epoxy resin and the epoxy resin curing agent.

The silane coupling agent is not particularly limited, and examples thereof include chloropropyltrimethoxysilane, vinyltrichlorosilane, γ-methacryloxypropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. The content of the silane coupling agent in the composition may be 0.01 to 20 parts by weight, or 0.05 to 10 parts by weight, or 0.1 to 5 parts by weight, relative to 100 parts by weight of the total of the epoxy resin and the curing agent for the epoxy resin.

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

Pigments or dyes are used as coloring agents to color the resin. Commonly used pigments include titanium dioxide, cadmium red, sintering green, carbon black, chrome green, chrome yellow, navy blue, sintering blue, etc.

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

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

The curing temperature and curing time can range from 50°C to 250°C and from 30 seconds to 10 hours. In one specific example, pre-curing can be performed under the conditions of 50°C to 120°C for 0.5 to 5 hours, and then post-curing can be performed under the conditions of 120°C to 180°C for 0.1 to 5 hours. In another specific example, first curing can be performed under the conditions of 50°C to 85°C for 0.5 to 5 hours, second curing can be performed under the conditions of 85°C to 105°C for 0.5 to 5 hours, third curing can be performed under the conditions of 105°C to 145°C for 0.5 to 5 hours, and fourth curing can be performed under the conditions of 145°C to 180°C for 0.5 to 5 hours. In other specific examples, for short-time curing, curing can be performed under conditions of 150°C to 250°C for 30 seconds to 30 minutes.

In one specific embodiment, the epoxy resin composition of the present invention may be stored separately as two or more components, for example, a component including a curing agent for an epoxy resin and a component including an epoxy resin, 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 subjected to curing as is. When stored as a thermosetting composition, it may be stored at a 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 including the cured product is provided.

The adhesive of the present invention may additionally contain additives that can be commonly used in epoxy 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 first to fifth polyol components>

Manufacturing Example A1: Manufacturing of anhydrous sugar alcohol composition using 97 wt% glucose content

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

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

The obtained anhydrous alcohol conversion solution (831 g) was placed in a thin film distiller (SPD) and distilled. At this time, the 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, about 242 g of an anhydrosugar alcohol composition was obtained, comprising 11.5 wt% of isosorbide (anhydrosugar alcohol) [second polyol component], 0.4 wt% of isomannide (anhydrosugar alcohol) [second polyol component], 7.4 wt% of sorbitan (anhydrosugar alcohol) [first polyol component], 2.5 wt% of a polysaccharide alcohol represented by the chemical formula 1 [third polyol component] and anhydrosugar alcohol derived therefrom (i.e., formed by removing water molecules from the polysaccharide alcohol) [fourth polyol component], and 78.2 wt% of a polymer thereof [fifth polyol component], wherein the number average molecular weight of the composition is 208 g/mol, the polydispersity index of the composition is 1.25, the hydroxyl value of the composition is 751 mg KOH/g, and the average number of -OH groups per molecule in the composition is 2.78.

Manufacturing Example A2: Manufacturing of anhydrous sugar alcohol composition using a sugar composition containing 50.2 wt% glucose

Except that a 50.2 wt% glucose-containing saccharide composition (50.2 wt% glucose and 49.8 wt% total of mannose, fructose, and polysaccharides (disaccharides or higher sugars such as maltose)) was used instead of the 97% pure glucose product, a hydrogenation reaction was performed in the same manner as in Manufacturing Example A1 to obtain 1,819 g of a liquid hydrogenated sugar composition having a concentration of 55 wt% (based on solid content, 48.5 wt% sorbitol, 3.6 wt% mannitol, and 47.9 wt% polysaccharide alcohols or higher sugars). This was placed in a batch reactor equipped with a stirrer and heated to 100°C to concentrate, whereby 1,000 g of a concentrated hydrogenated sugar composition was obtained.

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

Thin film distillation was performed on 890 g of the obtained anhydrous alcohol conversion solution using the same method as in Manufacturing Example A1 to obtain about 304 g of 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, about 586 g of an anhydrous sugar alcohol composition was obtained, comprising 0.9 wt% of isosorbide (anhydrous sugar alcohol), 2.1 wt% of isomannide (anhydrous sugar alcohol), 0.9 wt% of sorbitan (monoanhydrous sugar alcohol), 6.2 wt% of polysaccharide alcohols higher than disaccharides and anhydrous sugar alcohols derived therefrom, and 89.9 wt% of polymers thereof, wherein 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, and the average number of -OH groups per molecule in the composition is 19.92.

<Preparation of anhydrous alcohol-alkylene glycol composition>

Example A1: Anhydrous sugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of ethylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A1

100 parts by weight (100 g) of the anhydrous sugar alcohol composition obtained in the above Manufacturing Example A1 and 1.0 g of KOH were placed in a pressurized reactor, and the process of pressurizing and exhausting with nitrogen gas was repeated 3 times. Thereafter, the internal temperature of the reactor was raised to 100°C to remove moisture, and after all moisture was removed, 100 parts by weight (100 g) of ethylene oxide was slowly added while causing an addition reaction at 100°C to 140°C. Thereafter, 4 g of a metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and the reactor was stirred for 1 to 5 hours while maintaining the internal temperature at 100°C to 120°C and monitoring the residual metal content. When the metal was completely removed and no longer detected, the internal temperature of the reactor was cooled to 60°C to 90°C, and then filtered. By purifying the filtrate using a mixed ion exchange resin, an anhydrous sugar alcohol-alkylene glycol composition was obtained.

Example A2: Anhydrous alcohol-alkylene glycol composition prepared by addition reaction of 1,800 parts by weight of ethylene oxide per 100 parts by weight of the anhydrous alcohol composition of Preparation Example A1

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that the content of ethylene oxide was changed from 100 parts by weight (100 g) to 1,800 parts by weight (1,800 g).

Example A3: Anhydrous alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of propylene oxide per 100 parts by weight of the anhydrous alcohol composition of Preparation Example A1

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that 100 parts by weight (100 g) of propylene oxide was used instead of ethylene oxide.

Example A4: An anhydrous alcohol-alkylene glycol composition prepared by addition reaction of 1,500 parts by weight of propylene oxide per 100 parts by weight of the anhydrous alcohol composition of Preparation Example A1

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that 1,500 parts by weight (1,500 g) of propylene oxide was used instead of ethylene oxide.

Example A5: Anhydrous alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of ethylene oxide per 100 parts by weight of the anhydrous alcohol composition of Preparation Example A2

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example A2 was used instead of the anhydrous sugar alcohol composition of Preparation Example A1.

Example A6: Anhydrous sugar alcohol-alkylene glycol composition prepared by addition reaction of 560 parts by weight of ethylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A2

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example A2 was used instead of the anhydrous sugar alcohol composition of Preparation Example A1, and the content of ethylene oxide was changed from 100 parts by weight (100 g) to 560 parts by weight (560 g).

Example A7: Anhydrous alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of propylene oxide per 100 parts by weight of the anhydrous alcohol composition of Preparation Example A2

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example A2 was used instead of the anhydrous sugar alcohol composition of Preparation Example A1, and 100 parts by weight (100 g) of propylene oxide was used instead of ethylene oxide.

Example A8: An anhydrous sugar alcohol-alkylene glycol composition prepared by addition reaction of 470 parts by weight of propylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A2

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example A2 was used instead of the anhydrous sugar alcohol composition of Preparation Example A1, and 470 parts by weight (470 g) of propylene oxide was used instead of ethylene oxide.

Comparative Example A1: Anhydrous sugar alcohol-alkylene glycol composition prepared by addition reaction of 50 parts by weight of ethylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A1

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that the content of ethylene oxide was changed from 100 parts by weight (100 g) to 50 parts by weight (50 g).

Comparative Example A2: Anhydrous sugar alcohol-alkylene glycol composition manufactured by adding 2,000 parts by weight of ethylene oxide to 100 parts by weight of the anhydrous sugar alcohol composition of Manufacturing Example A1.

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that the content of ethylene oxide was changed from 100 parts by weight (100 g) to 2,000 parts by weight (2,000 g).

Comparative Example A3: An anhydrous sugar alcohol-alkylene glycol composition prepared by adding 50 parts by weight of propylene oxide to 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A1.

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that 50 parts by weight (50 g) of propylene oxide was used instead of ethylene oxide.

Comparative Example A4: An anhydrous alcohol-alkylene glycol composition prepared by addition reaction of 2,000 parts by weight of propylene oxide per 100 parts by weight of the anhydrous alcohol composition of Preparation Example A1

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that 2,000 parts by weight (2,000 g) of propylene oxide was used instead of ethylene oxide.

Comparative Example A5: Anhydrous sugar alcohol-alkylene glycol composition prepared by addition reaction of 50 parts by weight of ethylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A2

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example A2 was used instead of the anhydrous sugar alcohol composition of Preparation Example A1, and the content of ethylene oxide was changed from 100 parts by weight (100 g) to 50 parts by weight (50 g).

Comparative Example A6: An anhydrous sugar alcohol-alkylene glycol composition manufactured by adding 2,000 parts by weight of ethylene oxide to 100 parts by weight of the anhydrous sugar alcohol composition of Manufacturing Example A2.

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example A2 was used instead of the anhydrous sugar alcohol composition of Preparation Example A1, and the content of ethylene oxide was changed from 100 parts by weight (100 g) to 2,000 parts by weight (2,000 g).

Comparative Example A7: Anhydrous sugar alcohol-alkylene glycol composition prepared by addition reaction of 50 parts by weight of propylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A2

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example A2 was used instead of the anhydrous sugar alcohol composition of Preparation Example A1, and 50 parts by weight (50 g) of propylene oxide was used instead of ethylene oxide.

Comparative Example A8: An anhydrous sugar alcohol-alkylene glycol composition prepared by addition reaction of 2,000 parts by weight of propylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A2

An anhydrous sugar alcohol-alkylene glycol composition was obtained by performing the same method as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example A2 was used instead of the anhydrous sugar alcohol composition of Preparation Example A1, and 2,000 parts by weight (2,000 g) of propylene oxide was used instead of ethylene oxide.

The composition and properties of the anhydrous sugar alcohol-alkylene glycol compositions manufactured in the above examples and comparative examples are shown in Table 1 below.

<Method for Measuring the Properties of an Anhydrous Alcohol-Alkylene Glycol Composition>

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

(1) Each of 5 g of the anhydrous sugar alcohol-alkylene glycol compositions obtained in Examples A1 to A8 and Comparative Examples A1 to A8 was dissolved in 100 ml of chloroform, placed in a 500 ml round bottom flask containing 100 ml of acetic anhydride and 100 ml of pyridine, and stirred for 3 days, thereby acetylating the anhydrous sugar alcohol-alkylene glycol compositions obtained in Examples A1 to A8 and Comparative Examples A1 to A8. Thereafter, the acetylated anhydrous sugar alcohol-alkylene glycol compositions were washed with water, and the number average molecular weights of the anhydrous sugar alcohol-alkylene glycol compositions were measured using gel permeation chromatography (GPC).

Specifically, each of the above acetylated anhydrous sugar alcohol-alkylene glycol compositions was dissolved in tetrahydrofuran (THF) at 1 to 3 parts by weight, and then the number average molecular weight (Mn) was measured using a gel permeation chromatography apparatus (Agilent). The column used was GPC KF-802.5 (Shodex), the column temperature was 40°C, the developing solvent used was tetrahydrofuran, and it was used by flowing at a rate of 0.5 ml/min, and polystyrene (Aldrich) was used as a standard material.

(2) According to ASTM D-4274D, a hydroxyl value test standard, each of the anhydrous sugar alcohol-alkylene glycol compositions manufactured in Examples A1 to A8 and Comparative Examples A1 to A8 was subjected to an esterification reaction with an excess of phthalic anhydride in the presence of an imidazole catalyst, and then the residual phthalic anhydride was titrated with 0.5 N sodium hydroxide (NaOH), thereby measuring the hydroxyl value (unit: mg KOH/g) of each anhydrous sugar alcohol-alkylene glycol composition.

(3) The number average molecular weight and hydroxyl value of each measured anhydrous alcohol-alkylene glycol composition were used to measure the OH equivalent of the anhydrous alcohol-alkylene glycol compositions obtained in Examples A1 to A8 and Comparative Examples A1 to A8 using the following formula.

[OH equivalent] = (number average molecular weight of the measured anhydrous alcohol-alkylene glycol composition) / (OH functional group number through calculation of the hydroxyl value and number average molecular weight of the measured anhydrous alcohol-alkylene glycol composition)

[Table 1]

<Preparation of epoxy resin composition>

Example B1: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as a hardener

A difunctional epoxy resin of the diglycidyl ether of bisphenol A (DGEBA) type (YD-128, Kukdo Chemical Co., Ltd., epoxy equivalent weight (EEW): 187 g/eq, 1 equivalent) and an anhydrous sugar alcohol-alkylene glycol composition of Example A1 (HEW: 265 g/eq, 1 equivalent) as a hardener were mixed, and 0.1 part by weight of N,N-dimethylbutylamine (DMBA, Sigma aldrich) as a catalyst was added to 100 parts by weight of the mixture, thereby preparing an epoxy resin composition.

Example B2: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol 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 anhydrous sugar alcohol-alkylene glycol composition of Example A2 (HEW: 1,938 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as a curing agent.

Example B3: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Example A3 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that a cycloaliphatic difunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) was used instead of the diglycidyl ether of bisphenol A (DGEBA) as the epoxy resin, the anhydrous sugar alcohol-alkylene glycol composition of Example A3 (HEW: 281 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as the hardener, and 0.1 part by weight of 2-ethyl-4-methylimidazole (2E4M, Sigma Aldrich) was used instead of N,N-dimethylbutylamine as the catalyst.

Example B4: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Example A4 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that a cycloaliphatic difunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) was used instead of the diglycidyl ether of bisphenol A (DGEBA) as the epoxy resin, the anhydrous sugar alcohol-alkylene glycol composition of Example A4 (HEW: 1,889 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as the hardener, and 0.1 part by weight of 2-ethyl-4-methylimidazole was used instead of N,N-dimethylbutylamine as the catalyst.

Example B5: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Example A5 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that O-cresol novolac epoxy resin (YDCN-500-90P, Kookdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent) was used instead of the difunctional epoxy resin of the diglycidyl ether of bisphenol A (DGEBA) series as the epoxy resin, the anhydrous sugar alcohol-alkylene glycol composition of Example A5 (HEW: 738 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as the hardener, and 0.1 part by weight of triphenylphosphine (TPP, Sigma Aldrich) was used instead of N,N-dimethylbutylamine as the catalyst.

Example B6: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Example A6 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that O-cresol novolac epoxy resin (YDCN-500-90P, Kookdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent) was used instead of the difunctional epoxy resin of the diglycidyl ether of bisphenol A (DGEBA) series as the epoxy resin, the anhydrous sugar alcohol-alkylene glycol composition of Example A6 (HEW: 2,000 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as the hardener, and 0.1 part by weight of triphenylphosphine was used instead of N,N-dimethylbutylamine as the catalyst.

Example B7: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Example A7 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that the anhydrous sugar alcohol-alkylene glycol composition of Example A7 (HEW: 784 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as a curing agent.

Example B8: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Example A8 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that the anhydrous sugar alcohol-alkylene glycol composition of Example A8 (HEW: 1,969 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as a curing agent.

Comparative Example B1: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A1 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that a cycloaliphatic difunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) was used instead of the diglycidyl ether of bisphenol A (DGEBA) as the epoxy resin, the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A1 (HEW: 216 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as the hardener, and 0.1 part by weight of 2-ethyl-4-methylimidazole was used instead of N,N-dimethylbutylamine as the catalyst.

Comparative Example B2: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A2 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that a cycloaliphatic difunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) was used instead of the diglycidyl ether of bisphenol A (DGEBA) as the epoxy resin, the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A2 (HEW: 2,134 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as the hardener, and 0.1 part by weight of 2-ethyl-4-methylimidazole was used instead of N,N-dimethylbutylamine as the catalyst.

Comparative Example B3: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A3 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that O-cresol novolac epoxy resin (YDCN-500-90P, Kookdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent) was used instead of the difunctional epoxy resin of the diglycidyl ether of bisphenol A (DGEBA) series as the epoxy resin, the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A3 (HEW: 224 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as the hardener, and 0.1 part by weight of triphenylphosphine was used instead of N,N-dimethylbutylamine as the catalyst.

Comparative Example B4: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A4 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that O-cresol novolac epoxy resin (YDCN-500-90P, Kookdo Chemical Co., Ltd., EEW: 206.3 g/eq, 1 equivalent) was used instead of the difunctional epoxy resin of the diglycidyl ether of bisphenol A (DGEBA) series as the epoxy resin, that the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A4 (HEW: 2,463 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as the hardener, and that 0.1 part by weight of triphenylphosphine was used instead of N,N-dimethylbutylamine as the catalyst.

Comparative Example B5: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A5 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A5 (HEW: 171 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as a curing agent.

Comparative Example B6: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A6 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A6 (HEW: 5,951 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as a curing agent.

Comparative Example B7: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A7 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that a cycloaliphatic difunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) was used instead of the diglycidyl ether of bisphenol A (DGEBA) as the epoxy resin, the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A7 (HEW: 172 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as the hardener, and 0.1 part by weight of 2-ethyl-4-methylimidazole was used instead of N,N-dimethylbutylamine as the catalyst.

Comparative Example B8: Preparation of an epoxy resin composition using the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A8 as a hardener

An epoxy resin composition was prepared in the same manner as in Example B1, except that a cycloaliphatic difunctional epoxy resin (Celloxide 2021p, Daecel, EEW: 136.5 g/eq, 1 equivalent) was used instead of the diglycidyl ether of bisphenol A (DGEBA) as the epoxy resin, the anhydrous sugar alcohol-alkylene glycol composition of Comparative Example A8 (HEW: 6,867 g/eq, 1 equivalent) was used instead of the anhydrous sugar alcohol-alkylene glycol composition of Example A1 as the hardener, and 0.1 part by weight of 2-ethyl-4-methylimidazole was used instead of N,N-dimethylbutylamine as the catalyst.

<Manufacturing of adhesive specimens>

The epoxy resin compositions manufactured in Examples B1 to B8 and Comparative Examples B1 to B8 were used as adhesives, and the physical properties of adhesive specimens were measured by the following method, and the results are shown in Table 2 below.

<Measurement of physical properties>

(1) Shear strength (unit: MPa)

A stainless steel having a length of 100 mm × width of 20 mm × thickness of 1 mm was cleaned using ethanol. Each of the epoxy resin compositions obtained in Examples B1 to B8 and Comparative Examples B1 to B8 was applied as an adhesive to one surface of the cleaned stainless steel in a length of 20 mm × width of 20 mm, and then a small amount of micro beads were laminated thereon to maintain a constant adhesive thickness. Thereafter, another stainless steel was covered and fixed thereon, and then cured at 50°C for 30 minutes for the first time, at 90°C for 30 minutes for the second time, at 110°C for 30 minutes for the third time, and at 150°C for 30 minutes for the fourth time. After curing, the shear strength of the bonded specimen cooled to 23°C was measured using a universal materials testing machine (Instron 5967 product, Instron Co., Ltd.). At this time, the measurement of shear strength was performed by applying a load in the 180-degree direction at a tensile speed of 5 mm/min. Specifically, the shear strength was measured a total of five times for each bonded specimen, and their average value was calculated.

[Table 2]

As shown in Table 2, the epoxy adhesive specimens of Examples B1 to B8 according to the present invention exhibited a shear strength of 15 MPa or more, confirming that they exhibited excellent adhesive strength.

On the other hand, in the case of the epoxy adhesive specimens of Comparative Examples B1, B3, B5, and B7, the reactive activity of the anhydrous sugar alcohol-alkylene glycol composition used as the hardener was low, so that the adhesive strength was relatively low compared to the epoxy adhesive specimens of the examples, and in the case of the epoxy adhesive specimens of Comparative Examples B2, B4, B6, and B8, when the shear strength was measured, the epoxy adhesive specimens showed very poor adhesive strength with a shear strength of 9 MPa or less due to stretching at the adhesive interface.

Claims (16)

As a hardener for epoxy resin,
A composition comprising an anhydrous sugar alcohol-alkylene glycol composition prepared by addition reaction of an anhydrous sugar alcohol composition and an alkylene oxide,
The above anhydrous sugar alcohol composition comprises first to fifth polyol components, wherein the first polyol component is a monoanhydrous sugar alcohol; the second polyol component is a dianhydrous sugar alcohol; the third polyol component is a polysaccharide alcohol represented by the following chemical formula 1; the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from a polysaccharide alcohol represented by the following chemical formula 1; and the fifth polyol component is at least one polymer selected from the first to fourth polyol components;
The above anhydrous alcohol composition comprises, based on the total weight of the composition, a first polyol component in an amount of 0.1 to 20 wt%, a second polyol component in an amount of 0.1 to 28 wt%, a third polyol component and a fourth polyol component in a total content of 0.1 to 6.5 wt%, and a fifth polyol component in an amount of 55 to 90 wt%.
The OH equivalent (Hydroxyl equivalent weight) of the above anhydrous alcohol-alkylene glycol composition is 265 to 2,000 g/eq,
Hardener for epoxy resin:
[Chemical Formula 1]

In the above chemical formula 1, n is an integer from 0 to 4. In the first paragraph,
The first polyol component is a monohydric hexitol;
The second polyol component is the dimethyl ether hexitol;
A curing agent for an epoxy resin, wherein the fourth polyol component is selected from a compound represented by the following chemical formula 2, a compound represented by the following chemical formula 3, or a mixture thereof:
[Chemical formula 2]

[Chemical Formula 3]

In the above chemical formulas 2 and 3, n is each independently an integer from 0 to 4. In the first paragraph, a curing agent for an epoxy resin, wherein the fifth polyol component comprises at least one selected from the group consisting of condensation polymers prepared from the following condensation polymerization reaction:
- Condensation polymerization reaction of the first polyol component,
- Condensation polymerization reaction of the second polyol component,
- Condensation polymerization reaction of the third polyol component,
- Condensation polymerization reaction of the fourth polyol component,
- Condensation polymerization reaction of the first polyol component and the second polyol component,
- Condensation polymerization reaction of the first polyol component and the third polyol component,
- Condensation polymerization reaction of the first polyol component and the fourth polyol component,
- Condensation polymerization reaction of the second polyol component and the third polyol component,
- Condensation polymerization reaction of the second polyol component and the fourth polyol component,
- Condensation polymerization reaction of the third polyol component and the fourth polyol component,
- Condensation polymerization reaction of the first polyol component, the second polyol component, and the third polyol component;
- Condensation polymerization reaction of the first polyol component, the second polyol component, and the fourth polyol component;
- Condensation polymerization reaction of the first polyol component, the third polyol component, and the fourth polyol component;
- A condensation polymerization reaction of a second polyol component, a third polyol component and a fourth polyol component, or
- Condensation polymerization reaction of the first polyol component, the second polyol component, the third polyol component, and the fourth polyol component. In the first paragraph, the anhydrous sugar alcohol composition is a curing agent for epoxy resin satisfying the following i) to iii):
i) the number average molecular weight (Mn) of the anhydrous alcohol composition is 193 to 1,589 g/mol;
ii) the polydispersity index (PDI) of the anhydrous alcohol composition is 1.13 to 3.41;
iii) The average number of -OH groups per molecule in the anhydrous alcohol composition is 2.54 to 21.36. A curing agent for an epoxy resin, wherein in claim 1, the anhydrous sugar alcohol composition is prepared by subjecting a glucose-containing saccharide composition to a hydrogenation reaction to produce a hydrogenated sugar composition, heating the obtained hydrogenated sugar composition in the presence of an acid catalyst to cause a dehydration reaction, and thin-film distilling the obtained dehydration reaction resultant. A curing agent for an epoxy resin, wherein the glucose-containing saccharide composition in claim 5 contains 41 to 99.5 wt% of glucose based on the total weight of the saccharide composition. A curing agent for an epoxy resin, wherein in claim 1, more than 50 parts by weight and less than 2,000 parts by weight of an alkylene oxide is additionally reacted per 100 parts by weight of an anhydrous sugar alcohol composition. A curing agent for an epoxy resin, further comprising a curing agent component for an epoxy resin other than an anhydrous sugar alcohol-alkylene glycol composition in claim 1. Epoxy resin; and
A curing agent for an epoxy resin according to any one of claims 1 to 8;
Epoxy resin composition. In claim 9, the epoxy resin is a bisphenol A-epichlorohydrin resin or a nucleotide additive thereof, an epoxy novolac resin or a nucleotide additive thereof, an alicyclic (cycloaliphatic) epoxy resin or a nucleotide additive thereof, an aliphatic epoxy resin or a nucleotide additive thereof, a dissociated epoxy resin or a nucleotide additive thereof, a glycidyl ester-type epoxy resin or a nucleotide additive thereof, a brominated epoxy resin or a nucleotide additive thereof, a bio-derived epoxy resin or a nucleotide additive thereof, an epoxidized soybean oil resin or a nucleotide additive thereof, a novolac-type epoxy resin or a nucleotide additive thereof, a bisphenol-type epoxy resin or a nucleotide additive thereof, an aromatic glycidylamine-type epoxy resin or a nucleotide additive thereof, a hydroquinone-type epoxy resin or a nucleotide additive thereof, a biphenyl-type epoxy resin or a nucleotide additive thereof, a stilbene-type epoxy resin or a nucleotide additive thereof, a triphenolmethane-type epoxy resin or a nucleotide additive thereof. Nucleus-containing epoxy resin or nucleus-containing product, triphenolpropane-type epoxy resin or nucleus-containing product, alkyl-modified triphenolmethane-type epoxy resin or nucleus-containing product, triazine nucleus-containing epoxy resin or nucleus-containing product, dicyclopentadiene-modified phenol-type epoxy resin or nucleus-containing product, naphthol-type epoxy resin or nucleus-containing product, naphthalene-type epoxy resin or nucleus-containing product, aralkyl-type epoxy resin or nucleus-containing product, bisphenol F-type epoxy resin or nucleus-containing product, cresol novolac-type epoxy resin or nucleus-containing product, phenol novolac-type epoxy resin or nucleus-containing product, hydroquinone-type epoxy resin or nucleus-containing product, naphthalene skeleton-type epoxy resin or nucleus-containing product, tetraphenylolethane-type epoxy resin or nucleus-containing product, diphenylphosphate-type epoxy resin or nucleus-containing product, trishydroxyphenylmethane-type epoxy resin or nucleus-containing product An epoxy resin composition, wherein at least one is selected from the group consisting of a nucleus additive, a dicyclopentadienephenol-type epoxy resin or a nucleus additive thereof, a diglycidyl ether of a bisphenol A ethylene oxide adduct or a nucleus additive thereof, a diglycidyl ether of a bisphenol A propylene oxide adduct or a nucleus additive thereof, a diglycidyl ether of bisphenol A or a nucleus additive thereof, a phenyl glycidyl ether or a nucleus additive thereof, a cresyl glycidyl ether or a nucleus additive thereof, or a combination thereof. An epoxy resin composition in claim 9, wherein the equivalent ratio of the epoxy resin curing agent to the epoxy resin (equivalent amount of the epoxy resin curing agent/equivalent amount of the epoxy resin) is 0.9 to 1.1. An epoxy resin composition further comprising a curing catalyst in claim 9. An epoxy resin composition in claim 12, wherein the curing catalyst is at least one selected from the group consisting of an amine compound, an imidazole compound, an organophosphorus compound, or a combination thereof. An epoxy resin composition further comprising at least one additive selected from the group consisting of an antioxidant, a UV absorber, a filler, a resin modifier, a silane coupling agent, a diluent, a colorant, an anti-foaming agent, a defoaming agent, a dispersant, a viscosity regulator, a gloss regulator, a wetting agent, a conductivity-imparting agent, and mixtures thereof, in claim 9. A cured product obtained by curing the epoxy resin composition of claim 9. An adhesive comprising the cured product of clause 15.