KR20230140964A - Epoxy resin composition derived from polyol composition prepared by adding alkylene oxide to anhydrosugar alcohol composition crosslinked with epoxy compound modified with rubber, and method for preparing the same, and curable epoxy resin composition comprising the same and cured product thereof - Google Patents

Abstract

The present invention relates to an epoxy resin composition derived from a polyol composition prepared by adding an alkylene oxide to an anhydrous sugar alcohol composition crosslinked with an epoxy compound modified into rubber, a method for producing the same, a curable epoxy resin composition containing the same, and a cured product thereof. More specifically, it is a polyol obtained by crosslinking an anhydrous sugar alcohol composition derived from biomass with an epoxy compound modified into rubber and then adding alkylene oxide and having an OH equivalent weight (Hydroxyl equivalent weight) within a specific range. It is manufactured by reacting a mixture containing the composition and epihalohydrin at a weight ratio within a specific range, and exhibits excellent environmental friendliness, high manufacturing yield, increased reactivity, and improved usability due to the liquid phase, and when used in a curable epoxy resin composition, its hardening It relates to an epoxy resin composition capable of improving shear strength by increasing the crosslinking density of water, a method of manufacturing the same, and a curable epoxy resin composition containing the same and a cured product thereof.

Description

Epoxy resin composition derived from a polyol composition prepared by adding alkylene oxide to an anhydrous sugar alcohol composition crosslinked with an epoxy compound modified into rubber, a method for producing the same, and a curable epoxy resin composition containing the same and a cured product thereof {Epoxy resin composition derived from polyol composition prepared by adding alkylene oxide to anhydrosugar alcohol composition crosslinked with epoxy compound modified with rubber, and method for preparing the same, and curable epoxy resin composition comprising the same and cured product thereof}

The present invention relates to an epoxy resin composition derived from a polyol composition prepared by adding an alkylene oxide to an anhydrous sugar alcohol composition crosslinked with an epoxy compound modified into rubber, a method for producing the same, a curable epoxy resin composition containing the same, and a cured product thereof. More specifically, it is a polyol obtained by crosslinking an anhydrous sugar alcohol composition derived from biomass with an epoxy compound modified into rubber and then adding alkylene oxide and having an OH equivalent weight (Hydroxyl equivalent weight) within a specific range. It is manufactured by reacting a mixture containing the composition and epihalohydrin at a weight ratio within a specific range, and exhibits excellent environmental friendliness, high manufacturing yield, increased reactivity, and improved usability due to the liquid phase, and when used in a curable epoxy resin composition, its hardening It relates to an epoxy resin composition capable of improving shear strength by increasing the crosslinking density of water, a method of manufacturing the same, and a curable epoxy resin composition containing the same and a cured product thereof.

Epoxy resin has excellent heat resistance, mechanical properties, electrical properties and adhesive properties. Taking advantage of this characteristic, epoxy resin is used for encapsulation 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 extensive use as thermosets in many applications. They are used as a thermoset matrix in prepregs consisting of fibers embedded in a thermoset matrix. Additionally, due to their toughness, flexibility, adhesion and chemical resistance, they can be used as materials for surface coatings, for bonding, forming and laminating, all of which have applications in aerospace, automotive, electronics, construction, furniture, green energy and sporting goods. A variety of applications can be found in a wide range of different industrial sectors such as industry.

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

An epoxy resin is a chemical unit of molecules that compose it and necessarily has an epoxy bond. A representative example is one made by polymerizing epichlorohydrin and bisphenol A. Epoxy resin is never used alone, and is used by adding a hardener to change it into a thermoset material, so it would be appropriate to think of it as an intermediate to an ordinary resin. In other words, a cured product cannot be obtained using only epoxy resin, and a thermosetting structure can be obtained only by combining with an epoxy reactor to form immovable crosslinking points.

Substances that create these crosslinking points are called hardeners. Hardeners that can be used with epoxy resin include phenol, acid anhydride, and amine. Among them, since phenol can have various structures, various changes in physical properties obtained by changing the epoxy resin can also be obtained by changing the structure of the phenol-based resin curing agent. Due to these various properties, phenol-based resin curing agents are currently mainly used. It is being used. However, problems are arising due to free phenol present in phenol resin. Although free phenol disappears after hardening, problems are being raised about its use because it threatens the health of workers during work.

Hydrogenated sugar (also called “sugar alcohol”) refers to a compound obtained by adding hydrogen to the reducing terminal group of a saccharide, and is generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer from 2 to 5) ) and is classified into tetritol, pentitol, hexitol, and heptitol (carbon numbers 4, 5, 6, and 7, respectively) depending on the carbon number. Among them, hexitol with 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

Anhydrous sugar alcohol is a substance formed by removing one or more water molecules from the inside of a hydrogenated sugar. When one water molecule is removed, it takes the form of tetraol, which has 4 hydroxyl groups in the molecule, and has 2 water molecules. When removed, it has a diol form with two hydroxy groups in the molecule, and can be manufactured using hexitol derived from starch (e.g., Korean Patent No. 10-1079518, Korean Patent Publication No. No. 10-2012-0066904). Since anhydrous sugar alcohol is an eco-friendly material derived from renewable natural resources, there has been a lot of interest for a long time and research on its production method has been conducted. Among these anhydrous sugar alcohols, isosorbide prepared from sorbitol currently has the widest range of industrial applications.

The uses of anhydrous sugar alcohol are very diverse, including treatment of heart and blood vessel diseases, adhesive for patches, pharmaceuticals such as mouthwash, solvent for compositions in the cosmetics industry, and emulsifier 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 very useful in the plastic industry such as bioplastics. useful. It is also known to be used as an eco-friendly solvent for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

As such, non-sugar alcohol is receiving a lot of attention due to its diverse potential for use, and its use in actual industry is gradually increasing.

Republic of Korea Patent Publication No. 10-2016-0010133 discloses an eco-friendly epoxy resin obtained by reacting isosorbide, an anhydrous sugar alcohol, with epichlorohydrin. However, the epoxy resin obtained by the method disclosed in the above-mentioned published patent has a low crosslinking density of the cured product when cured after mixing with a curing agent, and thus exhibits poor shear strength, and is therefore not suitable for use as an adhesive.

Therefore, there is a need for the development of an epoxy resin material that is environmentally friendly and can exhibit improved shear strength due to the high crosslinking density of the cured product.

The object of the present invention is to provide an epoxy resin composition that utilizes an anhydrous sugar alcohol composition derived from biomass, is excellent in environmental friendliness, and can improve the adhesion of the cured product when cured after mixing with a curing agent, and a method for producing the same, and a method for producing the same. To provide a curable epoxy resin composition and a cured product thereof.

The first aspect of the present invention is an epoxy resin composition, which is manufactured by reacting a mixture containing a polyol composition and epihalohydrin, and the polyol composition is manufactured by addition reacting a crosslinked anhydrous sugar alcohol composition with alkylene oxide. The crosslinked anhydrous sugar alcohol composition is prepared from a crosslinking reaction of the anhydrous sugar alcohol composition and a rubber-modified epoxy compound, and the anhydrous sugar alcohol composition includes first to fifth polyol components, wherein the first The polyol component is monoanhydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, the third polyol component is a polysaccharide alcohol represented by the following formula (1), and the fourth polyol component is a polysaccharide alcohol represented by the following formula (1) It is an anhydrous sugar alcohol formed by removing water molecules from, the fifth polyol component is at least one polymer selected from the first to fourth polyol components, and the OH equivalent weight (Hydroxyl equivalent weight) of the polyol composition is 251 to 251. 2,035 g/eq, and the content of the epihalohydrin in the mixture is greater than 90 parts by weight and less than 4,600 parts by weight based on 100 parts by weight of the polyol composition.

[Formula 1]

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

A second aspect of the present invention is a method for producing an epoxy resin composition, comprising reacting a mixture containing a polyol composition and an epihalohydrin, wherein the polyol composition is a crosslinked anhydrous sugar alcohol composition and an alkylene It is manufactured by addition reaction of oxide, and the crosslinked anhydrous sugar alcohol composition is prepared from a crosslinking reaction of anhydrous sugar alcohol composition and a rubber-modified epoxy compound, and the anhydrous sugar alcohol composition includes the first to fifth polyol components. Here, the first polyol component is monoanhydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, the third polyol component is a polysaccharide alcohol represented by the formula 1, and the fourth polyol component is the formula It is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by 1, the fifth polyol component is one or more polymers selected from the first to fourth polyol components, and the OH equivalent (Hydroxyl) of the polyol composition equivalent weight) is 251 to 2,035 g/eq, and the content of the epihalohydrin in the mixture is greater than 90 parts by weight to less than 4,600 parts by weight based on 100 parts by weight of the polyol composition. Method for producing an epoxy resin composition provides.

A third aspect of the present invention is an epoxy resin composition according to the first aspect of the present invention; It provides a curable epoxy resin composition comprising; and a curing agent.

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

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

Since the epoxy resin composition according to the present invention can be manufactured using anhydrous sugar alcohol composition, which is a by-product obtained in the process of producing internal dehydration of hydrogenated sugar, it improves economic efficiency and improves eco-friendliness by solving the by-product disposal problem. It can be manufactured at a high yield, shows increased reactivity, has improved usability because it is obtained in a liquid form, and can improve the adhesion of the cured product when cured after mixing with a curing agent, increasing the adhesive strength of the adhesive using this. (In particular, shear strength) can be significantly improved.

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

[Epoxy resin composition]

The epoxy resin composition according to the first aspect of the present invention is prepared by reacting a mixture containing a polyol composition and epihalohydrin, wherein the polyol composition is obtained by addition reaction of a crosslinked anhydrous sugar alcohol composition and alkylene oxide. The crosslinked anhydrous sugar alcohol composition is prepared from a crosslinking reaction between the anhydrous sugar alcohol composition and a rubber-modified epoxy compound, and the polyol composition has an OH equivalent weight (Hydroxyl equivalent weight) of 251 to 2,035 g/eq, The content of the epihalohydrin in the mixture is greater than 90 parts by weight and less than 4,600 parts by weight based on 100 parts by weight of the polyol composition.

If the OH equivalent weight of the polyol composition is less than 251 g/eq, when the epoxy resin composition prepared using such polyol composition is mixed with a curing agent, the tensile strength of the cured product decreases, resulting in poor shear strength, and also the production yield of the epoxy resin composition There is a problem with this degradation. On the other hand, if the OH equivalent weight of the polyol composition exceeds 2,035 g/eq, when the epoxy resin composition prepared using such polyol composition is mixed with a curing agent, the adhesion of the cured product is insufficient, resulting in poor shear strength, and also the epoxy resin composition There is a problem that the manufacturing yield decreases.

In one embodiment, the OH equivalent weight of the polyol composition may be, for example, 251 g/eq or more, 252 g/eq or more, or 253 g/eq or more, and may also be 2,035 g/eq or less, 2,030 g/eq or less, and 2,025 g. /eq or less, 2,020 g/eq or less, 2,015 g/eq or less, 2,010 g/eq or less, 2,005 g/eq or less, 2,000 g/eq or less, or 1,995 g/eq or less, but is not limited thereto.

On the other hand, if the epihalohydrin content in the mixture containing the polyol composition and epihalohydrin is 90 parts by weight or less based on 100 parts by weight of the polyol composition, the epoxy resin in the reaction product is excessively polymerized due to chain extension. When mixed with a hardener, a hardening reaction does not occur. On the other hand, if the epihalohydrin content in the mixture is 4,600 parts by weight or more based on 100 parts by weight of the polyol composition, the molecular weight of the epoxy resin in the reaction product increases, and as a result, the tensile strength of the cured product decreases when mixed with the curing agent, causing shearing. There is a problem that the strength is poor, and the manufacturing yield of the epoxy resin composition is lowered due to the use of an excessive amount of epihalohydrin, resulting in lower productivity.

In one embodiment, the epihalohydrin content in the mixture containing the polyol composition and epihalohydrin is, for example, more than 90 parts by weight, more than 91 parts by weight, and 100 parts by weight, based on 100 parts by weight of the polyol composition. parts by weight or more, 110 parts by weight or more, 120 parts by weight or more, 130 parts by weight or more, 140 parts by weight or more, 150 parts by weight or more, 160 parts by weight or more, 170 parts by weight or more, or 180 parts by weight or more, and also less than 4,600 parts by weight. , 4,500 parts by weight or less, 4,400 parts by weight or less, 4,300 parts by weight or less, 4,200 parts by weight or less, 4,100 parts by weight or less, 4,000 parts by weight or less, 3,900 parts by weight, 3,800 parts by weight or less, 3,700 parts by weight or less, or 3,600 parts by weight or less. However, it is not limited to this.

The anhydrous sugar alcohol composition, rubber-modified epoxy compound, alkylene oxide, and epihalohydrin used in the production of the epoxy resin composition will be described in more detail below.

Anhydrosugar alcohol composition

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

The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is monoanhydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component has the formula below: It is a polysaccharide alcohol represented by 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 one of the first to fourth polyol components. It is one or more polymers selected from among.

[Formula 1]

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

Monohydrosugar alcohol, which is the first polyol component included in the anhydrosugar alcohol composition of the present invention; dianhydrosugar alcohol as the second polyol component; polysaccharide alcohol as the third polyol component; Anhydrosugar alcohol formed by removing water molecules from polysaccharide alcohol, which is the fourth polyol component; and one or more polymers selected from the first to fourth polyol components, which are the fifth polyol component, preferably two or more, more preferably all of them, to form a glucose-containing saccharide composition (e.g., glucose , a saccharide composition containing disaccharides or more polysaccharides including mannose, fructose, and maltose) is subjected to a hydrogenation reaction to prepare a hydrogenated sugar composition, the obtained hydrogenated sugar composition is heated under an acid catalyst to undergo a dehydration reaction, and the obtained dehydration reaction product is It can be obtained in the process of manufacturing 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 thin-film distillation of the obtained dehydration reaction product to obtain a thin-film distillate.

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 hydroxy groups in the molecule. In the present invention, the type of monosugar alcohol is not particularly limited, but is preferably monosususu 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 of these.

Dianhydrosugar alcohol, which is the second polyol component, is anhydrosugar alcohol formed by removing two water molecules from the inside of a hydrogenated sugar, has a diol form with two hydroxy groups in the molecule, and is made of hexitol derived from starch. It can be manufactured using Since dianhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, there has been a lot of interest for a long time and research on its production method has been conducted. 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 is preferably dianhydrosugar hexitol, and more specifically, 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

In one embodiment, the polysaccharide alcohol represented by Formula 1, which is the third polyol component, can be produced from a hydrogenation reaction of disaccharides or more polysaccharides, including maltose.

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

[Formula 2]

[Formula 3]

In Formulas 2 and 3, n is each independently an integer from 0 to 4.

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

- 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,

- condensation polymerization reaction of the second polyol component, the third polyol component and the 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 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 anhydrosugar alcohol composition is 1.13 to 3.41;

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

In one embodiment, 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 may also be 1,589 or less, 1,560 or less. , may be 1,550 or less, 1,520 or less, 1,500 or less, 1,490 or less, or 1,480 or less. In addition, 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 even more specifically It may be 202 to 1,500, and more specifically, it may be 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 containing a cured product of an epoxy resin composition manufactured using such anhydrous sugar alcohol composition may become poor.

In one embodiment, the polydispersity index (PDI) of the anhydrosugar alcohol composition may be 1.13 or higher, 1.15 or higher, 1.20 or higher, 1.23 or higher, or 1.25 or higher, and may also be 3.41 or lower, 3.40 or lower, 3.35 or lower, 3.30 or lower, 3.25 or lower. It may be 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 even more. Specifically, it may be 1.20 to 3.25, and even more specifically, it may be 1.23 to 3.22. If the polydispersity index of the anhydrosugar alcohol composition exceeds the above-mentioned level, the adhesive strength of an adhesive containing a cured product of an epoxy resin composition manufactured using such anhydrosugar alcohol composition may become poor.

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 may be 21.36 or more. Hereinafter, it may be 21.30 or less, 21.0, 20.5 or less, 20.0 or less, 19.95 or less, or 19.92 or less. In addition, in one embodiment, the average number of -OH groups per molecule in the anhydrosugar alcohol composition may be 2.54 to 21.36, more specifically 2.60 to 21.30, and even more specifically 2.65 to 21.36. It could be 21.0. If the average number of -OH groups per molecule in the anhydrous sugar alcohol composition exceeds the above-described level, the adhesive strength of the adhesive containing the cured product of the epoxy resin composition manufactured using such anhydrous sugar alcohol composition may become poor. .

In one embodiment, the anhydrous sugar alcohol composition contains, for example, 0.1 to 20% by weight of the first polyol component, specifically 0.6 to 20% by weight, more specifically 0.7 to 15% by weight, based on the total weight of the composition. may be included, and the second polyol component may be included in an amount of 0.1 to 28% by weight, specifically 1 to 25% by weight, and 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 60% by weight. It may be included at 89.9% by weight, more specifically 70 to 89.9% by weight, but is not particularly limited thereto.

In one embodiment, the anhydrous sugar alcohol composition is produced by hydrogenating a glucose-containing saccharide composition (e.g., a saccharide composition comprising glucose; mannose; fructose; and disaccharides or more polysaccharides including maltose) to produce a hydrogenated sugar composition; , the obtained hydrogenated sugar composition may be heated under an acid catalyst to undergo a dehydration reaction, and the obtained dehydration reaction product may be manufactured by thin film distillation. More specifically, the obtained dehydration reaction product may be thin film distilled to obtain a thin film distillate. Afterwards, the remaining by-products may be.

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° C. to 135° C. to produce a hydrogenated sugar composition, and dehydration of the obtained hydrogenated sugar composition. The reaction is performed 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 heating conditions of 150°C to 175°C. It may be performed under heating conditions, but is not limited thereto.

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

In one embodiment, the content of polysaccharide alcohol (disaccharide or more saccharide alcohol) included in the hydrogenated sugar composition is the total dry weight of the hydrogenated sugar composition (where dry weight refers to the weight of solids remaining after removing moisture from the hydrogenated sugar composition). (Based on), it may be 0.8% by weight or more, 1% by weight, 2% by weight, or 3% by weight or more, and may be 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 anhydrous sugar alcohol composition includes 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 compound, styrene-butadiene modified epoxy compound, epoxy-terminated butadiene acrylonitrile modified epoxy compound, amine-terminated butadiene acrylonitrile modified epoxy compound, hydroxy-terminated butadiene acrylonitrile modified epoxy compound or these. It may be one or more selected from the group consisting of a combination of, but is not limited to this. 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 that crosslinks with the anhydrous sugar alcohol composition may be more than 5 parts by weight and 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 become poor. On the other hand, even when the amount of the crosslinking rubber-modified epoxy compound 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 The adhesive strength of the adhesive included may become poor.

In one embodiment, the amount of the rubber-modified epoxy compound that crosslinks with the anhydrous sugar alcohol composition is, for example, more than 5 parts by weight, more than 6 parts by weight, more than 7 parts by weight, and 8 parts by weight, based on 100 parts by weight of the anhydrous sugar alcohol composition. It may be more than 9 parts by weight or more than 10 parts by weight, and may also be less than 55 parts by weight, less than 54 parts by weight, less than 53 parts by weight, less than 52 parts by weight, less than 51 parts by weight, or less than 50 parts by weight, but is not limited thereto. No.

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, may be 1.65 to 6.11. When the number average molecular weight and polydispersity index of the crosslinked anhydrous sugar alcohol composition are within the above range, the adhesive performance of an adhesive containing a cured epoxy resin cured with a polyol composition prepared using the crosslinked anhydrous sugar alcohol composition is improved. can be advantageous.

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, It may also 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. In addition, 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 may also be 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 ( 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 for 1 to 8 hours, but is not limited thereto.

alkylene oxide

In the present invention, the “polyol composition” is produced by addition reaction of the crosslinked anhydrous sugar alcohol composition and alkylene oxide.

That is, in the present invention, the polyol composition includes an adduct obtained by reacting alkylene oxide with a hydroxy group at one terminal or more 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 anhydrosugar alcohol-alkylene glycol”), and a second polyol component crosslinked with a rubber-modified epoxy compound. alkylene oxide adduct of a third polyol component crosslinked with a rubber-modified epoxy compound (hereinafter referred to as “second crosslinked anhydrosugar alcohol-alkylene glycol”) (hereinafter referred to as “second crosslinked anhydrosugar alcohol-alkylene glycol”) 3, referred to as “crosslinked anhydrosugar alcohol-alkylene glycol”), an alkylene oxide adduct of the fourth polyol component crosslinked with a rubber-modified epoxy compound (hereinafter referred to as “fourth crosslinked anhydrosugar 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 anhydrosugar alcohol-alkylene glycol”).

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

If the amount of alkylene oxide added to 100 parts by weight of the crosslinked anhydrous sugar alcohol composition is 50 parts by weight or less, when curing the epoxy resin with the resulting polyol composition, the reaction activity between the components of the polyol composition and the epoxy resin is If it is low, the reaction may not proceed sufficiently, and as a result, the adhesive strength of the adhesive containing the cured product of the epoxy resin may become poor.

In one embodiment, the amount of alkylene oxide added to 100 parts by weight of the crosslinked anhydrous sugar alcohol composition is, for example, greater 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. , may be 90 parts by weight or more or 100 parts by weight or more, but is not limited thereto.

There is no particular limit to the upper limit of the amount of alkylene oxide reacting per 100 parts by weight of the crosslinked anhydrous sugar alcohol composition, but if it is too much, the adhesive strength (particularly, the shear strength) of the adhesive containing the cured epoxy resin cured with the resulting polyol composition may decrease. ) can become poor. In this respect, the amount of alkylene oxide added to 100 parts by weight of the crosslinked anhydrous sugar alcohol composition may be, for example, less than 4,300 parts by weight or less than 4,200 parts by weight, but is not limited thereto.

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

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

Epihalohydrin

The epoxy resin composition according to the first aspect of the present invention is prepared by reacting a mixture containing the polyol composition described above and epihalohydrin.

That is, the epoxy resin composition according to the first aspect of the present invention is a reaction product of the first crosslinked anhydrosugar alcohol-alkylene glycol and epihalohydrin, and the second crosslinked anhydrosugar alcohol-alkylene glycol. and epihalohydrin, the reaction product of a third cross-linked anhydrosugar alcohol-alkylene glycol and epihalohydrin, and the fourth cross-linked anhydrosugar alcohol-alkylene glycol and epihalohydrin. and the reaction product of a fifth crosslinked anhydrosugar alcohol-alkylene glycol and epihalohydrin.

In one embodiment, the epihalohydrin may be an epihalohydrin substituted or unsubstituted with an alkyl group (e.g., C1-C4 alkyl), and it is environmentally friendly because it is a bio-based compound derived from biomass raw materials. From this point of view, it is desirable.

In one embodiment, the epihalohydrin is epichlorohydrin, epibromohydrin, epiiodohydrin, methyl epichlorohydrin, methyl epibromohydrin, methyl epiiodohydrin, or a combination thereof. It may be one or more selected from the group consisting of, but is not limited to this.

In one embodiment, the epoxy equivalent weight of the epoxy resin composition prepared by reacting the polyol composition described above with a mixture containing epihalohydrin may be 375 to 2,879 g/eq. If the epoxy equivalent weight of the epoxy resin composition is excessively lower than the above level, the adhesion of the adhesive containing the cured product of the epoxy resin composition may become poor and the manufacturing yield of the epoxy resin composition may be reduced, and conversely, if it is excessively higher than the above level, the When mixing an epoxy resin composition with a curing agent, a curing reaction may not occur.

More specifically, the epoxy equivalent weight of the epoxy resin composition may be, for example, 375 g/eq or more, 376 g/eq or more, or 377 g/eq or more, and may also be 2,879 g/eq or less, 2,850 g/eq or less, 2,800 g/eq or less. eq or less, 2,750 g/eq or less, or 2,711 g/eq or less, but is not limited thereto.

[Method for producing epoxy resin composition]

According to a second aspect of the present invention, a method for producing the epoxy resin composition according to the first aspect of the present invention is provided.

The method for producing an epoxy resin composition of the present invention includes reacting a mixture containing a polyol composition and epihalohydrin, wherein the polyol composition and epihalohydrin are as described above, and The epihalohydrin content in the mixture is greater than 90 parts by weight and less than 4,600 parts by weight based on 100 parts by weight of the polyol composition, and the epihalohydrin content in this mixture is the same as previously described.

In one embodiment, the reaction of the mixture containing the polyol composition and epihalohydrin may be performed in the presence of a catalyst. More specifically, the catalyst may be a basic compound, and more specifically, it may be an alkali metal salt, such as an alkali metal hydroxide such as sodium hydroxide (caustic soda), potassium hydroxide, or a combination thereof, but is not limited thereto.

In one embodiment, the amount of the catalyst used may be, for example, 10 to 99 parts by weight, more specifically 10 to 90 parts by weight, and even more specifically 20 parts by weight, based on 100 parts by weight of the polyol composition. It may be from 80 parts by weight, but is not limited thereto. If the amount of catalyst used is too less than the above level, the curing reaction may not occur, and conversely, if the amount of catalyst used is too much than the above level, unreacted catalyst may remain in the reaction product and affect its physical properties.

In one embodiment, the reaction of the mixture containing the polyol composition and epihalohydrin may be performed under room temperature to elevated temperature conditions, for example, 30 to 100°C, more specifically, 50 to 90°C. It may be performed under temperature conditions, but is not limited thereto.

In one embodiment, the reaction of the mixture containing the polyol composition and epihalohydrin may be performed under normal pressure or reduced pressure conditions, for example, normal pressure or reduced pressure conditions of 300 to 80 Torr, more specifically, normal pressure or 200 Torr. It may be performed under reduced pressure conditions of 100 Torr to 100 Torr, but is not limited thereto.

In one embodiment, the reaction of the mixture containing the polyol composition and epihalohydrin may be performed, for example, for 1 to 12 hours, more specifically for 2 to 10 hours, and even more specifically for 3 to 12 hours. It can be performed for 8 hours, but is not limited to this.

According to one embodiment of the present invention, the reaction of the mixture containing the polyol composition and epihalohydrin may be performed in a two-step reaction method consisting of a preliminary reaction and a main reaction.

In one embodiment, the preliminary reaction is performed after adding a relatively small amount of the above-described catalyst (for example, 1 to 10 parts by weight based on 100 parts by weight of the polyol composition) to a mixture containing the polyol composition and epihalohydrin. , can be performed for 1 to 3 hours under elevated temperature conditions (eg, 70 to 100°C) and normal pressure conditions.

In addition, in one embodiment, the main reaction is performed by adding a relatively large amount of catalyst (e.g., 20 to 80 parts by weight based on 100 parts by weight of the polyol composition) to the result of the preliminary reaction and then subjecting the catalyst to elevated temperature conditions (e.g., 50 parts by weight). to 90° C.) and reduced pressure conditions (e.g., 200 to 100 Torr) for 2 to 9 hours.

In the method for producing an epoxy resin composition of the present invention, while the reaction (more specifically, the main reaction) of the mixture containing the polyol composition and epihalohydrin is performed, water generated during the reaction is continuously released from the reaction mixture. can be removed. This removal of water may be performed using, for example, a decanter, but is not limited thereto.

The method for producing an epoxy resin composition of the present invention may further include the step of removing unreacted epihalohydrin from the reaction product after completion of the reaction between the polyol composition and the mixture containing epihalohydrin. Removal of such unreacted epihalohydrin may be performed under elevated temperature conditions (eg, 120 to 180° C.) and reduced pressure conditions (eg, 50 to 1 Torr), but is not limited thereto. The unreacted epihalohydrin removed can be recovered and reused.

[Curable epoxy resin composition, its cured product, and adhesive containing this cured product]

According to another aspect of the present invention, the epoxy resin composition according to the first aspect of the present invention; A curable epoxy resin composition is provided, including a curing agent.

In one embodiment, the curing agent may be one or more selected from the group consisting of anhydrous sugar alcohol, phenol-based compound, acid anhydride-based compound, amine-based compound, or a combination thereof, and more specifically, may be anhydrous sugar alcohol, More specifically, it may be isosorbide.

In one embodiment, the equivalent ratio of the curing agent to the epoxy resin composition of the present invention in the curable epoxy resin composition (equivalent weight of curing agent/equivalent weight of epoxy resin composition) may be, for example, 0.9 to 1.1, and more specifically, 0.92 to 1.1. It may be 1.08, and more specifically, it may be 0.95 to 1.05. If the equivalent weight of the curing agent relative to the equivalent weight of the epoxy resin composition is too small, there may be a problem of reduced mechanical strength and physical properties in terms of adhesive strength. Conversely, if the equivalent weight of the curing agent relative to the equivalent weight of the epoxy resin composition is too high, the mechanical strength may decrease. There may be a problem of deterioration of physical properties in terms of strength, thermal and adhesive strength.

In one embodiment, the curable 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 (e.g., tertiary amines) such as benzyldimethylamine, tris(dimethylaminomethyl)phenol, and dimethylcyclohexylamine; Imidazole-based compounds such as 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-methylimidazole; Organophosphorus compounds such as triphenylphosphine and triphenyl phosphite; Quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide; Diazabicycloalkenes such as 1,8-diazabicyclo[5.4.0]undecene-7 and organic acid salts thereof; Organometallic compounds such as zinc octylate, tin octylate, and aluminum acetylacetone complex; Quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide; Boron compounds such as boron trifluoride and triphenyl borate; Metal halides such as zinc chloride and stannic chloride; Latent curing catalyst (e.g., dicyandiamide, a high-melting point dispersible latent amine adduct obtained by adding an amine to an epoxy resin, etc.; a microcapsule-type latent catalyst in which the surface of an imidazole-based, phosphorus-based, or phosphine-based accelerator is coated with a polymer ; amine salt type latent catalyst; high temperature dissociation type thermal cation polymerization type latent catalyst such as Lewis acid salt, Bronsted salt, etc.) and combinations thereof, but is not limited thereto.

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

When a curing catalyst is included in the curable epoxy resin composition of the present invention, the amount used may be 0.01 parts by weight to 1.0 parts by weight, more specifically 0.05 parts by weight to 0.5 parts by weight, based on a total of 100 parts by weight of the epoxy resin composition and the curing agent. It may be parts by weight, and more specifically, it may be 0.08 parts by weight to 0.2 parts by weight, but it is not limited thereto. If the amount of curing catalyst used is too small, the curing reaction of the epoxy resin composition may not proceed sufficiently, which may lead to a problem of deterioration of mechanical and thermal properties. Conversely, if the amount of curing catalyst used is too large, the curing reaction may not proceed sufficiently even while the curable epoxy resin composition is stored. Because the curing reaction progresses slowly, there may be a problem of increased viscosity.

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

The antioxidant may be used to further improve the heat stability of the resulting cured product, and is not particularly limited, but includes, for example, phenol-based antioxidants (dibutylhydroxytoluene, etc.), sulfur-based antioxidants (mercaptopropionic acid derivatives, etc.) , phosphorus-based antioxidants (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.), and combinations thereof can be used. The content of the antioxidant in the curable epoxy resin 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 a total of 100 parts by weight of the epoxy resin composition and the curing agent.

The UV absorber is not particularly limited, and examples include benzotriazole-based UV absorbers such as TINUBIN P and TINUVIN 234 manufactured by BASF Japan Ltd.; Triazine-based UV absorbers such as TINUVIN 1577ED; One selected from the group consisting of hindered amine-based UV absorbers such as CHIMASSOLV 2020FDL and combinations thereof can be used. The content of the UV absorber in the curable epoxy resin 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 a total of 100 parts by weight of the epoxy resin composition and the curing agent.

The filler is used for the main purpose of improving the mechanical properties of the cured product by mixing it with an epoxy resin composition or curing agent, and generally, as the amount added increases, the mechanical properties improve. Inorganic fillers include extenders such as talc, sand, silica, talc, calcium carbonate, etc.; Reinforcing fillers such as mica, quartz, and glass fiber; There are special uses such as quartz powder, graphite, alumina, and Aerosil (for the purpose of imparting thixotropic properties), and metals such as aluminum, aluminum oxide, iron, iron oxide, and copper contribute to thermal expansion coefficient, wear resistance, thermal conductivity, and adhesiveness. There are those that provide flame retardancy, such as antimony oxide (SB ₂ O ₃ ), barium titanate, and lightweight fillers such as fine plastic spheres (phenol resin, urea resin, etc.) as organic substances. In addition, as fillers with reinforcing properties, various glass fibers and chemical fiber fabrics can be treated as fillers in a broad sense in the manufacture of laminated products. Thixotropic property of a resin (thixotropic or thixotropic) refers to the property of a resin that is attached to a vertical surface or immersed or impregnated into a laminate to be in a liquid state when flowing and in a solid state when stationary to prevent it from flowing or being lost during curing. fine particles with a large unit surface area are used to provide For example, colloidal silica (Aerosil) or bentonite-based clays are 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 can be used. The content of the filler in the curable epoxy resin 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 a total of 100 parts by weight of the epoxy resin composition and the curing agent.

The resin modifier is not particularly limited, and examples thereof include flexibility imparting agents such as polypropylene glycidyl ether, polymerized fatty acid polyglycidyl ether, polypropylene glycol, and urethane prepolymer. The content of the resin modifier in the curable epoxy resin 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 a total of 100 parts by weight of the epoxy resin composition and the curing agent.

The silane coupling agent is not particularly limited, but examples include chloropropyltrimethoxysilane, vinyltrichlorosilane, γmethacryloxypropyltrimethoxysilane, and γaminopropyltriethoxysilane. . The content of the silane coupling agent in the curable epoxy resin 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 a total of 100 parts by weight of the epoxy resin composition and the curing agent.

The diluent is used for the main purpose of lowering the viscosity by adding it to the epoxy resin composition or curing agent, and when used, it plays a role in improving flowability, defoaming, improving penetration into parts details, or effectively adding fillers. do. 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, the reactive diluent has one or more epoxy groups and participates in the reaction to form a cross-linked structure in the cured material, while the non-reactive diluent is only physically mixed and dispersed in the cured material. 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 DiButylPhthalate (DBP), DiOctylPhthalate (DOP), Nonyl-Phenol, and Hysol. In one embodiment, the diluent is not particularly limited, but includes, for example, n-butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, vinylcyclohexene dioxide, diglycidyl aniline, One selected from the group consisting of glycerin triglycidyl ether and combinations thereof may be used. The content of the diluent in the curable epoxy resin 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 a total of 100 parts by weight of the epoxy resin composition and the curing agent.

Pigments or dyes are used as colorants to add color to resin. Commonly used pigments include titanium dioxide, cadmium red, shining green, carbon black, chrome green, chrome yellow, navy blue, and shining blue.

In addition, antifoaming and defoaming agents used to remove air bubbles in the resin, dispersants to increase the dispersion effect between the resin and pigment, wetting agents to improve the adhesion between the epoxy resin and the material, and viscosity regulators. Various additives can be used, such as gloss control agents to control the gloss of the resin, additives to improve adhesion, additives to provide electrical properties, etc.

The method of curing the curable epoxy resin composition of the present invention is not particularly limited, and for example, conventionally known curing equipment 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 can be performed by conventionally known methods such as hot air circulation, infrared heating, and high frequency heating, for example.

Curing temperature and curing time may range from 30 seconds to 10 hours at 50°C to 250°C. In one specific example, pre-curing may be performed under conditions of 50°C to 120°C and 0.5 to 5 hours, and then post-curing may be performed under conditions of 120°C to 180°C and 0.1 to 5 hours. In another embodiment, primary curing is performed under conditions of 50°C to 85°C, 0.5 hours to 5 hours, secondary curing is performed under conditions of 85°C to 105°C, 0.5 hours to 5 hours, and 105°C to 145°C, 0.5 hours. The third hardening can be done under the conditions of time ~ 5 hours, and the fourth hardening can be done under the conditions of 145℃ ~ 180℃, 0.5 hours ~ 5 hours. In another embodiment, for short-term curing, curing may be performed under conditions of 150°C to 250°C and 30 seconds to 30 minutes.

In one embodiment, the curable epoxy resin composition of the present invention may be stored divided into two or more components, for example, a component containing a curing agent and a component containing the epoxy resin composition, and these may be combined before curing. In another specific example, the curable epoxy resin composition of the present invention may be stored as a thermosetting composition containing each component and used for curing as 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 curable epoxy resin composition of the present invention is provided.

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

The adhesive of the present invention may additionally include additives that can be 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 glucose

A liquid hydrogenated sugar composition with a concentration of 55% by weight (96% by weight of sorbitol, 0.9% by weight of mannitol based on solids) was obtained by hydrogenating a glucose product with a purity of 97% in the presence of a nickel catalyst, at a temperature of 125°C, and under a hydrogen pressure of 60 atm. % and 3.1% by weight of disaccharide or higher polysaccharide alcohol), 1,819 g was obtained, which was placed in a batch reactor equipped with a stirrer and concentrated by heating to 100°C, thereby obtaining 1,000 g of a concentrated hydrogenated sugar composition.

1,000 g of the concentrated hydrogenated sugar composition and 9.6 g of sulfuric acid were added to the reactor. Afterwards, the temperature inside the reactor was raised to about 135°C, and a dehydration reaction was performed under reduced pressure conditions 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 approximately 15.7 g of 50% aqueous sodium hydroxide solution was added to neutralize the reaction product. Afterwards, the temperature was cooled to 100°C or lower and concentrated for more than 1 hour under reduced pressure conditions 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 liquid by gas chromatography, the conversion content to isosorbide was 71.9% by weight, and through this, the molar conversion rate from sorbitol to isosorbide was calculated to be 77.6%.

831 g of the obtained anhydrous sugar alcohol conversion liquid was put into a thin film distiller (SPD) and distillation was performed. At this time, distillation was carried out at a temperature of 160°C and a vacuum pressure of 1 mbar, and approximately 589 g of distillate was obtained (distillation yield: approximately 70.9%). At this time, the purity of isosorbide in the distillate was measured to be 96.8%, and the distillation yield of isosorbide calculated from this was 95.3%. 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 (dianhydrosugar alcohol) [second polyol component] 11.5% by weight Alcohol) [first polyol component] 7.4% by weight, polysaccharide alcohol [third polyol component] represented by the above formula (1) and anhydrosugar alcohol derived therefrom (i.e., formed by removing water molecules from polysaccharide alcohol) [second polyol component] It contains 2.5% by weight of the polyol component of [No. 4] and 78.2% by weight of their polymer [the fifth polyol component], the number average molecular weight of the composition is 208 g/mol, the polydispersity index of the composition is 1.25, and the hydroxyl group of the composition is About 242 g of anhydrous sugar alcohol composition was obtained, with a value of 751 mg KOH/g and an average number of -OH groups per molecule in the composition of 2.78.

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

Production example, except that a 50.2% by weight glucose-containing saccharide composition (50.2% by weight glucose and 49.8% by weight total of mannose, fructose, and polysaccharides (disaccharides such as maltose) was used instead of a glucose product with 97% purity. The hydrogenation reaction was performed in the same manner as A1 to obtain 1,819 g of a liquid hydrogenated sugar composition with a concentration of 55% by weight (based on solids, 48.5% by weight of sorbitol, 3.6% by weight of mannitol, 47.9% by weight of disaccharide or higher polysaccharide alcohol), which was placed in a stirrer. It was placed in a batch reactor attached and concentrated by heating to 100°C, thereby obtaining 1,000 g of concentrated hydrogenated sugar composition.

1,000 of the above concentrated hydrogenated sugar composition, 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. g was converted into anhydrous sugar alcohol by performing a dehydration reaction in the same manner as in Preparation Example A1. The anhydrous sugar alcohol conversion liquid obtained as a result of the dehydration reaction was about 890 g, and as a result of analyzing the obtained anhydrous sugar alcohol conversion liquid by gas chromatography, the conversion content of isosorbide was 33.7% by weight, and through this, isosorbide was converted from sorbitol. The molar conversion of beads was calculated to be 77.1%.

Thin-film distillation was performed on 890 g of the obtained anhydrous sugar alcohol conversion liquid in the same manner as Preparation 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 from this was 98.3%. After separating the distillate, 0.9% by weight of isosorbide (dianhydrosugar alcohol), 2.1% by weight of isomannide (dianhydrosugar alcohol), 0.9% by weight of sorbitan (monohydrosugar alcohol), disaccharide or higher polysaccharide alcohols and derived from them. It contains 6.2% by weight of anhydrous sugar alcohol and 89.9% by weight of their polymer, the number average molecular weight of the composition is 1,480 g/mol, the polydispersity index of the composition is 3.19, and the hydroxyl value of the composition is 755 mg KOH/g. , about 586 g of anhydrous sugar alcohol composition with an average number of -OH groups per molecule in the composition of 19.92 was obtained.

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

Preparation Example B1: Preparation of anhydrous sugar alcohol composition crosslinked with a natural rubber (NR: Natural Rubber) modified epoxy compound (10 parts by weight of natural rubber modified epoxy compound used per 100 parts by weight of anhydrous sugar alcohol composition)

In a three-neck glass reactor equipped with a stirrer, 100.0 g of anhydrous sugar alcohol composition obtained in Preparation Example A1, 10.0 g of natural rubber modified epoxy compound (KR-909, Kukdo Chemical Co., Ltd.), and dibutyltin dilaurate as a reaction catalyst. 0.1 g (Aldrich (manufactured)) was added, the temperature inside the reactor was raised to 150°C, and the 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 anhydrous sugar alcohol composition was used to prepare the polyol composition described later without any additional treatment process.

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

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

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

104 g of the crosslinked anhydrous sugar alcohol composition was prepared in the same manner as Preparation Example B1, except that 100.0 g of the anhydrous sugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrous sugar alcohol composition obtained in Preparation Example A1. Obtained. The obtained anhydrous sugar alcohol composition was used to prepare the polyol composition described later without a separate treatment process.

Preparation Example B4: Preparation of anhydrous sugar alcohol composition crosslinked with natural rubber-modified epoxy compound (50 parts by weight of natural rubber-modified epoxy compound used 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 the natural rubber modified epoxy compound (KR-909, Kukdo Chemical Co., Ltd.) was adjusted to 10.0 g. Except for changing the weight to 50.0 g, the same method as Preparation Example B1 was performed to obtain 141 g of a cross-linked anhydrous sugar alcohol composition. The obtained anhydrous sugar alcohol composition was used to prepare the 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 (25 parts by weight of CTBN modified epoxy compound used per 100 parts by weight of anhydrosugar alcohol composition)

Except that 25.0 g of CTBN (Carboxyl-Terminated Butadiene-Acrylonitrile) modified epoxy compound (KR-818, manufactured by Kukdo Chemical) was used instead of natural rubber modified epoxy compound (KR-909, manufactured by Kukdo Chemical). , was carried out in the same manner as Preparation Example B1, to obtain 118 g of a cross-linked anhydrous sugar alcohol composition. The obtained anhydrous sugar alcohol composition was used to prepare the polyol composition described later without a separate treatment process.

Preparation Example B6: Preparation of anhydrous sugar alcohol composition crosslinked with natural rubber-modified epoxy compound (5 parts by weight of natural rubber-modified epoxy compound used 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 Preparation Example B1, except that the content of the natural rubber modified epoxy compound (KR-909, manufactured by Kukdo Chemical) was changed from 10.0 g to 5.0 g. Obtained. The obtained anhydrous sugar alcohol composition was used to prepare the polyol composition described later without a separate treatment process.

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

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

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

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

Preparation Example C1: Preparation of a polyol composition having an added content of 100 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar 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 internal temperature of 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 polyol composition was obtained.

Preparation Example C2: Preparation of a polyol composition having an added content of 4,200 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound.

By carrying out the same method as Preparation Example C1, except that the ethylene oxide content was changed from 100 g to 4,200 g, 4,090 g of polyol composition was obtained.

Preparation Example C3: Preparation of a polyol composition containing 100 parts by weight of propylene oxide per 100 parts by weight of 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 Preparation Example C1, except that 100 g of propylene oxide was used instead of ethylene oxide.

Preparation Example C4: Preparation of a polyol composition having an added content of 3,600 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound.

3,520 g of polyol composition was obtained in the same manner as Preparation Example C1, except that 3,600 g of propylene oxide was used instead of ethylene oxide.

Preparation Example C5: Preparation of a polyol composition having an added content of 100 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound.

195 g of polyol composition was obtained by carrying out the same method as Preparation C1, 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.

Preparation Example C6: Preparation of a polyol composition having an added content of 2,700 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound.

Preparation 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 the same method as C1, 2,745 g of polyol composition was obtained.

Preparation Example C7: Preparation of a polyol composition containing 100 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound.

Preparation Example C1, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B2 was used in place of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used in place of ethylene oxide. By performing the same method as above, 186 g of polyol composition was obtained.

Preparation Example C8: Preparation of a polyol composition having an added content of 2,300 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound.

Preparation example, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B2 was used in place of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 2,300 g of propylene oxide was used in place of ethylene oxide. By carrying out the same method as C1, 2,370 g of polyol composition was obtained.

Preparation Example C9: Preparation of a polyol composition having an added content of 100 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound.

180 g of polyol composition was obtained by carrying out the same method as Preparation C1, 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.

Preparation Example C10: Preparation of a polyol composition having an added content of 560 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

Preparation Example C1, 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 performing the same method as above, 602 g of polyol composition was obtained.

Preparation Example C11: Preparation of a polyol composition having an added content of 100 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound.

Preparation Example C1, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B3 was used in place of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used in place of ethylene oxide. By performing the same method as above, 185 g of polyol composition was obtained.

Preparation Example C12: Preparation of a polyol composition having an added content of 480 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound.

Preparation Example C1, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B3 was used in place of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 480 g of propylene oxide was used in place of ethylene oxide. By performing the same method as above, 507 g of polyol composition was obtained.

Preparation Example C13: Preparation of a polyol composition having an added content of 100 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound.

176 g of polyol composition was obtained by carrying out the same method as Preparation C1, 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. did.

Preparation Example C14: Preparation of a polyol composition having an added content of 550 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound.

Preparation Example C1, 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 performing the same method as above, 570 g of polyol composition was obtained.

Preparation Example C15: Preparation of a polyol composition containing 100 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound.

Preparation Example C1, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B4 was used in place of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used in place of ethylene oxide. By performing the same method as above, 181 g of polyol composition was obtained.

Preparation Example C16: Preparation of a polyol composition having an added content of 750 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound.

Preparation Example C1, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B4 was used in place of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 750 g of propylene oxide was used in place of ethylene oxide. By performing the same method as above, 822 g of polyol composition was obtained.

Preparation Example C17: Preparation of a polyol composition having an added content of 100 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 25 parts by weight of a CTBN-modified epoxy compound.

Preparation Example C1, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B5 was used in place of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used in place of ethylene oxide. By performing the same method as above, 190 g of polyol composition was obtained.

Preparation Example C18: Preparation of a polyol composition having an added content of 50 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound.

144g of polyol composition was obtained by carrying out the same method as Preparation Example C1, except that the ethylene oxide content was changed from 100g to 50g.

Preparation Example C19: Preparation of a polyol composition having an added content of 4,300 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound

By carrying out the same method as Preparation Example C1, except that the ethylene oxide content was changed from 100 g to 4,300 g, 4,220 g of polyol composition was obtained.

Preparation Example C20: Preparation of a polyol composition having an added content of 50 parts by weight of propylene oxide per 100 parts by weight of 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 Preparation Example C1, except that 50 g of propylene oxide was used instead of ethylene oxide.

Preparation Example C21: Preparation of a polyol composition having an added content of 3,700 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 10 parts by weight of a natural rubber-modified epoxy compound.

3,210 g of polyol composition was obtained by carrying out the same method as Preparation Example C1, except that 3,700 g of propylene oxide was used instead of ethylene oxide.

Preparation Example C22: Preparation of a polyol composition having an added content of 50 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound.

Preparation Example C1, 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 performing the same method as above, 125 g of polyol composition was obtained.

Preparation Example C23: Preparation of a polyol composition having an added content of 2,800 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound.

Preparation 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 the same method as C1, 2,150 g of polyol composition was obtained.

Preparation Example C24: Preparation of a polyol composition having an added content of 50 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound.

Preparation Example C1, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B2 was used in place of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 50 g of propylene oxide was used in place of ethylene oxide. By performing the same method as above, 130 g of polyol composition was obtained.

Preparation Example C25: Preparation of a polyol composition having an added content of 2,400 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 50 parts by weight of a natural rubber-modified epoxy compound.

Preparation example, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B2 was used in place of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 2,400 g of propylene oxide was used in place of ethylene oxide. By carrying out the same method as C1, 2,150 g of polyol composition was obtained.

Preparation Example C26: Preparation of a polyol composition having an added content of 100 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 5 parts by weight of a natural rubber-modified epoxy compound.

180 g of polyol composition was obtained by carrying out the same method as Preparation C1, 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.

Preparation Example C27: Preparation of a polyol composition having an added content of 4,200 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 5 parts by weight of a natural rubber-modified epoxy compound

Preparation 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 the same method as C1, 4,015 g of polyol composition was obtained.

Preparation Example C28: Preparation of a polyol composition containing 100 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 5 parts by weight of a natural rubber-modified epoxy compound.

Preparation Example C1, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B6 was used in place of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used in place of ethylene oxide. By performing the same method as above, 180 g of polyol composition was obtained.

Preparation Example C29: Preparation of a polyol composition having an added content of 3,600 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 5 parts by weight of a natural rubber-modified epoxy compound.

Preparation example, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B6 was used in place of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 3,600 g of propylene oxide was used in place of ethylene oxide. By carrying out the same method as C1, 3,480 g of polyol composition was obtained.

Preparation Example C30: Preparation of a polyol composition having an added content of 100 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 55 parts by weight of a natural rubber-modified epoxy compound.

175 g of polyol composition was obtained by carrying out the same method as Preparation C1, 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.

Preparation Example C31: Preparation of a polyol composition having an added content of 2,700 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 55 parts by weight of a natural rubber-modified epoxy compound.

Preparation 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 the same method as C1, 2,540 g of polyol composition was obtained.

Preparation Example C32: Preparation of a polyol composition containing 100 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 55 parts by weight of a natural rubber-modified epoxy compound.

Preparation Example C1, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B7 was used in place of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used in place of ethylene oxide. By performing the same method as above, 180 g of polyol composition was obtained.

Preparation Example C33: Preparation of a polyol composition having an added content of 2,300 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition crosslinked with 55 parts by weight of a natural rubber-modified epoxy compound.

Preparation example, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B7 was used in place of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 2,300 g of propylene oxide was used in place of ethylene oxide. By carrying out the same method as C1, 2,200 g of polyol composition was obtained.

The reaction materials and amounts used in Preparation Examples C1 to C33, and the OH equivalent weight of the obtained polyol composition are shown in Table 2 below.

[Method of measuring physical properties]

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

(1) 5 g of each of the polyol compositions obtained in Preparation Examples C1 to C33 were dissolved in 100 ml of chloroform, then added to a 500 ml round flask containing 100 ml of acetic anhydride and 100 ml of pyridine and stirred for 3 days, The polyol composition obtained in C33 was acetylated. Afterwards, the acetylated polyol compositions were washed with water, and then the number average molecular weight of the polyol compositions was measured through gel permeation chromatography (GPC).

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

(2) After esterifying each polyol composition prepared in Preparation Examples C1 to C33 and excess phthalic anhydride under an imidazole catalyst according to ASTM D-4274D, a hydroxyl value test standard, the remaining anhydride By titrating phthalic acid with 0.5N sodium hydroxide (NaOH), the hydroxyl value (unit: mg KOH/g) of each polyol composition was measured.

(3) The OH equivalent weight of the polyol compositions obtained in Preparation Examples C1 to C33 was measured using the number average molecular weight and hydroxyl value of each polyol composition measured above.

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

<Manufacture of epoxy resin composition>

Example A1: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

100 g of the polyol composition of Preparation Example C1 and 180 g of epichlorohydrin were added to a 1,000 ml round bottom flask equipped with a decanter, a stirrer, and a nitrogen inlet, and were dissolved while raising the temperature to 80°C. When the solution in the system was completely dissolved, 11 g of 50% caustic soda aqueous solution was quantitatively injected over 2 hours to proceed with the preliminary reaction. Afterwards, the reaction was carried out by quantitatively injecting 109 g of a 50% caustic soda aqueous solution over 200 minutes at a temperature of 65°C and a reduced pressure of 120 Torr. Water generated during this reaction was continuously removed through a decanter. After completion of the main reaction, the reaction product was filtered under reduced pressure with filter paper, and the remaining resin was washed with acetone. The filtered reactant was gradually heated and reduced to a temperature of 150°C and 5 Torr to recover unreacted epichlorohydrin, thereby obtaining an epoxy resin composition. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 405 g/eq.

Example A2: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C2 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,704 g/eq.

Example A3: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C3 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 425 g/eq.

Example A4: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C4 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,704 g/eq.

Example A5: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C5 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 377 g/eq.

Example A6: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C6 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,674 g/eq.

Example A7: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C7 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 383 g/eq.

Example A8: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C8 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,660 g/eq.

Example A9: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C9 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 909 g/eq.

Example A10: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C10 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,711 g/eq.

Example A11: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C11 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 959 g/eq.

Example A12: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C12 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,711 g/eq.

Example A13: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C13 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 921 g/eq.

Example A14: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C14 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,711 g/eq.

Example A15: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C15 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 971 g/eq.

Example A16: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C16 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,643 g/eq.

Example A17: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C17 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 682 g/eq.

Example A18: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epibromohydrin per 100 parts by weight of polyol composition

The same method as Example A1 was performed, except that 100 g of the polyol composition of Preparation Example C17 was used instead of the polyol composition of Preparation Example C1, and 3,600 g of epibromohydrin was used instead of epichlorohydrin. A resin composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 806 g/eq.

Comparative Example A1: Epoxy resin composition prepared by addition reaction of 90 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

The same method as Example A1 was performed except that the amount of epichlorohydrin was changed from 180g to 90g, but at this time, the components in the reaction product were excessively polymerized due to chain extension, making it difficult to measure the epoxy equivalent. It was impossible, and the calculation of the manufacturing yield was meaningless.

Comparative Example A2: Epoxy resin composition prepared by addition reaction of 4,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C2 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 4,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,912 g/eq.

Comparative Example A3: Epoxy resin composition prepared by addition reaction of 90 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

The same method as Example A1 was performed, except that 100 g of the polyol composition of Preparation Example C3 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 90 g, but in this case, The components in the reaction product were excessively polymerized due to chain extension, making it impossible to measure the epoxy equivalent weight, and the calculation of the manufacturing yield was meaningless.

Comparative Example A4: Epoxy resin composition prepared by addition reaction of 4,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C4 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 4,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,912 g/eq.

Comparative Example A5: Epoxy resin composition prepared by addition reaction of 90 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

The same method as Example A1 was performed, except that 100 g of the polyol composition of Preparation Example C5 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 90 g, but in this case, The components in the reaction product were excessively polymerized due to chain extension, making it impossible to measure the epoxy equivalent weight, and the calculation of the manufacturing yield was meaningless.

Comparative Example A6: Epoxy resin composition prepared by addition reaction of 4,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C6 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 4,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,880 g/eq.

Comparative Example A7: Epoxy resin composition prepared by addition reaction of 90 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

The same method as Example A1 was performed, except that 100 g of the polyol composition of Preparation Example C7 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 90 g, but at this time, The components in the reaction product were excessively polymerized due to chain extension, making it impossible to measure the epoxy equivalent weight, and the calculation of the manufacturing yield was meaningless.

Comparative Example A8: Epoxy resin composition prepared by addition reaction of 4,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

The same method as Example A1 was performed, except that 100 g of the polyol composition of Preparation Example C8 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 4,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,864 g/eq.

Comparative Example A9: Epoxy resin composition prepared by addition reaction of 90 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

The same method as Example A1 was performed, except that 100 g of the polyol composition of Preparation Example C9 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 90 g, but in this case, The components in the reaction product were excessively polymerized due to chain extension, making it impossible to measure the epoxy equivalent weight, and the calculation of the manufacturing yield was meaningless.

Comparative Example A10: Epoxy resin composition prepared by addition reaction of 4,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C10 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 4,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,919 g/eq.

Comparative Example A11: Epoxy resin composition prepared by addition reaction of 90 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

The same method as Example A1 was performed, except that 100 g of the polyol composition of Preparation Example C11 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 90 g, but in this case, The components in the reaction product were excessively polymerized due to chain extension, making it impossible to measure the epoxy equivalent weight, and the calculation of the manufacturing yield was meaningless.

Comparative Example A12: Epoxy resin composition prepared by addition reaction of 4,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C12 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 4,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,919 g/eq.

Comparative Example A13: Epoxy resin composition prepared by addition reaction of 90 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

The same method as Example A1 was performed, except that 100 g of the polyol composition of Preparation Example C13 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 90 g, but in this case, The components in the reaction product were excessively polymerized due to chain extension, making it impossible to measure the epoxy equivalent weight, and the calculation of the manufacturing yield was meaningless.

Comparative Example A14: Epoxy resin composition prepared by addition reaction of 4,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C14 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 4,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,919 g/eq.

Comparative Example A15: Epoxy resin composition prepared by addition reaction of 90 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

The same method as Example A1 was performed, except that 100 g of the polyol composition of Preparation Example C15 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 90 g, but in this case, The components in the reaction product were excessively polymerized due to chain extension, making it impossible to measure the epoxy equivalent weight, and the calculation of the manufacturing yield was meaningless.

Comparative Example A16: Epoxy resin composition prepared by addition reaction of 4,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C16 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 4,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 868 g/eq.

Comparative Example A17: Epoxy resin composition prepared by addition reaction of 4,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C17 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 4,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 682 g/eq.

Comparative Example A18: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C18 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 371 g/eq.

Comparative Example A19: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C19 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 6,130 g/eq.

Comparative Example A20: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C20 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 372 g/eq.

Comparative Example A21: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C21 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 6,153 g/eq.

Comparative Example A22: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C22 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 228 g/eq.

Comparative Example A23: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C23 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,976 g/eq.

Comparative Example A24: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C24 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 229 g/eq.

Comparative Example A25: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C25 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,976 g/eq.

Comparative Example A26: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C26 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 374 g/eq.

Comparative Example A27: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was produced in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C27 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 5,630 g/eq.

Comparative Example A28: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C28 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 371 g/eq.

Comparative Example A29: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C29 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 5,630 g/eq.

Comparative Example A30: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C30 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 213 g/eq.

Comparative Example A31: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

The same method as Example A1 was performed, except that 100 g of the polyol composition of Preparation Example C31 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,894 g/eq.

Comparative Example A32: Epoxy resin composition prepared by addition reaction of 180 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin composition was obtained in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C32 was used instead of the polyol composition of Preparation Example C1. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 213 g/eq.

Comparative Example A33: Epoxy resin composition prepared by addition reaction of 3,600 parts by weight of epichlorohydrin per 100 parts by weight of polyol composition

An epoxy resin was prepared in the same manner as in Example A1, except that 100 g of the polyol composition of Preparation Example C33 was used instead of the polyol composition of Preparation Example C1, and the amount of epichlorohydrin was changed from 180 g to 3,600 g. The composition was obtained. At this time, the epoxy equivalent weight of the produced epoxy resin composition was 2,881 g/eq.

<Method for measuring physical properties of epoxy resin composition>

1. Measurement of epoxy equivalent weight of epoxy resin composition

1 g of measurement sample was collected from the epoxy resin compositions obtained in Examples A1 to A18 and Comparative Examples A2, A4, A6, A8, A10, A12, A14, and A16 to A33, placed in a 100 ml Erlenmeyer flask, and dioxane solution. After adding and dissolving 10 ml, 25 ml of 0.2N HCl-methanol solution was added and left at room temperature (25 ± 3°C) for 30 minutes. Afterwards, Cresol red solution was added as an indicator, and titration was performed using 0.1N NaOH-Methanol solution. The point at which it changed from purple to yellow and then back to purple was set as the end point, and the titration amount of 0.1N NaOH-Methanol solution consumed was determined. was measured.

In addition, the titration of the blank test was performed in the same manner as above, except that 1 g of the measurement sample was not used, and the appropriate amount of the consumed 0.1N NaOH-Methanol solution was measured.

The epoxy equivalent of the epoxy resin composition was calculated using the appropriate amount of 0.1N NaOH-Methanol solution in the titration test using 1 g of the measurement sample and the appropriate amount of 0.1N NaOH-Methanol solution in the blank test as shown in the following equation.

EEW = 10,000 x (W/BT-A) x F

In the above formula, EEW is the epoxy equivalent weight, its unit is g/eq, W is the weight of the measured sample, BT is the appropriate amount of 0.1N NaOH-Methanol solution in the blank test, and A is the measurement This is the appropriate amount of 0.1N NaOH-Methanol solution in a titration test using 1g of sample, and F is the normal concentration coefficient of 0.1N NaOH-Methanol solution.

2. Calculation of manufacturing yield of epoxy resin composition

The production yield of the epoxy resin compositions obtained in Examples A1 to A18 and Comparative Examples A2, A4, A6, A8, A10, A12, A14, and A16 to A33 was calculated as follows.

Manufacturing yield (%) = (Weight of produced epoxy resin composition / Total weight of polyol composition and epihalohydrin added during production)

The reaction materials and amounts used in Examples A1 to A18 and Comparative Examples A1 to A33, and the epoxy equivalent weight of the obtained epoxy resin composition are listed in Table 3 below.

<Preparation of curable epoxy resin composition>

Example B1: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A1

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A1 with 18 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine (DMBA, Sigma aldrich) as a catalyst.

Example B2: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A2

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A2 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and 100 parts by weight of the mixture was added. In contrast, 0.1 part by weight of N,N-dimethylbutylamine was added as a catalyst to prepare a curable epoxy resin composition.

Example B3: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A3

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A3 with 17 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B4: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A4

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A4 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B5: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A5

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A5 with 19 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B6: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A6

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A6 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B7: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A7

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A7 with 19 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B8: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A8

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A8 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B9: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A9

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A9 with 8 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B10: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A10

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A10 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B11: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A11

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A11 with 8 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B12: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A12

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A12 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B13: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A13

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A13 with 8 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B14: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A14

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A14 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B15: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A15

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A15 with 8 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B16: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A16

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A16 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B17: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A17

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A17 with 11 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Example B18: Preparation of a curable epoxy resin composition using the epoxy resin composition of Example A17

A mixture was prepared by mixing 100 g of the epoxy resin composition of Example A17 with 9 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B1: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A1

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A1 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B2: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A2

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A2 with 3 g of isosorbide (Samyang Corporation, Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and 100 parts by weight of the mixture was added. For , a curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B3: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A3

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A3 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B4: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A4

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A4 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B5: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A5

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A5 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B6: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A6

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A6 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B7: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A7

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A7 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B8: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A8

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A8 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B9: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A9

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A9 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B10: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A10

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A10 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B11: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A11

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A11 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B12: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A12

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A12 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B13: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A13

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A13 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B14: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A14

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A14 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B15: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A15

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A15 with 8 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B16: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A16

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A16 with 8 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B17: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A17

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A17 with 11 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B18: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A18

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A18 with 20 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B19 Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A19

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A19 with 1 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B20: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A20

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A20 with 20 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B21: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A21

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A21 with 1 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B22: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A22

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A22 with 32 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B23: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A23

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A23 with 2 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B24: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A24

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A24 with 32 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B25: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A25

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A25 with 2 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B26: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A26

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A26 with 20 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B27: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A27

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A27 with 1 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B28: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A28

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A28 with 20 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B29: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A29

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A29 with 1 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B30: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A30

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A30 with 34 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B31: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A31

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A31 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B32: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A32

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A32 with 34 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

Comparative Example B33: Preparation of a curable epoxy resin composition using the epoxy resin composition of Comparative Example A33

A mixture was prepared by mixing 100 g of the epoxy resin composition of Comparative Example A33 with 3 g of isosorbide (Samyang Co., Ltd., Hydroxy equivalent weight (HEW): 73 g/eq, 1 equivalent) as a curing agent, and based on 100 parts by weight of the mixture, A curable epoxy resin composition was prepared by adding 0.1 part by weight of N,N-dimethylbutylamine as a catalyst.

<Manufacture of adhesive specimen>

Adhesive specimens were prepared using the curable epoxy resin compositions prepared in Examples B1 to B18 and Comparative Examples B1 to B33 as an adhesive, and the physical properties of the adhesive specimens were measured in the following manner, and the results are shown in the table below. It is shown in 4.

<Measurement of physical properties>

(1) Shear strength (unit: MPa)

Stainless steel measuring 100 mm in length × 20 mm in width × 1 mm in thickness was cleaned using ethanol. Each of the curable epoxy resin compositions obtained in Examples B1 to B18 and Comparative Examples B1 to B33 was applied as an adhesive to one surface of the cleaned stainless steel in a surface of 20 mm in length × 20 mm in width, and then applied with a certain adhesive thickness thereon. A small amount of microbeads were stacked to maintain the structure. Afterwards, another stainless steel was covered and fixed on top, and then first hardened at 110°C for 1 hour and secondly hardened at 150°C for 1 hour. The shear strength of the adhesive specimen cooled to 23°C after curing was measured using a universal testing machine (Instron 5967 product, manufactured by Instron). At this time, the shear strength was measured while applying a load in a 180-degree direction at a tensile speed of 5 mm/min.

Specifically, the shear strength was measured a total of five times for each adhesive specimen, and their average value was calculated.

<Ingredients Description>

- ISB: Isosorbide

- DMBA: N,N-dimethylbutylamine

- Catalyst (parts by weight) content: Based on 100 parts by weight of the total content of epoxy resin composition and curing agent

As shown in Table 4, Examples B1 to B18 according to the present invention exhibited excellent adhesion with a shear strength of 20 MPa or more.

However, in the case of Comparative Examples B1, B3, B5, B7, B9, B11, B13, and B15, since an epoxy resin composition with excessive polymerization was used, the curing reaction of the curable epoxy resin composition did not occur, making it impossible to measure the shear strength. . In addition, in the case of Comparative Examples B2, B4, B6, B8, B10, B12, B14, B16, and B17, an excessive amount of epihalohydrin was used during the preparation of the epoxy resin composition to remove unreacted epihalohydrin. Because the content was too high, the manufacturing yield decreased, which led to a decrease in productivity. In addition, in the case of Comparative Examples B18, B20, B22 and B24, the amount of alkylene oxide added during the preparation of the crosslinked anhydrosugar alcohol-alkylene glycol composition was too small, so an epoxy resin composition with a low epoxy equivalent weight was obtained, and as a result, a relatively short The tensile force was reduced due to the chain length, and the shear strength was poor at 6 MPa or less. In the case of Comparative Examples B19, B21, B23, and B25, the amount of alkylene oxide added was too large when preparing the crosslinked anhydrosugar alcohol-alkylene glycol composition. An epoxy resin composition with a high epoxy equivalent weight was obtained, and as a result, the shear strength was poor at 9 MPa or less due to insufficient tensile force due to the relatively long chain length.

In addition, in the case of Comparative Examples B26 to B29, when preparing the crosslinked anhydrosugar alcohol-alkylene glycol composition, the crosslinking content of the rubber-modified epoxy compound was too small, resulting in an increase in functional groups, resulting in insufficient tensile strength due to the short chain length, which was lowered to 6 MPa or less. It was poor, and in the case of Comparative Examples B30 to B33, when preparing the crosslinked anhydrosugar alcohol-alkylene glycol composition, the crosslinking content of the rubber-modified epoxy compound was too high, and some polymerization occurred, creating a portion where curing reaction did not occur, resulting in shear strength. was poor at less than 9 MPa.

Claims (22)

An epoxy resin composition,
It is manufactured by reacting a mixture containing a polyol composition and epihalohydrin,
The polyol composition is prepared by addition reaction of a crosslinked anhydrous sugar alcohol composition and alkylene oxide,
The crosslinked anhydrous sugar alcohol composition is prepared from a crosslinking reaction of 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 monoanhydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component has the formula below: It is a polysaccharide alcohol represented by 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 one of the first to fourth polyol components. One or more polymers selected from,
The OH equivalent weight (Hydroxyl equivalent weight) of the polyol composition is 251 to 2,035 g/eq,
The content of the epihalohydrin in the mixture is greater than 90 parts by weight and less than 4,600 parts by weight, based on 100 parts by weight of the polyol composition.
Epoxy resin composition:
[Formula 1]

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

[Formula 3]

In Formulas 2 and 3, n is each independently an integer from 0 to 4. The epoxy resin composition of 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:
- 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,
- condensation polymerization reaction of the second polyol component, the third polyol component and the 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. The epoxy resin composition 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 anhydrosugar alcohol composition is 1.13 to 3.41;
iii) The average number of -OH groups per molecule in the anhydrosugar alcohol composition is 2.54 to 21.36. The method of claim 1, wherein the anhydrous sugar alcohol composition is prepared by hydrogenating a glucose-containing saccharide composition, the obtained hydrogenated sugar composition is subjected to a dehydration reaction by heating under an acid catalyst, and the obtained dehydration reaction product is An epoxy resin composition prepared by thin film distillation. The epoxy resin composition according to claim 5, wherein the glucose-containing saccharide composition contains 41% by weight 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, and an acrylonitrile-butadiene-modified epoxy compound. , 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 combinations thereof. One or more epoxy resin compositions. The epoxy resin composition according to claim 1, wherein the amount of the rubber-modified epoxy compound that crosslinks with the anhydrous sugar alcohol composition is from more than 5 parts by weight to less than 55 parts by weight based on 100 parts by weight of the anhydrous sugar alcohol composition. The epoxy resin composition according to claim 1, wherein the amount of alkylene oxide that addition reacts with the crosslinked anhydrous sugar alcohol composition is more than 50 parts by weight based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition. The epoxy resin composition of claim 1, wherein the alkylene oxide is a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms. The epoxy resin composition according to claim 1, wherein the epihalohydrin is an epihalohydrin substituted or unsubstituted with a C1-C4 alkyl group. The method of claim 1, wherein the epihalohydrin is epichlorohydrin, epibromohydrin, epiiodohydrin, methyl epichlorohydrin, methyl epibromohydrin, methyl epiiodohydrin, or a combination thereof. At least one epoxy resin composition selected from the group consisting of. The epoxy resin composition of claim 1, wherein the epoxy resin composition has an epoxy equivalent weight of 375 to 2,879 g/eq. As a method for producing an epoxy resin composition,
It includes: reacting a mixture containing a polyol composition and epihalohydrin,
The polyol composition is prepared by addition reaction of a crosslinked anhydrous sugar alcohol composition and alkylene oxide,
The crosslinked anhydrous sugar alcohol composition is prepared from a crosslinking reaction of 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 monoanhydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component has the formula below: It is a polysaccharide alcohol represented by 1, the fourth polyol component is anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1), and the fifth polyol component is one of the first to fourth polyol components. One or more polymers selected from,
The OH equivalent weight (Hydroxyl equivalent weight) of the polyol composition is 251 to 2,035 g/eq,
The content of the epihalohydrin in the mixture is greater than 90 parts by weight and less than 4,600 parts by weight, based on 100 parts by weight of the polyol composition,
Method for producing epoxy resin composition:
[Formula 1]

In Formula 1, n is an integer from 0 to 4. The epoxy resin composition of any one of claims 1 to 13; and
Containing a hardener;
Curable epoxy resin composition. The curable epoxy resin composition according to claim 15, wherein the curing agent is at least one selected from the group consisting of anhydrous sugar alcohol, phenol-based compound, acid anhydride-based compound, amine-based compound, or a combination thereof. The curable epoxy resin composition according to claim 15, wherein the equivalent ratio of the curing agent to the epoxy resin composition (equivalent weight of curing agent/equivalent weight of epoxy resin composition) is 0.9 to 1.1. 16. The curable epoxy resin composition of claim 15, further comprising a curing catalyst. The curable epoxy resin composition according to claim 18, wherein the curing catalyst is at least one selected from the group consisting of an amine-based compound, an imidazole-based compound, an organophosphorus-based compound, or a combination thereof. The method of claim 15, wherein the group consisting of antioxidants, UV absorbers, fillers, resin modifiers, silane coupling agents, diluents, colorants, anti-foaming agents, defoamers, dispersants, viscosity modifiers, gloss modifiers, wetting agents, conductivity imparting agents, or combinations thereof. A curable epoxy resin composition further comprising one or more additives selected from. A cured product obtained by curing the curable epoxy resin composition of claim 15. An adhesive comprising the cured product of claim 21.