KR20180130111A - Epoxy resin composition comprising eco-friendly curing agent and cured product thereof - Google Patents

Abstract

The present invention relates to an epoxy resin composition containing an environment-friendly curing agent and a cured product thereof. More particularly, the present invention relates to an epoxy resin composition which can achieve a curing degree (curing rate) equal to or higher than that of a conventional epoxy resin curing agent by including an anhydrosugar alcohol or an anhydrosugar alcohol-alkylene glycol as a curing agent for epoxy resins and can solve environmental problems by being environment-friendly, and to a cured product thereof.

Description

EPOXY RESIN COMPOSITION AND EPOXY RESIN COMPOSITION CONTAINING THE SAME United States

The present invention relates to an epoxy resin composition containing an environmentally-friendly curing agent and a cured product thereof, and more particularly, to a cured product of a conventional epoxy resin curing agent and a cured product thereof by including an anhydrosugar alcohol or an anhydride alcohol- To an epoxy resin composition and a cured product of the epoxy resin composition which are environmentally friendly and can solve environmental problems while achieving a curing degree (curing rate) of an equivalent level or higher.

Epoxy resins have excellent heat resistance, mechanical properties, electrical properties and adhesiveness. Taking advantage of these properties, epoxy resins are used for encapsulating materials such as wiring boards, circuit boards, and circuit boards, semiconductor chips, coils, and electric circuits in which these are multilayered. Alternatively, the epoxy resin is also used as a resin for adhesives, paints and fiber-reinforced resins.

Epoxy resins find wide application as thermosetting resins in many applications. They are used as thermosetting matrices in prepregs made of fibers included in thermosetting matrices. They can also be used as surface coating materials for bonding, molding and lamination due to toughness, flexibility, adhesiveness and chemical resistance, all of which can be used in aerospace, automotive, electronics, construction, furniture, And a wide variety of industrial applications.

A wide variety of epoxy resins can be readily used and can be used depending on their reactivity required for a particular application. For example, the resins can be solid, liquid or semi-solid and can have a variety of reactivity depending on the application to which they are to be applied. The reactivity of the epoxy resin is often measured in terms of the epoxy equivalent, which is the molecular weight of the resin containing a single reactive epoxy group. The lower the epoxy equivalent, the higher the reactivity of the epoxy resin. Various reactivity is required for various epoxy resin applications, but it depends on whether it exists as a matrix of fiber-reinforced prepregs, adhesive coatings, and structural adhesives.

Epoxy resin is a chemical unit of the molecule that constitutes it and it always has an epoxy bond. It is typical that it is made by polymerizing epichlorohydrin and bisphenol A. Since epoxy resin is not used alone, it is used by changing a thermosetting material by adding a curing agent, so it would be appropriate to consider it as an intermediate of a resin. That is, a cured product can not be obtained only with an epoxy resin, and a thermosetting structure can be obtained only by forming crosslinking points that can not move by bonding with an epoxy reactor.

The materials that make these bridging points are also called hardeners. Curing agents usable with the epoxy resin include phenol, acid anhydride, amine and the like. Among them, since various structures may exist in phenol, various physical property changes obtained by changing the epoxy resin can be obtained by changing the structure of the phenol resin curing agent. Due to these various properties, phenolic resin curing agent is mainly used . However, problems arise due to the free phenol present in the phenolic resin. Glass phenol disappears after curing, but it poses a problem in use because it threatens the health of workers during work.

Accordingly, development of an epoxy resin composition using a curing agent that is eco-friendly and capable of solving environmental problems while achieving a curing degree (curing rate) equal to or higher than that of a conventional curing agent has been demanded.

Korean Patent Publication No. 10-2016-0099533 Korean Patent Publication No. 10-2015-0082250 Korean Patent Publication No. 10-2016-0119139

DISCLOSURE Technical Problem In order to solve the above problems, the present invention provides an epoxy resin composition using a curing agent that is environmentally friendly and capable of solving environmental problems while achieving a curing degree (curing rate) equal to or higher than that of a conventional curing agent, It is intended to provide cargo.

Disclosure of the Invention In order to solve the above technical problems, And an epoxy resin composition containing anhydrosugar alcohol, a dihydric alcohol-alkylene glycol, or a mixture thereof as a curing agent.

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

According to another aspect of the present invention, there is provided a molded article comprising the cured product of the present invention.

According to the present invention, when an anhydrosugar alcohol or a derivative thereof is used instead of an existing curing agent (for example, a phenol resin curing agent) as a curing agent for epoxy resins, it is possible to achieve a degree of curing (curing rate) In addition, since there is no component such as free phenol, there is no harmful and environment-friendly. Therefore, the environmental problem can be solved. Since the curing agent has powdery form, it is stable at room temperature and excellent in storage stability. There is an advantage that a small amount can be used.

Hereinafter, the present invention will be described in detail.

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

In one embodiment, examples of the epoxy resin include bisphenol A-epichlorohydrin resin, epoxy novolac resin, alicyclic epoxy resin, aliphatic epoxy resin, cyclic epoxy resin, glycidyl ester type epoxy resin, brominated epoxy resin, A bio-derived epoxy resin, an epoxidized soybean oil, and combinations thereof. However, the present invention is not limited thereto.

In another embodiment, examples of the epoxy resin include bisphenol-type epoxy resins such as novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin, bisphenol A type epoxy resin and bisphenol F type epoxy resin, N , Aromatic glycidylamine type epoxy resins such as N-diglycidyl aniline, N, N-diglycidyl toluidine, diaminodiphenyl methane type glycidyl amine and aminophenol type glycidyl amine, A phenol type epoxy resin, a biphenyl type epoxy resin, a stilbene type epoxy resin, a triphenol methane type epoxy resin, a triphenolpropane type epoxy resin, an alkyl modified triphenol methane type epoxy resin, a triazine nucleus containing epoxy resin, a dicyclopentadiene modified Phenol type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, phenol aralkyl type epoxy resins having phenylene and / or biphenylene skeleton, phenylene and / or Alicyclic epoxy resins such as naphthol aralkyl type epoxy resins having a biphenylene skeleton, alicyclic epoxy resins such as vinyl cyclohexene dioxide, dicyclopentadiene oxide and alicyclic diepoxy-adipate, and aliphatic epoxy resins such as But are not limited to, those selected from the group consisting of combinations.

In another embodiment, examples of the epoxy resin include bisphenol F type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, biphenyl type epoxy resin, steel type epoxy resin, hydroquinone type epoxy resin, naphthalene skeleton Type epoxy resin, tetraphenylol ethane type epoxy resin, diphenyl phosphate (DPP) type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol A ethylene oxide adduct diglycidyl Ether, glycidyl ether having one epoxy group such as diglycidyl ether of bisphenol A propylene oxide adduct, diglycidyl ether of bisphenol A, phenyl glycidyl ether and cresyl glycidyl ether, A nucleus-modified epoxy resin which is a nuclear hydrogenated product of the resin, and a combination thereof. However, Not limited to.

In the present invention, anhydrosugar alcohol, anhydrosugar alcohol-alkylene glycol, or a mixture thereof is used as a curing agent for an epoxy resin.

The anhydrosugar alcohol used in the present invention is prepared from hydrogenated sugars derived from natural products.

Hydrogenated sugar (also referred to as " sugar alcohol ") refers to a compound obtained by adding hydrogen to the reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (wherein n is an integer of 2 to 5 ), And classified into tetritol, pentitol, hexitol and heptitol (C 4, 5, 6 and 7, respectively), depending on the number of carbon atoms.

Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like, and sorbitol and mannitol are particularly useful substances.

Anhydrous alcohol has a diol form with two hydroxyl groups in the molecule and can be prepared using hexitol derived from starch. Since alcohol-free alcohol is an eco-friendly substance derived from renewable natural resources, there has been much interest for a long time and studies on the manufacturing method have been carried out. Among these alcohol-free alcohols, isosorbide prepared from sorbitol has the widest industrial application currently.

The use of anhydrous alcohol is widely used in the treatment of cardiovascular diseases, patches, adhesives, oral cleansers and the like, solvents for compositions in the cosmetics industry, and emulsifiers in the food industry. In addition, it is possible to increase the glass transition temperature of a polymer substance such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, to improve the strength of these materials, and to be an environmentally friendly material derived from natural materials. useful. It is also known to be used as an environmentally friendly solvent for adhesives, environmentally friendly plasticizers, biodegradable polymers, and water-soluble lacquers. As such, alcohol-free alcohol has attracted a great deal of attention due to its versatility and its use in real industry is increasing.

In the present invention, as the alcohol without sugar, dianhydrohexitol, which is a dehydrate of hexitol, may be used, more preferably isosorbide (1,4-3,6-dianhydroisorbitol), isomannide 1,4,3,6-dianhydro- mannitol), isoidide (1,4-3,6-dianhydroiditol) and mixtures thereof, and most preferably isosorbide is used .

Anhydrosugar alcohol-alkylene glycol used in the present invention is an adduct obtained by reacting an alkylene oxide with a hydroxyl group at both terminals or one terminal (preferably both terminals) of anhydrosugar alcohol.

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

In one embodiment, the anhydride alcohol-alkylene glycol may be a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ and R ² each independently represent a linear or branched alkylene group having 2 to 8 carbon atoms and a branched alkylene group having 3 to 8 carbon atoms,

m and n each independently represent an integer of 0 to 15,

m + n represents an integer of 1 to 30;

More preferably, in Formula 1,

R ¹ and R ² each independently represent an ethylene group, a propylene group or an isopropylene group, and preferably, R ¹ and R ² are the same as each other,

m and n each independently represent an integer of 1 to 14,

m + n represents an integer of 2 to 15;

In one embodiment, the anhydrosugar alcohol-alkylene glycol may include the following isosorbide-propylene glycol, isosorbide-ethylene glycol, or mixtures thereof.

[Isosorbide-propylene glycol]

In the above formula, a + b may be an integer of 1 to 30, and more preferably an integer of 2 to 15.

[Isosorbide-ethylene glycol]

In the above formula, c + d may be an integer of 1 to 30, more preferably an integer of 2 to 15.

In the epoxy resin composition of the present invention, the content ratio of the epoxy resin and the curing agent may be such that the equivalent ratio of the curing agent to the epoxy resin (equivalence of the curing agent / equivalence of the epoxy resin) is, for example, in the range of 0.25 to 1.75 , More specifically, the equivalence ratio may be in the range of 0.75 to 1.25, and more specifically, the equivalence ratio may be in the range of 0.95 to 1.05. If the equivalent weight of the curing agent relative to the equivalent weight of the epoxy resin is too small, there may be a problem that the mechanical strength is lowered and the physical properties are deteriorated in terms of thermal and adhesive strength. Conversely, when the equivalent weight of the curing agent to the equivalent weight of the epoxy resin is too large, There may be a problem that the physical properties are deteriorated in terms of strength, thermal and adhesive strength.

Since room temperature curing of an epoxy resin usually requires a temperature of 15 ° C or higher and a curing time of 24 hours or more, rapid curing and low-temperature curing are sometimes required.

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

Examples of the curing catalyst usable in the present invention include amine compounds (e.g., tertiary amines) such as benzyldimethylamine, tris (dimethylaminomethyl) phenol and dimethylcyclohexylamine; Imidazole compounds such as 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole and 1-benzyl-2-methylimidazole; Organophosphorus compounds such as triphenylphosphine, triphenyl phosphite and the like; Quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide; Diazabicyclo [5.4.0] undecene-7 and the like, and organic acid salts thereof; Organometallic compounds such as zinc octylate, tin octylate or aluminum acetyl acetone complex; Quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide; Boron compounds such as boron trifluoride, triphenylborate and the like; Metal halides such as zinc chloride and tin chloride; A latent curing catalyst (for example, a high melting point dispersed latent amine adduct in which dicyandiamide, an amine is added to an epoxy resin or the like, a microcapsule type latent catalyst in which a surface of an imidazole, phosphorus, or phosphine accelerator is coated with a polymer ; Amine salt type latent catalysts; latent acid type cationic polymerization type latent catalysts such as Lewis acid salts and Bronsted acid salts, etc.), and combinations thereof.

In one embodiment, the curing catalyst may be selected from the group consisting of amine compounds, imidazole compounds, organic phosphorus compounds, and combinations thereof.

When the curing catalyst is included in the epoxy resin composition of the present invention, the amount of the curing catalyst may be 0.01 part by weight to 1.0 part by weight based on 100 parts by weight of the total amount of the epoxy resin and the curing agent, more specifically 0.05 part by weight to 0.5 part by weight And more specifically 0.08 part by weight to 0.2 part by weight, but is not limited thereto. If the amount of the curing catalyst to be used is too small, the curing reaction of the epoxy resin may not proceed sufficiently, resulting in deterioration of mechanical properties and thermal properties. On the other hand, if the amount of the curing catalyst is excessively large, The viscosity may be increased.

The epoxy resin composition of the present invention may further contain at least one additive component which is usually used in the epoxy resin composition, if necessary.

Examples of such additive components include antioxidants, UV absorbers, fillers, resin modifiers, silane coupling agents, diluents, colorants, defoamers, defoamers, dispersants, viscosity regulators, gloss control agents, wetting agents, conductivity imparting agents, May be used.

The antioxidant may be used in order to further improve the heat-resistant stability of the resulting cured product, and is not particularly limited. For example, a phenolic antioxidant (dibutylhydroxytoluene), a sulfur-based antioxidant (mercaptopropionic acid derivative, etc.) (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.) and combinations thereof. The content of the antioxidant in the composition may be 0.01 to 10 parts by weight, or 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and the curing agent.

Examples of the UV absorber include, but are not limited to, a benzotriazole UV absorber represented by TINUBIN P or TINUVIN 234 manufactured by BASF Japan Ltd.; Triazine based UV absorbers such as TINUVIN 1577ED; Hindered amine-based UV absorbers such as CHIMASSOLV 2020FDL, and combinations thereof. The content of the UV absorber in the composition may be 0.01 to 10 parts by weight, or 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and the curing agent.

The filler is used mainly for the purpose of improving the mechanical properties of the cured product by mixing with an epoxy resin or a curing agent. In general, when the amount of the filler is increased, the mechanical properties are improved. Examples of inorganic fillers include fillers such as talc, sand, silica, talc, and calcium carbonate; Reinforcing fillers such as mica, quartz, and glass fiber; There is a specific use such as quartz powder, graphite, alumina, Aerosil (for the purpose of imparting plasticity), and the metallic material contributes to thermal expansion coefficient, abrasion resistance, thermal conductivity and adhesion of aluminum, aluminum oxide, iron, iron oxide, (Sb ₂ O ₃ ), barium titanate, and lightweight fillers such as fine plastic spheres (phenol resin, urea resin, etc.) as the organic material. In addition, as a filler having a reinforcing property, various kinds of glass fiber or chemical fiber can be treated as a filler in a wide range in the production of a laminate. Thixotropic (Thixotropic) is a phenomenon in which a resin adhered by a vertical surface or dipping method or impregnated in a laminated material does not flow down or is lost during curing. Fine particles having a large unit surface area are used. For example, colloidal silica (Aerosil) or bentonite-based clay is used. In one embodiment, the filler is not particularly limited, but may be selected from the group consisting of, for example, glass fiber, carbon fiber, titanium oxide, alumina, talc, mica, aluminum hydroxide and combinations thereof. The content of the filler in the composition may be 0.01 to 80 parts by weight, or 0.01 to 50 parts by weight, or 0.1 to 20 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent.

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

Examples of the silane coupling agent include, but are not limited to, chloropropyltrimethoxysilane, vinyltrichlorosilane,? -Methacryloxypropyltrimethoxysilane,? -Aminopropyltriethoxysilane, and the like. . The content of the silane coupling agent in the composition may be 0.01 to 20 parts by weight, or 0.05 to 10 parts by weight, or 0.1 to 5 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and the curing agent.

The diluent is used for the main purpose of decreasing the viscosity by adding it to an epoxy resin or a curing agent, and it plays a role of improving the flowability, the defoaming property at the time of use, improving penetration into the details of the parts, . The diluent is generally not volatilized unlike the solvent and remains in the cured product when the resin is cured, and is divided into a reactive and a non-reactive diluent. Wherein the reactive diluent has one or more epoxy groups and participates in the reaction to enter the crosslinked structure in the cured product and the nonreactive diluent is only physically mixed and dispersed in the cured product. Commonly used reactive diluents are butyl glycidyl ether (BGE), phenyl glycidyl ether (PGE), aliphatic glycidyl ether (C12-C14) , Modified t-carboxyl glycidyl ester, and the like. Examples of commonly used non-reactive diluents include di-butyl phthalate (DBP), di-octyl phthalate (DOP), nonyl-phenol, and hy- dro. In one embodiment, the diluent is not particularly limited and includes, for example, n-butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, vinyl cyclohexene dioxide, diglycidyl aniline, Glycerin triglycidyl ether, and combinations thereof. The content of the diluent in the composition may be 0.01 to 80 parts by weight, or 0.01 to 50 parts by weight, or 0.1 to 20 parts by weight based on 100 parts by weight of the total of the epoxy resin and the curing agent.

As a coloring agent for coloring the resin, a pigment or a dye is used. Colorants such as titanium dioxide, cadmium red, shading green, carbon black, chrome green, chrome yellow, navy blue, and shining blue are generally used as pigments.

In addition, a defoaming agent and a defoaming agent used for the purpose of removing bubbles of resin, a dispersing agent for enhancing the dispersing effect of the resin and the pigment, a wetting agent for improving the adhesion between the epoxy resin and the material, , A gloss-adjusting agent for adjusting the gloss of a resin, an additive for improving adhesion, an additive for imparting electrical properties, and the like.

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

The curing temperature and curing time may range from 80 ° C to 250 ° C for 30 seconds to 10 hours. In one specific example, post-curing can be carried out under the conditions of 120 ° C to 180 ° C for 0.1 hour to 5 hours after precuring under the conditions of 80 ° C to 120 ° C for 0.5 hours to 5 hours. In one specific example, curing can be carried out under the conditions of 150 ° C to 250 ° C for 30 seconds to 30 minutes for short time curing.

In one embodiment, the epoxy resin composition of the present invention may be divided into two or more components, for example, a component containing a curing agent and a component containing an epoxy resin, and these components may be combined before curing. In another embodiment, the epoxy resin composition of the present invention may be stored as a thermosetting composition in which the respective components are blended and directly provided in the curing. When preserved as a thermosetting composition, it can be stored at a low temperature (usually -40 캜 to 15 캜).

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

According to still another aspect of the present invention, there is provided a molded article comprising the cured product.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.

[ Example ]

Example  One

Epoxy equivalent weight (EEW): 187 g / eq, 1 equivalent) of a diglycidyl ether of bisphenol A (DGEBA) based on a bisphenol A (YD-128, Kukdo Chemical Co., And isosorbide (ISB, Samyang Corp., hydroxyl equivalent weight (HEW: 73 g / eq, 1 equivalent) were mixed and 100 parts by weight of the mixture was mixed with N, N-dimethylbutylamine (N, N-dimethylbutylamine, DMBA, Sigma aldrich) were added to prepare an epoxy resin composition.

Differential scanning calorimeter (DSC) of TA instruments was used to perform differential scanning calorimetry. Specifically, the epoxy resin composition prepared above was sealed in an aluminum pan, and differential scanning calorimetry was performed from room temperature to 250 DEG C at a temperature rising rate of 10 DEG C / min in a high purity nitrogen atmosphere. At this time, the curing of the epoxy resin composition was confirmed by the measured heating value (Enthalpy). The measured calorific value is shown in Table 1.

Example  2

(IC52, IC chemical, HEW: 182.74 g / eq, 1.05 equivalent) of cycloaliphatic difunctional epoxy resin (Celloxide 2021p, Daicel, EEW: 136.5 g / And 0.1 part by weight of 2-ethyl-4-methylimidazole (2E4M, Sigma aldrich) as a catalyst was added to 100 parts by weight of the mixture to prepare an epoxy resin composition.

Differential scanning calorimetry was performed using Q20, a differential scanning calorimeter (DSC) from TA Instruments. Specifically, the epoxy resin composition prepared above was sealed in an aluminum pan, and differential scanning calorimetry was performed from room temperature to 250 DEG C at a temperature rising rate of 10 DEG C / min in a high purity nitrogen atmosphere. At this time, the curing of the epoxy resin composition was confirmed by the measured heating value (Enthalpy). The measured calorific value is shown in Table 1.

Example  3

Epoxy resin powder (Samwha paint, EEW: 756.4 g / eq, 1 eq.) Containing bisphenol A-epichlorohydrin resin and 3 moles of ISB-PO (propylene oxide) adduct (IC39, IC chemical, HEW: 158.7 g / eq, 0.95 eq.) were mixed. To 100 parts by weight of the mixture, 0.1 part by weight of 2-ethyl-4-methylimidazole (2E4M, Sigma aldrich) was added as a catalyst to prepare an epoxy resin composition.

Differential scanning calorimetry was performed using Q20, a differential scanning calorimeter (DSC) from TA Instruments. Specifically, the epoxy resin composition prepared above was sealed in an aluminum pan, and differential scanning calorimetry was performed from room temperature to 250 DEG C at a temperature rising rate of 10 DEG C / min in a high purity nitrogen atmosphere. At this time, the curing of the epoxy resin composition was confirmed by the measured heating value (Enthalpy). The measured calorific value is shown in Table 1.

Example  4

O-cresol novolac epoxy resin (YDCN-500-90P, Kukdo Chemical Co., Ltd., EEW: 206.3 g / eq, 1 equivalent) and ISB (Samyang Co., HEW: 73 g / eq, 1 equivalent) And 0.1 part by weight of triphenylphosphine (TPP, Sigma aldrich) as a catalyst was added to 100 parts by weight of the mixture to prepare an epoxy resin composition.

Differential scanning calorimetry was performed using Q20, a differential scanning calorimeter (DSC) from TA Instruments. Specifically, the epoxy resin composition prepared above was sealed in an aluminum pan, and differential scanning calorimetry was performed from room temperature to 250 DEG C at a temperature rising rate of 10 DEG C / min in a high purity nitrogen atmosphere. At this time, the curing of the epoxy resin composition was confirmed by the measured heating value (Enthalpy). The measured calorific value is shown in Table 1.

Comparative Example  One

Bisphenol A diglycidyl ether (DGEBA) based difunctional epoxy resin (YD-128 available from Kukdo Chemical Co., Ltd., EEW: 187 g / eq, 1 equivalent) and polyoxypropylenediamine (Jeffamine D-230, Huntsman , 1 equivalent) were mixed. To 100 parts by weight of the mixture, 0.1 part by weight of N, N-dimethylbutylamine (DMBA, Sigma aldrich) was added as a catalyst to prepare an epoxy resin composition.

Differential scanning calorimetry was performed using Q20, a differential scanning calorimeter (DSC) from TA Instruments. Specifically, the epoxy resin composition prepared above was sealed in an aluminum pan, and differential scanning calorimetry was performed from room temperature to 250 DEG C at a temperature rising rate of 10 DEG C / min in a high purity nitrogen atmosphere. At this time, the curing of the epoxy resin composition was confirmed by the measured heating value (Enthalpy). The measured calorific value is shown in Table 1.

Comparative Example  2

Cyclohexane-4-methylphthalic anhydride (HMPA, Sigma Aldrich, HEW: 84 g / eq) (cycloaliphatic difunctional epoxy resin (Celloxide 2021p, Daicel, EEW: 136.5 g / , 1.05 equivalent) were mixed. To 100 parts by weight of the mixture, 0.1 part by weight of 2-ethyl-4-methylimidazole (2E4M, Sigma aldrich) was added as a catalyst to prepare an epoxy resin composition.

Differential scanning calorimetry was performed using Q20, a differential scanning calorimeter (DSC) from TA Instruments. Specifically, the epoxy resin composition prepared above was sealed in an aluminum pan, and differential scanning calorimetry was performed from room temperature to 250 DEG C at a temperature rising rate of 10 DEG C / min in a high purity nitrogen atmosphere. At this time, the curing of the epoxy resin composition was confirmed by the measured heating value (Enthalpy). The measured calorific value is shown in Table 1.

Comparative Example  3

84 g / eq. Of HMPA, Sigma Aldrich, HEW) and an epoxy powder coating (bisphenol A-epichlorohydrin resin-containing epoxy powder coating (Samhwa paint, EEW: 756.4 g / eq, 0.95 eq.) Were mixed. To 100 parts by weight of the mixture, 0.1 part by weight of 2-ethyl-4-methylimidazole (2E4M, Sigma aldrich) was added as a catalyst to prepare an epoxy resin composition.

Differential scanning calorimetry was performed using Q20, a differential scanning calorimeter (DSC) from TA Instruments. Specifically, the epoxy resin composition prepared above was sealed in an aluminum pan, and differential scanning calorimetry was performed from room temperature to 250 DEG C at a temperature rising rate of 10 DEG C / min in a high purity nitrogen atmosphere. At this time, the curing of the epoxy resin composition was confirmed by the measured heating value (Enthalpy). The measured calorific value is shown in Table 1.

Comparative Example  4

XL-4L (phenol curing agent, Mitsui Chemicals, HEW: 169 g / eq, 1 eq.) Was added to the solution in the same manner as in Example 1, And 0.1 part by weight of triphenylphosphine (TPP, Sigma aldrich) as a catalyst was added to 100 parts by weight of the mixture to prepare an epoxy resin composition.

Differential scanning calorimetry was performed using Q20, a differential scanning calorimeter (DSC) from TA Instruments. Specifically, the epoxy resin composition prepared above was sealed in an aluminum pan, and differential scanning calorimetry was performed from room temperature to 250 DEG C at a temperature rising rate of 10 DEG C / min in a high purity nitrogen atmosphere. At this time, the curing of the epoxy resin composition was confirmed by the measured heating value (Enthalpy). The measured calorific value is shown in Table 1.

[Table 1] Measurement results of calorific value upon curing of epoxy resin composition

As shown in Table 1, in the case of curing the epoxy resin compositions of Examples 1 to 4 according to the present invention, the heating amounts of the epoxy resin compositions of Comparative Examples 1 to 4 using the conventional curing agent It can be seen that it was measured. From this, it can be seen that when anhydrosugar alcohol or anhydride alcohol-alkylene glycol is used as a curing agent for an epoxy resin, it is possible to achieve a curing degree (curing rate) equal to or higher than that of a conventional epoxy resin curing agent including a phenol- At the same time, it is environmentally friendly, so it can be confirmed that the environmental problem can be solved.

Claims (14)

Epoxy resin; And
An epoxy resin composition comprising an anhydrosugar alcohol, a dihydric alcohol-alkylene glycol, or a mixture thereof as a curing agent. The epoxy resin composition according to claim 1, wherein the epoxy resin is at least one selected from the group consisting of a bisphenol A-epichlorohydrin resin, an epoxy novolac resin, an alicyclic epoxy resin, an aliphatic epoxy resin, a cyclic epoxy resin, a glycidyl ester type epoxy resin, Derived epoxy resin, an epoxidized soybean oil, and combinations thereof. The epoxy resin composition according to claim 1, wherein the epoxy resin is selected from the group consisting of a novolac epoxy resin, a bisphenol epoxy resin, an aromatic glycidylamine epoxy resin, a hydroquinone epoxy resin, a biphenyl epoxy resin, a stilbene epoxy resin, Epoxy resin, triphenolpropane type epoxy resin, alkyl modified triphenolmethane type epoxy resin, triazine nucleus containing epoxy resin, dicyclopentadiene modified phenol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, aralkyl type epoxy resin , An alicyclic epoxy resin, and combinations thereof. The epoxy resin composition according to claim 1, wherein the epoxy resin is at least one selected from the group consisting of bisphenol F epoxy resin, cresol novolak epoxy resin, phenol novolac epoxy resin, biphenyl epoxy resin, steel bendable epoxy resin, hydroquinone epoxy resin, Resin, tetraphenylol ethane type epoxy resin, diphenyl phosphate type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, diglycidyl ether of bisphenol A ethylene oxide adduct, bisphenol A propylene Diglycidyl ether of bisphenol A, phenylglycidyl ether, cresyl glycidyl ether, nucleus-derived epoxy resin which is a nuclear hydrogenated product of these epoxy resins, and combinations thereof ≪ / RTI > The epoxy resin composition of claim 1, wherein the anhydrosugar alcohol is selected from the group consisting of isosorbide, isomannide, isoidide, and combinations thereof. The epoxy resin composition according to claim 1, wherein the anhydropoly alcohol-alkylene glycol is an adduct obtained by reacting an endless or one-terminal hydroxy group of anhydrosugar alcohol with an alkylene oxide. 7. The composition of claim 6 wherein the anhydrosugar alcohol is selected from the group consisting of isosorbide, isomannide, isoidide, and combinations thereof, wherein the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, and combinations thereof , An epoxy resin composition. The epoxy resin composition according to claim 1, wherein the equivalent ratio of the curing agent to the epoxy resin (equivalents of the curing agent / equivalent amounts of the epoxy resin) is from 0.95 to 1.05. The epoxy resin composition of claim 1, further comprising a curing catalyst. The epoxy resin composition according to claim 9, wherein the curing catalyst is selected from the group consisting of an amine compound, an imidazole compound, an organic phosphorus compound, and combinations thereof. The epoxy resin composition according to claim 9, wherein the content of the curing catalyst is 0.01 part by weight to 1.0 part by weight based on 100 parts by weight of the total amount of the epoxy resin and the curing agent. A composition according to any of claims 1 to 3, further comprising at least one compound selected from the group consisting of antioxidants, UV absorbers, fillers, resin modifiers, silane coupling agents, diluents, colorants, defoamers, defoamers, dispersants, viscosity modifiers, gloss modifiers, wetting agents, ≪ / RTI > wherein the epoxy resin composition further comprises an additive. A cured product obtained by curing the epoxy resin composition of any one of claims 1 to 12. A molded article comprising the cured product of claim 13.