KR102454213B1 - Novel acid anhydride-based epoxy compound, epoxy adhesive composition containing the same, and cured product prepared therefrom - Google Patents

Abstract

Since the acid anhydride-based epoxy compound according to the present invention participates directly in the curing reaction, phase separation does not occur when an impact is applied from the outside, and the mechanical properties of the cured product can be improved as a whole. In addition, the epoxy adhesive composition comprising the same can provide a cured product having excellent impact strength and flexural strength, and by preventing structural deformation due to external impact, it can exhibit significantly superior durability than the existing epoxy composition.
Through the introduction of the acid anhydride-based epoxy compound according to the present invention, it is possible to manufacture products by designing desired mechanical properties by supplementing the brittleness of conventional epoxy resins. Specifically, it is possible to improve the impact strength and flexural strength of the product by adding it to the lightweight dissimilar material adhesive and coating composition for automobiles. In addition, the acid anhydride-based epoxy compound according to the present invention, an epoxy adhesive composition comprising the same, and a cured product thereof can be usefully used as a functional adhesive in aircraft, spacecraft, railway, ship, sports equipment and computer industries.

Description

An acid anhydride-based epoxy compound, an epoxy adhesive composition comprising the same, and a cured product prepared therefrom

The present invention relates to a novel acid anhydride-based epoxy compound, an epoxy adhesive composition comprising the same, and a cured product prepared therefrom.

Recently, in the automobile industry, there is a demand for a new adhesive technology that can replace the existing coupling parts for the purpose of reducing the weight of the automobile. This must be able to strengthen the bond between mechanical parts to increase the strength in the bonded area. Adhesives having these properties can be widely used in automobiles and aerospace industries.

Epoxy adhesives that are typically used have excellent mechanical properties, chemical resistance, electrical properties, etc. and are applied to industrial fields such as adhesion, coating, fiber-reinforced composite materials and automobiles, but have a disadvantage in that they lack toughness.

In order to solve the above problems, various toughening agents such as rubber or urethane are sometimes used, but these toughening agents have low mutual bonding strength with the epoxy base, causing phase separation. That is, when a toughening agent is added to the epoxy adhesive composition, the toughening agent absorbs an impact from the outside and the impact properties can be improved, but the epoxy and the toughening agent, which are mattresses, cause phase separation, and consequently mechanical strength is reduced.

Therefore, it is urgently required to research and develop an epoxy adhesive composition that has excellent toughness and excellent strength against external impacts and at the same time has excellent mechanical strength such as flexural strength.

KR 10-2020-0027716 A (2020.03.13)

The present invention provides an acid anhydride-based epoxy compound prepared from a novel acid anhydride-based compound.

In addition, the present invention provides an epoxy adhesive composition comprising the acid anhydride-based epoxy compound of the present invention and a cured product thereof.

In order to achieve the above object, the present inventors have continuously studied to develop an epoxy adhesive composition excellent in mechanical strength such as impact strength and flexural strength due to excellent toughness and a cured product prepared therefrom. In the case of an epoxy adhesive composition containing an acid anhydride-based epoxy compound, it was found that it has excellent compatibility with the epoxy base material, excellent toughness without phase separation, and excellent mechanical strength such as impact strength and flexural strength, and completed the invention.

The present invention provides an epoxy adhesive composition comprising an acid anhydride-based epoxy compound represented by the following formula (1).

[Formula 1]

(In Formula 1,

R ₁ to R ₆ are each independently hydrogen or C _1-10 alkyl;

R ₁ and R ₂ are not simultaneously hydrogen;

Y is hydrocarbylene or heterohydrocarbylene.)

Preferably, in Formula 1 according to an embodiment of the present invention, R ₁ to R ₂ are each independently hydrogen or methyl; R ₃ to R ₆ are each independently hydrogen or C _1-7 alkyl; The case where R ₁ and R ₂ are hydrogen at the same time may be excluded.

More preferably, in Formula 1 according to an embodiment of the present invention, Y is C _5-60 alkylene, C _3-60 cycloalkylene, C _6-60 arylene or C _3-60 heteroarylene; Alkylene, cycloalkylene, arylene and heteroarylene of Y are optionally hydroxy, halogen, nitro, cyano, amino, carboxyl, carboxylate, C _1-20 alkyl, C _1-20 alkenyl, C _1-20 Haloalkyl, C _1-20 Alkoxy, C _1-20 Alkoxycarbonyl, C _3-30 Cycloalkyl, C 6-30 _{ArylC 1-20} Alkyl, C _6-30 Aryl and C _3-30 Hetero It may be substituted with one or more selected from aryl.

More preferably, the acid anhydride-based epoxy compound of Formula 1 according to an embodiment of the present invention may be represented by Formula 2 below in terms of being used as an adhesive composition and having more improved physical properties.

[Formula 2]

(In Formula 2,

R ₁ is C _1-7 alkyl;

R ₃ to R ₆ are each independently hydrogen or C _1-7 alkyl;

Y may be hydrocarbylene or heterohydrocarbylene.)

In Formula 2 according to an embodiment of the present invention, Y is C _5-30 alkylene, C _3-30 cycloalkylene, C _6-30 arylene or C _3-30 heteroarylene; Said alkylene, cycloalkylene, arylene and heteroarylene are optionally hydroxy, halogen, nitro, cyano, amino, carboxyl, carboxylate, C _1-10 alkyl, C _1-10 alkenyl, C ₁ in _-10 haloalkyl, C _1-10 alkoxy, C _1-10 alkoxycarbonyl, C _3-20 cycloalkyl, C _{6-20 arylC 1-10} alkyl, C _6-20 aryl and C _3-20 heteroaryl It may be substituted with one or more selected.

More preferably, Chemical Formula 1 according to an embodiment of the present invention may be represented by Chemical Formulas 3 to 4 below.

[Formula 3]

[Formula 4]

(In Formulas 3 to 4,

R ₁ is C _1-7 alkyl;

A is -CO-, -SO-, -SO ₂ - or -C(R ₁₁ )(R ₁₂ )-, R ₁₁ to R ₁₂ are each independently hydrogen, C _1-7 alkyl, C _1-7 halo alkyl or C _6-12 aryl, or R ₁₁ to R ₁₂ may be linked to each other to form a C _3-10 alicyclic ring;

n is an integer from 1 to 10.)

The epoxy adhesive composition according to an embodiment of the present invention may further include a base epoxy resin, a curing agent, and a curing accelerator, and the base epoxy resin and the acid anhydride-based epoxy compound may be included in a molar ratio of 1 to 9: 9 to 1. .

In addition, the present invention provides a cured product of the epoxy adhesive composition according to an embodiment of the present invention.

In addition, the present invention provides an acid anhydride-based epoxy compound represented by the following formula (1).

[Formula 1]

(In Formula 1,

R ₁ to R ₆ are each independently hydrogen or C _1-10 alkyl;

R ₁ and R ₂ are not simultaneously hydrogen;

Y is hydrocarbylene or heterohydrocarbylene.)

In addition, the present invention provides an acid anhydride-based compound represented by the following formula (5).

[Formula 5]

(In Formula 5,

R is hydrogen, an alkali metal or an alkaline earth metal;

R ₂₁ to R ₂₆ are each independently hydrogen or C ₁ -C ₁₀ alkyl;

Except when R ₂₁ and R ₂₂ are hydrogen at the same time.)

In addition, the acid anhydride compound of Formula 5 according to an embodiment of the present invention may be selected from the following compounds.

Since the acid anhydride-based epoxy compound according to the present invention participates directly in the curing reaction, phase separation does not occur when an impact is applied from the outside, and the mechanical properties of the cured product can be improved as a whole.

Therefore, the epoxy adhesive composition including the same can provide a cured product having excellent impact strength and flexural strength, and by preventing structural deformation due to external impact, it can express remarkably excellent durability compared to the existing epoxy composition.

Accordingly, the epoxy adhesive composition employing the acid anhydride-based epoxy compound of the present invention compensates for the brittleness of conventional epoxy resins and has desired mechanical properties, so that various products can be used as adhesives. Specifically, it is possible to improve the impact strength and flexural strength of the product by adding it to the lightweight dissimilar material adhesive and coating composition for automobiles.

In addition, the epoxy adhesive composition comprising the acid anhydride-based epoxy compound of the present invention can be usefully used as a functional adhesive in aircraft, spacecraft, railway, ship, sports equipment and computer industries.

1 is a graph showing the Fourier Transform-Infrared spectroscopy (FT-IR) results of the acid anhydride-based epoxy compound prepared in Examples 1 and 2 of the present invention.
2 is a graph showing the results of H ¹ NMR analysis of the acid anhydride-based epoxy compound prepared in Examples 1 and 2 of the present invention.

Hereinafter, an acid anhydride compound, an acid anhydride-based epoxy compound, an epoxy adhesive composition comprising the same, and a cured product prepared therefrom according to the present invention will be described in detail. At this time, unless there are other definitions in the technical terms and scientific terms used, it has the meaning commonly understood by those of ordinary skill in the technical field to which this invention belongs, and in the following description, it may unnecessarily obscure the subject matter of the present invention. Descriptions of possible known functions and configurations will be omitted.

As used herein, the singular form may also be intended to include the plural form unless the context dictates otherwise.

In addition, in the present specification, the unit used without special mention is based on the weight, for example, the unit of % or ratio means weight % or weight ratio, and weight % means any one component of the entire composition unless otherwise defined. It means % by weight in the composition.

In addition, the numerical range used herein includes the lower limit and upper limit and all values within the range, increments logically derived from the form and width of the defined range, all values defined therein, and the upper limit of the numerical range defined in different forms. and all possible combinations of lower limits. Unless otherwise defined in the specification of the present invention, values outside the numerical range that may occur due to experimental errors or rounding of values are also included in the defined numerical range.

As used herein, "comprises" is an open-ended substrate having an equivalent meaning to expressions such as "comprises", "contains", "has" or "characterizes", and elements and materials not listed further or process is not excluded.

As used herein, "substituted" means that the hydrogen atom of the moiety being substituted (eg, alkyl, aryl, heteroaryl, heterocycle or cycloalkyl) is replaced by a substituent. In one embodiment, each carbon atom of the group being substituted is unsubstituted by more than two substituents. In another embodiment, each carbon atom of the group being substituted is unsubstituted by more than one substituent. In the case of a keto substituent, the two hydrogen atoms are replaced by an oxygen attached to the carbon by a double bond. Optionally substituted substituents of the present invention include hydroxy, halogen, nitro, cyano, amino, carboxyl, carboxylate, C _1-10 alkyl, C _1-10 alkenyl, unless otherwise stated with respect to the substituent. , C _1-10 haloalkyl, C _1-10 alkoxy, C _1-10 alkoxycarbonyl, C _3-20 cycloalkyl, C _{6-20 arylC 1-10} alkyl, C _6-20 aryl and C _3-20 heteroaryl; and the like.

As used herein, "hydrocarbon" refers to a chemical group containing only hydrogen and carbon atoms.

As used herein, "hydrocarbylene" or "heterohydrocarbylene" refers to a radical having two bonding positions derived from hydrocarbon or heterohydrocarbon, and the meaning of hetero is that carbon is B, O, N, C (=O), P, P(=O), S, S(=O) ₂ and Si means substituted with one or more heteroatoms selected from atoms.

As used herein, "alicyclic ring" is cycloalkyl, which means a non-aromatic monocyclic or multicyclic ring system having 3 to 10 carbon atoms, a 3 to 10 membered ring, preferably 5 It may be a 7-membered ring, and may have an unsaturated bond in the ring.

As used herein, "alkyl" includes both straight-chain or comminuted forms, and may contain from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms.

As used herein, "halogen" and "halo" mean fluorine, chlorine, bromine or iodine.

As used herein, "haloalkyl" means an alkyl group in which one or more hydrogen atoms are each replaced by a halogen atom. For example, haloalkyl is -CF ₃ , -CHF ₂ , -CH ₂ F, -CBr ₃ , -CHBr ₂ , -CH ₂ Br, -CC1 ₃ , -CHC1 ₂ , -CH ₂ CI, -CI ₃ , -CHI ₂ , -CH ₂ I, -CH ₂ -CF ₃ , -CH ₂ -CHF ₂ , -CH ₂ -CH ₂ F, -CH ₂ -CBr ₃ , -CH ₂ -CHBr ₂ , -CH ₂ -CH ₂ Br, -CH ₂ -CC1 ₃ , -CH ₂ -CHC1 ₂ , -CH ₂ -CH ₂ CI, -CH ₂ -CI ₃ , -CH ₂ -CHI ₂ , -CH ₂ -CH ₂ I, and the like include that Alkyl and halogen herein are as defined above.

* As used herein, "alkenyl" means a saturated straight-chain or branched acyclic hydrocarbon containing 2 to 30, preferably 2 to 20 carbon atoms and at least one carbon-carbon double bond. Representative linear and branched C _2-10 alkenyls are -vinyl, -allyl, -1-butenyl, -2-butenyl, -isobutylenyl, -1-pentenyl, -2-pentenyl, -3 -Methyl-1-butenyl, -2-methyl-2-butenic, -2,3-dimethyl-2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl , -1-heptenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, -2-octenyl, -3 octenyl, -1-nonenyl, -2-nonenyl , -3-nonenyl, -1-dicenyl, -2-dicenyl, and -3-dicenyl. These alkenyl groups may be optionally substituted.

"Alkoxy" as described in the present invention is -OCH ₃ , -OCH ₂ CH ₃ , -O(CH ₂ ) ₂ CH ₃ , -O(CH ₂ ) ₃ CH ₃ , -O(CH ₂ ) ₄ CH ₃ , -O -O-(alkyl), including (CH ₂ ) ₅ CH ₃ , and the like, wherein alkyl is as defined above.

,

,

도 아릴에 포함된다.As used herein, "aryl" refers to a carbocyclic aromatic group containing 5 to 10 ring atoms. Representative examples include phenyl, tolyl, xylyl, naphthyl, tetrahydronaphthyl, anthracenyl, fluorenyl, indenyl, azulenyl, etc. including, but not limited to. Further, aryl is a carbocyclic aromatic group and group connected by alkylene or alkenylene, or B, O, N, C(=O), P, P(=O), S, S(=O)2 and Si atoms Also included are those connected by one or more heteroatoms selected from. As a specific example,

,

,

Also included in aryl.

As used herein, “cycloalkyl” and “cycloaliphatic ring” refer to a monocyclic or polycyclic saturated ring having carbon and hydrogen atoms and no carbon-carbon multiple bonds. Examples of cycloalkyl groups include, but are not limited to, C _3-10 cycloalkyl (eg, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl). Cycloalkyl groups may be optionally substituted. In one embodiment, the cycloalkyl group is a monocyclic or bicyclic ring (ring).

As used herein, "heteroaryl" has at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, and contains 5 to 10 members comprising at least one carbon atom, including mono- and bicyclic ring systems. of an aromatic heterocycle ring. Representative heteroaryls include triazolyl, tetrazolyl, oxadiazolyl, pyridyl, furyl, benzofuranyl, thiophenyl, benzothiophenyl, quinolinyl, pyrrolyl, indolyl, oxazolyl, benzoxazolyl ( benzoxazolyl), imidazolyl, benzimidazolyl, thiazolyl, benzothiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, tria Zinyl, cinnolinyl, phthalazinyl, quinazolinyl, pyrimidyl, oxetanyl, azepinyl, piperazinyl, morpholinyl, dioxanyl, thietanyl and oxazolyl. A heteroaryl group may be monocyclic or bicyclic. Heteroaryl may be used interchangeably with the term heteroaryl ring, heteroaryl group, or heteroaromatic, and all of these terms may include an optionally substituted ring.

As used herein, “alkoxycarbonyl” refers to an alkoxy-C(=O)-* radical, where “alkoxy” is as defined above. Examples of such alkoxycarbonyl radicals include, but are not limited to, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, propoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, and the like. not limited

As used herein, "arylalkyl" refers to one or more hydrogens of alkyl substituted with aryl, and includes benzyl and the like.

,

,

도 아릴렌에 포함된다.As used herein, “alkylene,” “cycloalkylene,” “arylene,” and “heteroarylene” refer to the removal of one hydrogen from “alkyl,” “cycloalkyl,” “aryl,” and “heteroaryl,” respectively. refers to a divalent organic radical derived by Further, arylene is a carbocyclic aromatic group and a group connected by alkylene or alkenylene, or B, O, N, C(=O), P, P(=O), S, S(=O)2 and Si Also included are those linked by one or more heteroatoms selected from atoms. As a specific example,

,

,

also included in arylene.

As used herein, "hydroxy" means -OH, "nitro" means -NO ₂ , "cyano" means -CN, "amino" means -NH ₂ , ""Carboxyl" means -COOH and "carboxylate" means -COOM. M may be an alkali metal or an earth metal.

The "alkali metal" described in the present invention is a chemical element other than hydrogen in Group 1 of the periodic table, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr) ), and "alkaline earth metal" means beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra), which are group 2 elements of the periodic table.

The "epoxy resin" described in the present invention also refers to a state that has been scientifically reacted with a curing agent, but is a raw material for an epoxy composition as is commonly used in the technical field, and has an epoxy group and an epoxy compound that can react with the curing agent may include

In addition, the "cured product" described in the present invention may be a cured product of the epoxy adhesive composition in a general sense. In addition, the cured product may include a semi-cured material.

Hereinafter, the present invention will be specifically described.

The present invention is to provide an epoxy adhesive composition with improved durability and a cured product thereof having excellent strength against external impact and excellent tensile and flexural strength at the same time, wherein the epoxy adhesive composition of the present invention comprises an acid represented by the following formula (1) anhydride-based epoxy compounds.

[Formula 1]

In Formula 1, R ₁ to R ₆ are each independently hydrogen or C _1-10 alkyl, R ₁ and R ₂ are not hydrogen at the same time, and Y may be hydrocarbylene or heterohydrocarbylene.

The epoxy adhesive composition according to an embodiment of the present invention includes the acid anhydride-based epoxy compound represented by Chemical Formula 1, thereby effectively improving toughness compared to conventional epoxy resins, thereby remarkably improving durability.

In terms of having more improved durability, preferably in Formula 1 according to an embodiment of the present invention, R ₁ to R ₂ may be each independently hydrogen or methyl, and R ₃ to R ₆ are each independently hydrogen or C _{1 -7} may be alkyl, and R ₁ and R ₂ may not be hydrogen at the same time.

More preferably, in Formula 1 according to an embodiment of the present invention, Y may be C _5-60 alkylene, C _3-60 cycloalkylene, C _6-60 arylene or C _3-60 heteroarylene, wherein Y Alkylene, cycloalkylene, arylene and heteroarylene of are optionally hydroxy, halogen, nitro, cyano, amino, carboxyl, carboxylate, C _1-20 alkyl, C _1-20 alkenyl, C ₁ in _-20 haloalkyl, C _1-20 alkoxy, C _1-20 alkoxycarbonyl, C _3-30 cycloalkyl, C _{6-30 arylC 1-20} alkyl, C _6-30 aryl and C _3-30 heteroaryl It may be substituted with one or more selected.

More preferably, in Formula 1, Y may be C _6-30 arylene or C _3-30 heteroarylene, and the arylene and heteroarylene are optionally hydroxy, halogen, nitro, cyano, amino, Carboxyl, Carboxylate, C _1-20 Alkyl, C _1-20 Alkenyl, C _1-20 Haloalkyl, C _1-20 Alkoxy, C _1-20 Alkoxycarbonyl, C _3-30 Cycloalkyl, C _6-30 It may be substituted with one or more selected from aryl C _1-20 alkyl, C _6-30 aryl and C _3-30 heteroaryl.

Formula 1 according to an embodiment of the present invention may be represented by Formula 2 below.

[Formula 2]

In Formula 2, R ₁ may be C _1-7 alkyl, R ₃ to R ₆ may be each independently hydrogen or C _1-7 alkyl, and Y may be hydrocarbylene or heterohydrocarbylene. Preferably, in Formula 2 according to an embodiment of the present invention, R ₁ may be C _1-5 alkyl, R ₃ to R ₆ may be each independently hydrogen or C _1-5 alkyl, and Y is substituted or unsubstituted cyclic C _6-30 arylene; or substituted or unsubstituted C _6-30 heteroarylene, more preferably R ₁ may be C _1-3 alkyl, more preferably methyl, and R ₃ to R ₆ are each independently hydrogen or C may be _1-5 alkyl, Y is substituted or unsubstituted C _6-30 arylene; Or it may be a substituted or unsubstituted C _6-30 heteroarylene.

According to an embodiment of the present invention, in Y of Formula 2, the hydrocarbylene may be C _5-30 alkylene, C _3-30 cycloalkylene, C _6-30 arylene, or C _3-30 heteroarylene. wherein said alkylene, cycloalkylene, arylene and heteroarylene are optionally hydroxy, halogen, nitro, cyano, amino, carboxyl, carboxylate, C _1-10 alkyl, C _1-10 alkenyl, C _1-10 haloalkyl, C _1-10 alkoxy, C _1-10 alkoxycarbonyl, C _3-20 cycloalkyl, C _{6-20 arylC 1-10} alkyl, C _6-20 aryl and C _3-20 hetero It may be substituted with one or more selected from an aryl group. Specifically, the hydrocarbylene may be C _6-30 arylene, and the C _6-30 arylene is optionally hydroxy, halogen, nitro, cyano, amino, carboxyl, carboxylate, C _1-10 alkyl, C _1-10 alkenyl, C _1-10 haloalkyl, C _1-10 alkoxy, C _1-10 alkoxycarbonyl, C _3-20 cycloalkyl, (C _6-20 )aryl(C _1-10 )alkyl, It may be substituted with one or more selected from C _6-20 aryl and C _3-20 heteroaryl groups. The C _6-30 arylene may also include a form in which a plurality of arylene groups are linked through a straight-chain or branched C _1-10 alkylene, C _1-10 cycloalkylene or hetero atom, as defined herein. and may specifically include a bisphenol-based structure.

In addition, Y in Formulas 1 and 2 may be an organic group derived from an epoxy compound. The epoxy compound has a bifunctional group and may be an aliphatic epoxy compound, an alicyclic epoxy compound, or an aromatic epoxy compound.

As an example of the aliphatic epoxy compound, pentaerythritol polyglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, neopentyl glycol diglycidyl ether, trimethylolpropane Polyglycidyl ether, 2,2-bis(3-glycidyl-4-glycidyloxyphenyl)propane, dimethyloltricyclodecanediglycidylether, etc. are mentioned, The said alicyclic epoxy compound Specific examples may be hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, and the like, and as a specific example of the aromatic epoxy compound, bisphenol A diglycidyl ether Dil ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, novolac type epoxy resin (For example, a phenol-novolak-type epoxy resin, a cresol-novolak-type epoxy resin, and a brominated phenol-novolak-type epoxy resin), but is not limited thereto.

Preferably, Y in Formulas 1 and 2 according to an embodiment of the present invention may be an aromatic epoxy resin, and preferred examples thereof include bisphenol A-based, bisphenol AF-based, bisphenol AP-based, bisphenol B-based, bisphenol C-based, and bisphenol E. Any one or more bisphenol-type epoxy compounds, glycidyl ether-based epoxy compounds, glycidyl amine-based epoxy Any one or a mixture of two or more selected from a compound, a phenol novolak-type epoxy compound, a cresol novolak-type epoxy compound, etc. can be mentioned. More preferably, it may be selected from a bisphenol A-based epoxy compound and a bisphenol F-based epoxy compound in terms of maximally improving adhesive performance, flexural strength and impact strength.

Y in Formulas 1 and 2 may be selected from the following compounds, but is not particularly limited.

(In the compound, n may be an integer of 1 or more, but is not particularly limited as long as the physical properties described in the present invention are not impaired.)

More preferably, the acid anhydride-based epoxy compound according to an embodiment of the present invention may be represented by the following Chemical Formula 3 or 4.

[Formula 3]

[Formula 4]

In Formulas 3 to 4, R ₁ may be C _1-7 alkyl, A may be -CO-, -SO-, -SO ₂ - or -(R ₁₁ )(R ₁₂ )-, R ₁₁ to R ₁₂ may be each independently hydrogen, C _1-7 alkyl, C _1-7 haloalkyl or C _6-12 aryl, or R ₁₁ to R ₁₂ may be connected to each other to form a C _3-10 alicyclic ring, n may be an integer from 1 to 10.

Preferably, in Formulas 3 to 4, R ₁ may be C _1-5 alkyl, A may be —SO ₂ — or —C(R ₁₁ )(R ₁₂ )-, and R ₁₁ to R ₁₂ are each independently hydrogen, C _1-7 alkyl, C _1-7 haloalkyl or C _6-12 aryl, or R ₁₁ to R ₁₂ may be linked to each other to form a C _3-10 alicyclic ring, and n is an integer from 1 to 10 can More preferably, R ₁ may be C _1-3 alkyl, A may be —SO ₂ — or —C(R ₁₁ )(R ₁₂ )-, and R ₁₁ to R ₁₂ are each independently hydrogen, C _{1 -7} alkyl or C _1-7 haloalkyl, or R ₁₁ to R ₁₂ may be connected to each other to form a C _3-10 alicyclic ring, and n may be an integer of 1 to 5.

The acid anhydride-based epoxy compound of Chemical Formulas 3 to 4 according to an embodiment of the present invention may be selected from the following structures, but is not limited thereto.

(In the compound, R ₁ , A and n are the same as defined in Formulas 3 to 4 above.)

The epoxy equivalent weight of the acid anhydride-based epoxy compound according to an embodiment of the present invention is 200 to 400 g/eq. may be specifically 250 to 350 g/eq. It may satisfy the range, and when an acid anhydride-based epoxy compound satisfying the above range is used, mechanical properties such as impact strength and flexural strength of the epoxy adhesive composition can be further improved.

The epoxy adhesive composition according to an embodiment of the present invention may be a curable epoxy adhesive composition, specifically active energy ray curing type, moisture curing type, thermosetting type or room temperature curing type, etc., preferably a thermosetting type. The thermal curing process can achieve the physical properties described in the present invention by appropriately designing and changing the temperature and time according to the constituent components of the epoxy adhesive composition and its content. Specifically, it may be thermally cured at a temperature of 80 to 250°C, or thermally cured at a temperature of 100 to 200°C for 3 hours or more, or at 120°C for 1 hour, at 150°C for 1 hour, at 180°C for 1 hour. The thermal curing process may be performed sequentially.

The epoxy adhesive composition according to an embodiment of the present invention may further include a base epoxy resin, a curing agent, and a curing accelerator.

The base epoxy resin may be a main component of the epoxy adhesive composition. The base epoxy resin has two or more epoxy groups in the molecule, and may be one selected from saturated, unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic and heterocyclic polyepoxy compounds, but a conventional epoxy As long as it is used as the subject of the composition, it may be used without particular limitation. Specifically, it may be any one or a mixture of two or more selected from a bisphenol type epoxy resin, a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolak type epoxy resin, and a cresol novolak type epoxy resin, Preferably, it may be any one or a mixture of two or more selected from a bisphenol-type epoxy resin, more preferably a bisphenol A-based epoxy resin, a bisphenol F-based, and a bisphenol S-based epoxy resin.

In addition, the base epoxy resin may be liquid at room temperature, and may have an epoxy equivalent weight of 100 to 600 g/eq, or 150 to 550 g/eq. When used in combination with an acid anhydride-based epoxy compound by satisfying the above range, mechanical properties such as impact strength and flexural strength of the epoxy adhesive composition may be improved.

The acid anhydride-based epoxy compound may be used as the main agent or toughening agent of the epoxy adhesive composition.

The base epoxy resin and the acid anhydride-based epoxy compound according to an embodiment of the present invention may be included in a molar ratio of 9 to 1: 1 to 9, preferably 7 to 3: 9 to 1, more preferably 8 to 2: It may be 9 to 1, and when it satisfies the above range, the epoxy adhesive composition of the present invention has a more improved curing behavior and can be easily cured, and external impact by showing superior tensile strength, impact strength and flexural strength By preventing the structural deformation caused by the epoxy composition, it is possible to compensate for insufficient toughness, which is a disadvantage of the conventional epoxy composition, and to express more excellent durability.

The curing agent according to an embodiment of the present invention is not particularly limited as long as it is a compound capable of curing reaction with an epoxy resin, and a curing agent commonly used may be appropriately selected and used, for example, an acid anhydride-based curing agent, a phenol-based curing agent, and an amino-based curing agent. It may be selected from the like. The curing agent may be used alone or in combination.

Examples of the acid anhydride-based curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, and any one or two or more selected from methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, but is not limited thereto.

An example of the phenol-based curing agent is phenol such as formaldehyde condensed resol phenol resin, non-formaldehyde condensed phenol resin, novolak-type phenol resin, novolac-type phenol formaldehyde resin, and polyhydroxystyrene resin. Suzy; resol-type phenolic resins such as aniline-modified resol resins and melamine-modified resol resins; novolac-type phenolic resins such as phenol novolac resins, cresol novolac resins, tert-butylphenol novolac resins, nonylphenol novolac resins and naphthol novolac resins; special phenolic resins such as dicyclopentadiene-modified phenolic resins, terpene-modified phenolic resins, triphenolmethane-type resins, phenolaralkyl resins having a phenylene skeleton or diphenylene skeleton, and naphtholaralkyl resins; and any one or two or more selected from a polyhydroxystyrene resin such as poly(p-hydroxystyrene), but is not limited thereto.

Examples of the amino curing agent include dimethyl dicykan (DMDC), dicyandiamide (DICY), isophoronediamine (IPDA), diethylenetriamine (DETA), triethylenetetramine (TETA), bis( p-aminocyclohexyl)methane (PACM), methylenedianiline (eg 4,4′-methylenedianiline), polyetheramines such as polyetheramine D230, diaminodiphenylmethane (DDM), Diaminodiphenylsulfone (DDS), 2,4-toluenediamine, 2,6-toluenediamine, 2,4-diamino-1-methylcyclohexane, 2,6-diamino-1-methylcyclohexane, 2 ,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene, 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-dia minobenzene, diaminodiphenyl oxide, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl and 3,3'-dimethyl-4,4'-diaminodiphenyl, etc. Any one or two or more may be selected, but the present invention is not limited thereto.

In addition, the curing agent according to an embodiment of the present invention per total epoxy equivalent weight (EEW) of the base epoxy resin and the acid anhydride-based epoxy compound contained in the epoxy adhesive composition of the present invention per active hydrogen equivalent weight (AHEW) of the curing agent It may be preferable to set the content of the curing agent so that the ratio is 1:0.8 to 1.5, preferably 1: 0.9 to 1.2.

The curing accelerator according to an embodiment of the present invention is for controlling the curing rate, and may be selected from an imidazole-based accelerator and a urea-based accelerator. The curing accelerator may be used alone or in combination.

Examples of the imidazole accelerator include 2-methyl imidazole, 2-heptadecyl imidazole, 2-phenyl imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-Ethyl-4-methylimidazole, 2-methylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2 ,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2-undecylimidazole, 3-heptadecylimidazole, 2-phenyl imidazole, 2-phenylimidazoline, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and One or two or more selected from 1-cyanoethyl-2-undecylimidazole and the like may be mentioned, but the present invention is not limited thereto.

As an example of the urea-based accelerator, any one selected from p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea and 3,4-dichlorophenyl-N,N-dimethylurea or the like Two or more may be mentioned, but are not limited thereto.

In addition, the curing accelerator may include 0.01 to 5 parts by weight, preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the sum of the base epoxy resin and the acid anhydride-based epoxy compound included in the epoxy adhesive composition, but limited thereto it's not going to be

In addition to this, one or more other additives may be optionally added to the epoxy adhesive composition according to an embodiment of the present invention. For example, the additives include inorganic fillers, stabilizers, viscosity modifiers, surfactants, pigments or dyes, matting agents, flame retardants, curing inhibitors, defoamers, wetting agents, colorants, thermoplastics, processing aids, ultraviolet (UV) blockers, fluorescent compounds. , a UV stabilizer, an antioxidant, a mold release agent, and mixtures thereof. The additive may be used in a range that does not impair the physical properties of the adhesive composition of the present invention.

It is possible to provide a cured product of the epoxy adhesive composition according to an embodiment of the present invention.

When the cured product according to an embodiment of the present invention contains the base epoxy resin and the acid anhydride-based epoxy compound in a molar ratio of 8:2, the impact strength may satisfy 90 J/m or more. This may satisfy the impact strength improved by 1.5 times or more, or 1.7 times or more, or 1.9 times or more when compared with the epoxy adhesive composition except for the acid anhydride-based epoxy compound alone.

When the cured product according to an embodiment of the present invention contains the base epoxy resin and the acid anhydride-based epoxy compound in a molar ratio of 9:1, the flexural strength may satisfy 110 MPa or more or 120 MPa or more.

The present invention also provides a novel acid anhydride-based epoxy compound included in the epoxy adhesive composition of the present invention, the acid anhydride-based epoxy compound of the present invention may be represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ to R ₆ are each independently hydrogen or C _1-10 alkyl, R ₁ and R ₂ are not hydrogen at the same time, and Y may be hydrocarbylene or heterohydrocarbylene. The description for Y and examples of specific compounds are the same as described above.

Chemical Formula 1 according to an embodiment of the present invention may be represented by Chemical Formulas 2 to 4, and the acid anhydride-based epoxy compound of the present invention may be used as a main agent or a toughening agent for the epoxy adhesive composition.

In addition, the present invention to provide an acid anhydride-based compound for the preparation of the acid anhydride-based epoxy compound of the present invention, the acid anhydride-based compound of the present invention may be represented by the following formula (5).

In Formula 5, R may be hydrogen, an alkali metal, or an alkaline earth metal, R ₂₁ to R ₂₆ may be each independently hydrogen or C ₁ -C ₁₀ alkyl, and R ₂₁ and R ₂₂ are hydrogen at the same time. can be excluded.

Preferably, in Formula 5 according to an embodiment of the present invention, R is hydrogen or an alkali metal; R ₂₁ to R ₂₆ are each independently hydrogen or C ₁ -C ₅ alkyl; R ₂₁ and R ₂₂ may be excluded when they are hydrogen at the same time, more preferably R is hydrogen; R ₂₁ to R ₂₆ are each independently hydrogen or C ₁ -C ₃ alkyl; R ₂₁ and R ₂₂ may be excluded when they are hydrogen at the same time.

Specifically, the acid anhydride-based compound according to an embodiment of the present invention may be selected from the following compounds, but is not limited thereto.

The acid anhydride-based epoxy compound according to an embodiment of the present invention can be prepared by any method that can be recognized by those skilled in the art, but for example, an acid anhydride-based compound is prepared from an acid anhydride and glycidol as in Scheme 1 below, and the It can be prepared by reacting with an epoxy compound again.

[Scheme 1]

(Y, R ₁ to R ₆ in Scheme 1 are the same as described in Formula 1.)

Specifically, the acid anhydride-based epoxy compound according to an embodiment of the present invention may be prepared by reacting glycidol with an acid anhydride as in Scheme 1, and then further reacting the epoxy compound thereto. Specifically, the acid anhydride compound represented by Chemical Formula 5 can be prepared by reacting with glycidol while the ring of the acid anhydride is opened to form a structure having an epoxy group at the terminal thereof. Then, an epoxy compound is reacted thereto to prepare an acid anhydride-based epoxy compound represented by Formula 1 having an epoxy group at both ends.

The acid anhydride may be used without particular limitation as long as it is commonly used, but methyltetrahydrophthalic anhydride (MTHPA) may be preferably used. The epoxy compound has a bifunctional group and may be an aliphatic epoxy compound, an alicyclic epoxy compound, or an aromatic epoxy compound, and specific examples thereof are the same as those described in Y of Formula 1 above.

Through the introduction of the acid anhydride-based epoxy compound according to the present invention, it is possible to manufacture a product by designing desired mechanical properties by supplementing the toughness of the conventional epoxy resin. Specifically, it is possible to improve the impact strength and flexural strength of the product by adding it to the composition of the lightweight dissimilar material adhesion and coating material for automobiles. In addition, the epoxy adhesive composition comprising the acid anhydride-based epoxy compound according to the present invention can be usefully used as a functional adhesive in aircraft, spacecraft, railway, ship, sports equipment and computer industries.

Hereinafter, an epoxy adhesive composition comprising an acid anhydride-based epoxy compound according to the present invention will be described in more detail through Examples. However, the following examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms. Also, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, the terminology used in the description in the present invention is only for effectively describing specific embodiments, and is not intended to limit the present invention.

[Assessment Methods]

1. Epoxy equivalent weight [g/eq.]

Epoxy equivalent weight was measured according to ASTM D1652-04.

2. Impact strength [J/m]

Impact strength was measured according to ASTM D 256-10 using an Izod-type impact tester (JJHBT-6501, JJ-test).

3. Tensile strength [MPa]

It was measured using a universal testing machine (UTM 5982, INSTRON), and the test was performed according to ASTM D 638 standard.

4. Flexural strength [MPa]

Flexural strength was measured according to ASTM D7264M using a universal testing machine (UTM 5982, INSTRON).

5. Hardening behavior

It was measured using a differential scanning calorimeter (DSC Q2000, TA instruments), and the temperature increase test was analyzed at a temperature increase rate of 10 °C in a temperature range of -80 to 250 °C.

[Example 1] Preparation of acid anhydride-based compound (MTPA-ME)

After putting 158.0 g (0.76 mol) of methyltetrahydrophthalic anhydride (MTHPA) and 59.0 g (0.76 mol) of glycidol in a round flask, the reaction mixture was sampled while stirring at 60 ° C. for 3 hours, The reaction was terminated at the point where the epoxy equivalent weight became 242.27 g/eq. by the ASTM D1652 method to obtain an acid anhydride-based compound (MTPA-ME).

MTPA-ME obtained by the above method was analyzed through FT-IR and H ¹ NMR, which is shown in FIG. 1 . As shown in FIG. 1 , it was confirmed that the acid anhydride ring was opened as 1875 cm ^-1 , the peak of the symmetric anhydride, disappeared, and the target product MTPA by confirming that an epoxy structure was added as a newly generated peak in the 910 cm ^-1 region. The production of -ME was confirmed.

[Example 2] Preparation of acid anhydride-based epoxy compound (MTPA-MFE)

Bisphenol F diglycidyl ether having an epoxy group at the end of a round flask and The compound of Example 1 (MTPA-ME) was added in a molar ratio of 1:1, and the reaction mixture was sampled while stirring at 60° C. for 3 hours, and the epoxy equivalent weight measured by ASTM D1652 was 302.8 g/eq. The reaction was terminated in

The MTPA-MFE obtained by the above method was analyzed by FT-IR and NMR, and it is shown in FIGS. 1 and 2 . As shown in FIG. 1, an ester peak and an epoxy peak corresponding to each epoxy were generated, and as shown in FIG. 2, it was confirmed that the title compound, MTPA-MFE, was prepared by confirming that a proton peak corresponding to the structure was generated.

[Examples 3 to 5]

The composition shown in Table 1 was added to a planetary mixer and stirred at room temperature for 30 minutes under vacuum conditions to prepare an epoxy adhesive composition. A cured product was prepared by sequentially curing the prepared epoxy adhesive composition using a mold for each test piece in a curing oven at 120° C. for 1 hour, 150° C. for 1 hour, and 180° C. for 1 hour.

Specifically, bisphenol A diglycidyl ether (DGEBA, Momentive, EPIKOTE 828) was used as the base epoxy resin, and the molar ratio of the base epoxy resin and the acid anhydride-based epoxy compound (MTPA-MFE) of Example 2, respectively 9: 1, 8: 2, 7.5: MTPA-MFE was added so that each epoxy adhesive composition was prepared. As a curing agent, dicyandiamide (DICY, AIR PRODUCTS) was used, and the total epoxy equivalent weight of the base epoxy resin and MTPA-MFE included in the composition and the active hydrogen equivalent weight of dicyandiamide (AHEW) were 1:1. was added accordingly. The curing accelerator, 2-methylimidazole, was added in 0.2 parts by weight based on 100 parts by weight of the sum of the base epoxy resin and the MTPA-MFE of Example 2.

The epoxy adhesive composition prepared in each was heat-cured in a curing oven to prepare a cured product, and each cured product was prepared by a composition containing the base epoxy resin and MTPA-MFE in a molar ratio of 9: 1, and the cured product was MTPA. A cured product prepared from a composition containing -MFE 10 and a molar ratio of 8: 2 was denoted as MTPA-MFE 20, and a cured product prepared from a composition containing a molar ratio of 7.5: 2.5 was denoted as MTPA-MFE 25.

In addition, physical properties of the prepared cured product were measured through the evaluation method described above, and the measured results are shown in Table 2 below.

[Comparative Example 1]

A cured product was prepared in the same manner as in Example 3, except that MTPA-MFE, which is the acid anhydride-based epoxy compound of Example 2 of the present invention, was not added in Example 3 above.

The prepared cured product was measured for physical properties by the evaluation method described above, and the measured results are shown in Table 2 below.

Acid anhydride-based epoxy compound Bisphenol A diglycidyl ether (molar ratio)
type content (molar ratio) Example 3
(MTPA-MFE 10) MTPA-MFE One 9 Example 4
(MTPA-MFE 20) MTPA-MFE 2 8 Example 5
(MTPA-MFE 25) MTPA-MFE 2.5 7.5 Comparative Example 1
(Reference) - 10

DSC impact strength
(J/m) The tensile strength
(MPa) flexural strength
(MPa) T _Peak
(℃) T _Onset
(℃) Example 3
(MTPA-MFE 10) 176.67 160.29 81.30 (±7.1) 65.10 (±5.16) 120.3 (±2.34) Example 4 (MTPA-MFE 20) 177.18 160.37 93.34 (±2.33) 55.70 (±5.76) 116.1 (±5.70) Example 5
(MTPA-MFE 25) 178.62 160.47 80.41 (±3.94) 48.20 (±4.93) 112.8 (±9.51) Comparative Example 1
(Reference) 153.73 127.23 47.30 (±0.95) 63.69 (±3.54) 108.1 (±1.05)

As shown in Table 2, the epoxy adhesive composition comprising the acid anhydride-based epoxy compound (MTPA-MFE) of the present invention exhibited improved impact strength and flexural strength. Specifically, Example 4 exhibited 97.3% improved impact strength and 7.4% improved flexural strength compared to Comparative Example 1, and Example 3 exhibited 71.9% improved impact strength and 11.3% improved flexural strength compared to Comparative Example 1. In addition, the onset temperature of the epoxy adhesive compositions containing the acid anhydride-based epoxy compound of the present invention was observed around 155 to 170 ℃, it can be seen that as the content of the acid anhydride-based epoxy compound increases, the T _peak also increases. From this, it can be seen that the increase in T _peak originates from the acid anhydride-based epoxy compound. The epoxy adhesive composition of the present invention has more improved physical properties compared to the comparative example in impact strength and flexural strength, and the base epoxy of the present invention It can be seen that when the resin and the acid anhydride-based epoxy compound are included in a molar ratio of 7.5 to 9: 1 to 2.5, they have extremely excellent physical properties.

Through this, the epoxy adhesive composition containing the acid anhydride-based epoxy compound according to the present invention can provide a cured product having excellent impact strength and flexural strength, and is significantly superior to the existing epoxy composition by preventing structural deformation due to external impact. It was confirmed that excellent durability can be expressed. In particular, it is possible to improve the impact strength and flexural strength of the product by adding it to the composition of the lightweight dissimilar material adhesion and coating material for automobiles.

As described above, in the present invention, specific matters and limited examples and comparative examples have been described, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the present invention is not limited to the above examples. Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (12)

An epoxy adhesive composition comprising an acid anhydride-based epoxy compound represented by the following formula (1).
[Formula 1]

In Formula 1,
R ₁ to R ₆ are each independently hydrogen or C _1-10 alkyl;
R ₁ and R ₂ are not simultaneously hydrogen;
Y is hydrocarbylene or heterohydrocarbylene. The method of claim 1,
In Formula 1, R ₁ to R ₂ are each independently hydrogen or methyl;
R ₃ to R ₆ are each independently hydrogen or C _1-7 alkyl;
R ₁ and R ₂ are not hydrogen at the same time, the epoxy adhesive composition. The method of claim 1,
In Formula 1, Y is C _5-60 alkylene, C _3-60 cycloalkylene, C _6-60 arylene, or C _3-60 heteroarylene;
Alkylene, cycloalkylene, arylene and heteroarylene of Y are optionally hydroxy, halogen, nitro, cyano, amino, carboxyl, carboxylate, C _1-20 alkyl, C _1-20 alkenyl, C _1-20 haloalkyl, C _1-20 alkoxy, C _1-20 alkoxycarbonyl, C _3-30 cycloalkyl, (C _6-30 )aryl(C _1-20 )alkyl, C _6-30 aryl and C Which may be substituted with one or more selected from _3-30 heteroaryl, the epoxy adhesive composition. The method of claim 1,
The acid anhydride-based epoxy compound of Formula 1 is an epoxy adhesive composition represented by Formula 2 below.
[Formula 2]

In the above formula (2),
R ₁ is C _1-7 alkyl;
R ₃ to R ₆ are each independently hydrogen or C _1-7 alkyl;
Y is hydrocarbylene or heterohydrocarbylene. 5. The method of claim 4,
In Formula 2, Y is C _5-30 alkylene, C _3-30 cycloalkylene, C _6-30 arylene or C _3-30 heteroarylene;
Said alkylene, cycloalkylene, arylene and heteroarylene are optionally hydroxy, halogen, nitro, cyano, amino, carboxyl, carboxylate, C _1-10 alkyl, C _1-10 alkenyl, C ₁ in _-10 haloalkyl, C _1-10 alkoxy, C _1-10 alkoxycarbonyl, C _3-20 cycloalkyl, C _{6-20 arylC 1-10} alkyl, C _6-20 aryl and C _3-20 heteroaryl Which may be substituted with one or more selected, the epoxy adhesive composition. 5. The method of claim 4,
The acid anhydride-based epoxy compound of Chemical Formula 2 is an epoxy adhesive composition represented by the following Chemical Formulas 3 to 4.
[Formula 3]

[Formula 4]

In Formulas 3 to 4,
R ₁ is C _1-7 alkyl;
A is -CO-, -SO-, -SO ₂ - or -C(R ₁₁ )(R ₁₂ )-, R ₁₁ to R ₁₂ are each independently hydrogen, C _1-7 alkyl, C _1-7 halo alkyl or C _6-12 aryl, or R ₁₁ to R ₁₂ may be linked to each other to form a C _3-10 alicyclic ring;
n is an integer from 1 to 10; The method of claim 1,
The epoxy adhesive composition is an epoxy adhesive composition further comprising a base epoxy resin, a curing agent and a curing accelerator. 8. The method of claim 7,
The epoxy adhesive composition of the base epoxy resin and the acid anhydride-based epoxy compound is included in a molar ratio of 1 to 9: 9 to 1. A cured product of the epoxy adhesive composition of any one of claims 1 to 8. An acid anhydride-based epoxy compound represented by the following formula (1).
[Formula 1]

In Formula 1,
R ₁ to R ₆ are each independently hydrogen or C _1-10 alkyl;
R ₁ and R ₂ are not simultaneously hydrogen;
Y is hydrocarbylene or heterohydrocarbylene. An acid anhydride compound represented by the following formula (5).
[Formula 5]

In Formula 5,
R is hydrogen, an alkali metal or an alkaline earth metal;
R ₂₁ to R ₂₆ are each independently hydrogen or C ₁ -C ₁₀ alkyl;
Except when R ₂₁ and R ₂₂ are hydrogen at the same time. 12. The method of claim 11,
The acid anhydride compound of Formula 5 is an acid anhydride compound selected from the following compounds.

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