KR102454135B1 - Two part epoxy adhesive composition containing acid anhydride-based epoxy compound modified with fatty acid and cured product prepared therfrom - Google Patents

Abstract

Through the introduction of a fatty acid-modified acid anhydride-based epoxy compound according to the present invention, it is possible to prepare a composition by designing desired mechanical properties by effectively improving the toughness of conventional epoxy resins. Specifically, by adding the fatty acid-modified acid anhydride-based epoxy compound to the composition of an adhesive and coating material for a lightweight heterogeneous material of automobiles, the compound can be used as a functional adhesive composition for different materials by improving adhesive performance such as tensile strain, shear strength, T-peel strength and the like of a product.<quillbot-extension-portal></quillbot-extension-portal>

Description

A two-part epoxy adhesive composition comprising a fatty acid-modified acid anhydride-based epoxy compound and a cured product prepared therefrom

The present invention relates to a two-part epoxy adhesive composition comprising a fatty acid-modified acid anhydride-based epoxy compound and a cured product prepared therefrom.

The demand for functional adhesives is increasing as the requirements for bonding and assembling production of high value-added materials are diversified in the domestic point/adhesive industry. For example, when bonding between dissimilar materials (steel-aluminum, steel-plastic, steel-composite materials, etc.) Because welding is difficult, functional adhesives are used. Such functional adhesives require mechanical properties such as impact strength, shear strength and peel strength as well as high elongation properties.

Among them, the epoxy adhesive has excellent mechanical properties, chemical resistance, electrical properties, etc., but lacks toughness, so it is difficult to use as an adhesive for different materials. To solve this problem, various toughening agents such as rubber or urethane are used, but these toughening agents have low mutual bonding strength with the epoxy base material, which may cause phase separation, and as a result, the adhesive performance such as shear strength and peel strength is lowered. do.

Therefore, it is urgently required to develop an adhesive that can improve the toughness of the conventional epoxy resin to satisfy high elongation characteristics and realize excellent mechanical properties and adhesive performance.

In order to solve the above problems, the present invention provides a two-component epoxy adhesive composition having excellent shear strength and T-peel strength.

In addition, the present invention provides a two-part epoxy adhesive composition comprising a novel fatty acid-modified acid anhydride-based epoxy compound and a cured product prepared therefrom.

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

In order to achieve the above object, the present inventors improved toughness than conventional epoxy resins to satisfy high elongation characteristics, and at the same time, to develop an epoxy adhesive composition that can realize excellent mechanical properties and adhesive performance. , Surprisingly, in the case of a two-component epoxy adhesive composition containing a specific fatty acid-modified acid anhydride-based epoxy compound, phase separation does not occur due to excellent compatibility with the base epoxy base material, and toughness is remarkably improved, such as shear strength and T-peel strength. The invention was completed by discovering that the adhesive performance was excellent.

The present invention provides a two-part epoxy adhesive composition comprising a base epoxy resin, a fatty acid-modified acid anhydride-based epoxy compound represented by the following Chemical Formula 1, a toughening agent, and a filler.

[Formula 1]

(In Formula 1,

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

Y is hydrocarbylene or heterohydrocarbylene;

Z is hydrocarbylene;

k is an integer greater than or equal to 1;

는 단일결합 또는 이중결합이다.)

is a single bond or a double bond.)

According to an embodiment of the present invention, the two-part epoxy adhesive composition comprises a first agent comprising a base epoxy resin, a fatty acid-modified acid anhydride-based epoxy compound represented by Formula 1, a toughening agent and a filler; and a second agent including a curing agent.

According to an embodiment of the present invention, in Formula 1, R _One To R ₂ They are each independently hydrogen or methyl; R ₃ to R ₆ may be each independently hydrogen or C _1-7 alkyl.

According to an embodiment of the present invention, Y in Formula 1 may be derived from an epoxy compound having a difunctional group.

According to an embodiment of the present invention, Z in Formula 1 may be derived from an unsaturated fatty acid.

According to an embodiment of the present invention, Z in Formula 1 is a branched type including one or more side chains, and may be derived from a dimer fatty acid.

According to an embodiment of the present invention, Z in Formula 1 may satisfy the following structure.

[rescue]

(In the above structure,

Z ₁ and Z ₃ are saturated or unsaturated C _3-30 alkylene or C _3-30 alkenylene;

Z ₂ and Z ₄ are saturated or unsaturated C _3-30 alkenyl or C _3-30 alkyl.)

According to an embodiment of the present invention, the total number of double bonds included in Z ₁ to Z ₄ of the structure may be 1 to 10.

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

[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 is C _6-50 hydrocarbylene or heterohydrocarbylene;

Z is hydrocarbylene derived from C _4-50 unsaturated fatty acids;

k is an integer greater than or equal to 1;

는 단일결합 또는 이중결합이다.)

is a single bond or a double bond.)

According to an embodiment of the present invention, Y in Formula 2 may be derived from an epoxy compound having a difunctional group.

According to an embodiment of the present invention, Z in Formula 2 is a branched type including one or more side chains, and may be derived from a dimer fatty acid.

According to an embodiment of the present invention, Chemical Formula 2 may be represented by the following Chemical Formulas 3 to 4.

[Formula 3]

[Formula 4]

(In Formulas 3 to 4,

R ₁₁ to R ₁₂ are each independently hydrogen or C _1-7 alkyl;

A is -CO-, -SO-, -SO ₂ - or -C(R ₁₃ )(R ₁₄ )-, and R ₁₃ to R ₁₄ are each independently hydrogen, C _1-7 alkyl, C _1-7 halo alkyl or C _6-12 aryl, or R ₁₃ to R ₁₄ may be linked to each other to form a C _3-10 alicyclic ring;

Z ₁ and Z ₃ are saturated or unsaturated C _3-30 alkylene or C _3-30 alkenylene;

Z ₂ and Z ₄ are saturated or unsaturated C _3-30 alkenyl or C _3-30 alkyl;

k is an integer greater than or equal to 1.)

According to an embodiment of the present invention, the toughening agent may be a urethane-based toughening agent, a rubber-based toughening agent, or a mixture thereof.

According to an embodiment of the present invention, the first agent of the two-part epoxy adhesive composition is based on 100 parts by weight of the base epoxy resin, 0.1 to 30 parts by weight of the fatty acid-modified acid anhydride-based epoxy compound represented by Formula 1, toughness It may contain 10 to 150 parts by weight of the agent and 0.1 to 50 parts by weight of the filler.

According to an embodiment of the present invention, the weight ratio of the base epoxy resin and the curing agent of the two-part epoxy adhesive composition may be 1 to 9: 9 to 1.

According to an embodiment of the present invention, the first agent of the two-part epoxy adhesive composition may further include a coupling agent.

According to an embodiment of the present invention, the second agent of the two-part epoxy adhesive composition may further include a filler.

According to an embodiment of the present invention, the second agent of the two-part epoxy adhesive composition may include 0.01 to 100 parts by weight of a filler based on 100 parts by weight of the curing agent.

A cured product obtained by curing the two-part epoxy adhesive composition according to an embodiment of the present invention may be provided. In addition, the cured product may be a two-part epoxy adhesive composition cured at room temperature.

The present invention provides an acid anhydride-based epoxy compound represented by the following formula (5).

[Formula 5]

(In Formula 5,

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;

k is an integer greater than or equal to 1.)

Preferably, in Formula 5 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; R ₁ and R ₂ may not be hydrogen at the same time.

More preferably, Y in Formula 5 according to an embodiment of the present invention 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 5 according to an embodiment of the present invention may be represented by Formula 6 below.

[Formula 6]

(In Formula 6,

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;

k is an integer greater than or equal to 1.)

In Formula 6 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, the acid anhydride-based epoxy compound of Chemical Formula 5 according to an embodiment of the present invention may be represented by the following Chemical Formulas 7 to 8.

[Formula 7]

[Formula 8]

(In Formulas 7 to 8,

R ₁ is C _1-7 alkyl;

A is -CO-, -SO-, -SO ₂ - or -C(R ₁₃ )(R ₁₄ )-, and R ₁₃ to R ₁₄ are each independently hydrogen, C _1-7 alkyl, C _1-7 halo alkyl or C _6-12 aryl, or R ₁₃ to R ₁₄ may be linked to each other to form a C _3-10 alicyclic ring;

m is a real number greater than or equal to 0.1.)

The present invention may provide an epoxy adhesive composition comprising an acid anhydride-based epoxy compound according to an embodiment of the present invention.

Specifically, the epoxy adhesive composition may further include a base epoxy resin, a curing agent, and a curing accelerator.

Preferably, 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.

The present invention may provide a fatty acid-modified 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;

Y is hydrocarbylene or heterohydrocarbylene;

Z is hydrocarbylene;

k is an integer greater than or equal to 1;

는 단일결합 또는 이중결합이다.)

is a single bond or a double bond.)

Preferably, Chemical Formula 1 may be represented by the following Chemical Formulas 3 to 4.

[Formula 3]

[Formula 4]

(In Formulas 3 to 4,

R ₁₁ to R ₁₂ are each independently hydrogen or C _1-7 alkyl;

A is -CO-, -SO-, -SO ₂ - or -C(R ₁₃ )(R ₁₄ )-, and R ₁₃ to R ₁₄ are each independently hydrogen, C _1-7 alkyl, C _1-7 halo alkyl or C _6-12 aryl, or R ₁₃ to R ₁₄ may be linked to each other to form a C _3-10 alicyclic ring;

Z ₁ and Z ₃ are saturated or unsaturated C _3-30 alkylene or C _3-30 alkenylene;

Z ₂ and Z ₄ are saturated or unsaturated C _3-30 alkenyl or C _3-30 alkyl;

k is an integer greater than or equal to 1.)

In the two-part adhesive composition containing the fatty acid-modified acid anhydride-based epoxy compound according to the present invention, phase separation does not occur when the fatty acid-modified acid anhydride-based epoxy compound directly participates in the curing reaction, so that when an impact is applied from the outside, the cured product It can effectively improve mechanical properties such as shear strength and T-peel strength and adhesive performance.

A two-part epoxy adhesive composition comprising a fatty acid-modified acid anhydride-based epoxy compound according to the present invention and a cured product prepared therefrom can be usefully used as functional adhesives in automobiles, aircraft, spacecraft, railways, ships, sports equipment and computer industries. can

1 (a) is a Fourier Transform-Infrared spectroscopy (Fourier Transform-Infrared spectroscopy, FT-IR) result graph of the fatty acid-modified acid anhydride-based epoxy compound (MHFA) prepared in Preparation Example 3 of the present invention, ( b) is a graph of the result of Fouray transform infrared spectroscopy analysis of the fatty acid-modified acid anhydride-based epoxy compound (MHJA) prepared in Preparation Example 4 of the present invention.

Hereinafter, an epoxy adhesive composition comprising a fatty acid-modified acid anhydride-based epoxy compound according to the present invention and a cured product prepared therefrom 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 from 2 to 30, preferably from 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. Heteroaryl groups can 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. Here, 'aryl' is as defined above.

,

,

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.

As used herein, "unsaturated" means the presence of one or more double bonds in a hydrocarbon chain, which double bonds may occur at any other internal position between the chains. One or more double bonds may exist continuously or may exist discontinuously.

As used herein, "unsaturated fatty acid" means a long hydrocarbon chain comprising at least one carbon-carbon double bond and terminated with a carboxylic acid. Specifically, the unsaturated fatty acid may have 4 to 50 carbon atoms, preferably 6 to 40 carbon atoms. The carbon-carbon double bond may be present at any position in the chain, and the unsaturated fatty acid may be linear or branched. The unsaturated fatty acid may be obtained or synthesized by saponification of a fatty acid ester, but is not particularly limited as long as it is commonly used in the art.

The "dimer fatty acid" described in the present invention means a dicarboxylic acid prepared by dimerizing an unsaturated fatty acid. The dimerization of unsaturated fatty acids can be realized using methods known in the art, and commercially available products can be used.

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 provides a two-part epoxy adhesive composition comprising a base epoxy resin, a fatty acid-modified acid anhydride-based epoxy compound represented by the following Chemical Formula 1, a toughening agent, and a filler.

[Formula 1]

는 단일결합 또는 이중결합일 수 있다. 바람직하게 상기 화학식 1에서 R₁ 내지 R₂는 서로 독립적으로 수소 또는 메틸이며; R₃ 내지 R₆은 서로 독립적으로 수소 또는 C_1-7알킬인 것일 수 있다.In Formula 1, R ₁ to R ₆ are each independently hydrogen or C _1-10 alkyl, Y is hydrocarbylene or heterohydrocarbylene, Z is hydrocarbylene, and k is an integer of 1 or more,

may be a single bond or a double bond. Preferably, in Formula 1, R ₁ to R ₂ are each independently hydrogen or methyl; R ₃ to R ₆ may be each independently hydrogen or C _1-7 alkyl.

According to an embodiment of the present invention, Y in Formula 1 may be derived from an epoxy compound having a difunctional group. The epoxy compound 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 Formula 1 may be an aromatic epoxy compound, and preferred examples thereof include bisphenol A-based, bisphenol AF-based, bisphenol AP-based, bisphenol B-based, bisphenol C-based, bisphenol E-based, bisphenol F-based, and bisphenol G-based. , at least one bisphenol type epoxy compound selected from bisphenol M type, bisphenol S type, bisphenol P type and bisphenol Z type, etc., glycidyl ether type epoxy compound, glycidyl amine type epoxy compound, phenol novolak type epoxy compound, and Any one or a mixture of two or more selected from a cresol novolak-type epoxy compound, etc. can be mentioned. More preferably, in terms of maximally improving shear strength and T-peel strength, it may be selected from a bisphenol A-based epoxy compound and a bisphenol F-based epoxy compound.

Y in Formula 1 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.

According to an embodiment of the present invention, Z in Formula 1 may be derived from an unsaturated fatty acid. The unsaturated fatty acid is selected from the group consisting of crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid and stearic acid It may be one or more, but is not limited thereto. In addition, the Z may mean a portion that does not include a carboxyl group in a unit derived from an unsaturated fatty acid.

Specifically, Z in Formula 1 according to an embodiment of the present invention may be a unit derived from a dimer fatty acid prepared by dimerizing the unsaturated fatty acid, and the dimer fatty acid includes one or more side chains (branched chain). may be branched. The side chain may be, but is not limited to, saturated or unsaturated C _3-30 alkenyl or C _3-30 alkyl. In addition, Z may mean a portion that does not include a carboxyl group in a unit derived from a dimer fatty acid.

More specifically, the dimer fatty acid may be a compound prepared by dimerizing the unsaturated fatty acid in the presence of a catalyst of bentonite, montmorillonite, kaolinite, hectorite or attapulgite clay. The dimer fatty acid may have one or more saturated or unsaturated side chains and may have two carboxylic acids at the ends. Specific examples include, but are not limited to, dimerized or trimerized oleic acid, dimerized or trimerized linoleic acid, dimerized or trimerized linolenic acid, or mixtures thereof. As such, the dimer fatty acid may be prepared by dimerizing the unsaturated fatty acid, or a commercially available product may be used.

In addition, the dimer fatty acid may be an acyclic dimer fatty acid, a cyclic dimer fatty acid, a polycyclic dimer fatty acid, or an aromatic dimer fatty acid. These dimer fatty acids may be prepared by dimerizing the unsaturated fatty acids, may be commercially available products, and specific examples may be those represented by the following compounds, but are not limited thereto.

In the compound, n may be an integer of 1 or more, specifically 1 to 10, and more specifically 1 to 5.

Preferably, the dimer fatty acid may have a carbon number of C _4-50 , specifically, a carbon number of C _6-40 , and the molecular weight of the dimer fatty acid is 200 to 1500 g/mol, specifically 300 to 1100. g/mol, more specifically, may have a molecular weight of 400 to 800 g/mol. In addition, the acid value may be 150 to 250 mgKOH/g, but the carbon number, molecular weight, and acid value range are not particularly limited as long as the physical properties targeted by the present invention are not impaired.

In addition, the dimer fatty acid may include one or more double bonds at any position of the chain, and may include a side chain and be branched. Specifically, according to an embodiment of the present invention, Z in Formula 1 may satisfy the following structure.

[rescue]

In the above structure, Z ₁ and Z ₃ are saturated or unsaturated C _3-30 alkylene or C _3-30 alkenylene, Z ₂ and Z ₄ are saturated or unsaturated C _3-30 alkenyl or C _3-30 alkyl may be, specifically Z ₁ and Z ₃ are saturated or unsaturated C _3-20 alkylene or C _3-20 alkenylene, Z ₂ and Z ₄ are saturated or unsaturated C _3-20 alkenyl or C _{3 -20} alkyl. The alkenylene and alkenyl may include one or more double bonds at any position in the chain, and the total number of double bonds included in Z ₁ to Z ₄ is 1 to 10, preferably 2 to 8. can In addition, two or more selected from Z ₁ to Z ₄ may be connected to form one or more alicyclic rings, and the alicyclic rings may include one or more double bonds. In the case of Z having the above structure, the two-component epoxy adhesive composition of the present invention may exhibit high elongation properties compared to conventional epoxy resins.

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

[Formula 2]

는 단일결합 또는 이중결합이다. 구체적으로 R₁ 은 메틸이며, R₃ 내지 R₆은 서로 독립적으로 수소 또는 메틸이고, Y는 C_6-50 하이드로카빌렌 또는 헤테로하이드로카빌렌이고, Z는 C_4-50 불포화 지방산 유래 하이드로카빌렌이며, k는 1 내지 5의 정수이다. 상기 Y, Z 및 불포화 지방산에 대한 설명 및 구체적인 화합물의 예는 앞서 화학식 1에서 서술한 바와 동일하다.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 is C _6-50 hydrocarbylene or heterohydrocarbylene, and Z is C _4-50 hydrocarbylene derived from unsaturated fatty acids, k is an integer of 1 or more,

is a single bond or a double bond. Specifically, R ₁ is methyl, R ₃ to R ₆ are each independently hydrogen or methyl, Y is C _6-50 hydrocarbylene or heterohydrocarbylene, and Z is C _4-50 hydrocarbylene derived from unsaturated fatty acids. and k is an integer from 1 to 5. Descriptions of Y, Z and unsaturated fatty acids and examples of specific compounds are the same as those described in Formula 1 above.

According to an embodiment of the present invention, Chemical Formula 2 may be represented by the following Chemical Formulas 3 to 4.

[Formula 3]

[Formula 4]

In Formulas 3 to 4, R ₁₁ to R ₁₂ are each independently hydrogen or C _1-7 alkyl, and A is -CO-, -SO-, -SO ₂ - or -C(R ₁₃ )(R ₁₄ )- and R ₁₃ to R ₁₄ are each independently hydrogen, C _1-7 alkyl, C _1-7 haloalkyl, or C _6-12 aryl, or R ₁₃ to R ₁₄ are linked to each other to form a C _3-10 alicyclic ring Z ₁ and Z ₃ are saturated or unsaturated C _3-30 alkylene or C _3-30 alkenylene, Z ₂ and Z ₄ are saturated or unsaturated C _3-30 alkenyl or C _3-30 alkyl, and k is 1 or more or an integer of 1 to 5. Specifically, R ₁₁ to R ₁₂ may be each independently hydrogen or methyl, Z ₁ and Z ₃ are saturated or unsaturated C _3-20 alkylene or C _3-20 alkenylene, and Z ₂ and Z ₄ are saturated Or it may be an unsaturated C _3-20 alkenyl or C _3-20 alkyl, and the total number of double bonds included in Z ₁ to Z ₄ may be 2 to 8. When a two-component epoxy adhesive composition is prepared using a fatty acid-modified acid anhydride-based epoxy compound that satisfies the above range, the shear strength and T-peel strength are improved, thereby exhibiting adhesive properties suitable as an adhesive for different materials.

The epoxy equivalent weight of the fatty acid-modified acid anhydride-based epoxy compound according to an embodiment of the present invention is 500 to 1500 g/eq. may be specifically 600 to 1300 g/eq. It may satisfy the range, and when a fatty acid-modified acid anhydride-based epoxy compound satisfying the above range is used, the adhesive properties such as shear strength and T-peel strength of the two-component epoxy adhesive composition can be further improved. good night.

The two-component 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 at room temperature or thermosetting type have. The room temperature curing type may be cured at room temperature for 3 to 10 days, but if curing is completed at room temperature, the curing time is not particularly limited. In addition, 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, at a temperature of 80 to 250 ° C., more specifically, it may be thermally cured at a temperature of 80 to 150 ° C., and preferably thermally cured at a temperature of 80 to 120 ° C. for 10 minutes or more, but is not limited thereto.

According to an embodiment of the present invention, the two-part epoxy adhesive composition comprises a first agent comprising a base epoxy resin, a fatty acid-modified acid anhydride-based epoxy compound represented by Formula 1, a toughening agent and a filler; and a second agent including a curing agent.

The base epoxy resin may be used without limitation as long as it is conventionally used in the relevant field. For example, any one or more bisphenol-type epoxy resins selected from bisphenol A, bisphenol E, bisphenol F, bisphenol M, bisphenol S, and bisphenol H; and any one or a mixture of two or more selected from a glycidyl ether-based epoxy resin, a glycidyl amine-based epoxy resin, a phenol novolak-type epoxy resin, and a cresol novolak-type epoxy resin. Preferably, any one or two or more selected from the bisphenol A-based epoxy resin and the bisphenol F-based epoxy resin may be used in terms of maximally improving the adhesive performance, shear strength and T-peel strength.

In addition, the base epoxy resin may be a liquid at room temperature, and may have an epoxy equivalent weight (EEW) of 100 to 600 g/eq, or 150 to 550 g/eq. When the above range is satisfied, it may have more advantageous properties in that adhesive performance such as shear strength and T-peel strength to the bonding site is improved as well as the above-described effects.

According to an embodiment of the present invention, the first agent of the two-part epoxy adhesive composition is based on 100 parts by weight of the base epoxy resin, 0.1 to 30 parts by weight of the fatty acid-modified acid anhydride-based epoxy compound represented by Formula 1 above, preferably 1 to 30 parts by weight, more preferably 5 to 25 parts by weight. In the case of a two-component epoxy adhesive composition having a content in the above range, not only adhesion performance such as elongation, shear strength and T-peel strength is excellent, but also its utility as an adhesive for dissimilar materials can be further expanded.

According to an embodiment of the present invention, the toughening agent may be a urethane-based toughening agent, a rubber-based toughening agent, or a mixture thereof.

The urethane-based toughening agent may be used to increase elongation (tensile strain), shear strength and T-peel strength of the adhesive composition of the present invention, and is not limited as long as it is commonly used in the field. In addition, in order to effectively improve the shear strength and T-peel strength targeted in the present invention, specifically, for example, a polyol compound having a molecular weight of 1,000 to 3,000 g/mol and a polyisocyanate compound are reacted using a tin-based catalyst, and , one prepared by capping with a phenol-based capping agent such as lysocinol may be used. In this case, the polyol compound may be specifically polyether diol, and the polyisocyanate compound may be an alicyclic diisocyanate compound such as isophorone diisocyanate.

The rubber-based toughening agent may include rubber, a rubber copolymer, or a rubber derivative. Specific examples include butadiene rubbers such as terminal vinylized butadiene rubber, chlorinated butadiene rubber, chlorosulfonated butadiene rubber, nitrile butadiene rubber, and styrene butadiene rubber; chlorosulfonated polyethylene; silicone rubber; rubber copolymers such as a styrene-butadiene-polymethylmethacrylate triblock copolymer, an acrylonitrile-butadiene-styrene copolymer, and a styrene-butadiene-styrene copolymer; or a rubber derivative, and the like, and any one or a mixture of two or more thereof may be used.

In addition, the rubber-based toughening agent may be a core-shell type rubber-based toughening agent. Specific examples include acrylic rubber, silicone rubber, urethane rubber, styrene-butadiene rubber, butadiene rubber, and the like. The core part and the shell part do not have to be the same type of rubber, and the core part is silicone rubber and the shell part is acrylic rubber, or the core part is butadiene rubber and the shell part is acrylic rubber. not available and available. In the preparation, it can be prepared by a well-known method, for example, emulsion polymerization, suspension polymerization, microsuspension polymerization, and the like. The core-shell type rubber-based toughening agent is preferably spherical. In addition, although not limited, the average particle diameter may be 0.01 to 20 μm, preferably 0.1 to 5 μm.

The toughening agent may be used in an amount of 10 to 150 parts by weight based on 100 parts by weight of the base epoxy resin, preferably 50 to 100 parts by weight, and more preferably 55 to 75 parts by weight, but does not impair the physical properties described in the present invention. Otherwise, the content range is not particularly limited.

The filler may be used to improve mechanical strength, thermal dimensional stability and moisture resistance. Specifically, for example, quartz, limestone, mica, fumed silica, calcium carbonate, magnesium carbonate, aluminum nitride, boron nitride, silicon nitride, aluminum hydroxide, hydrotalcite, magnesium hydroxide, calcium hydroxide, wollastonite, bentonite, silica , alumina, titanium oxide, barium sulfate, calcium sulfate, any one selected from the group consisting of talc and glass fiber, or a mixture of two or more may be used. The filler may be used in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the base epoxy resin, preferably 10 to 40 parts by weight, and more preferably 15 to 30 parts by weight. It is good that it can exhibit excellent shear strength and T-peel strength in the above range, but the content range is not particularly limited as long as it does not impair the physical properties described in the present invention. can be used

According to an aspect of the present invention, the first agent of the two-part epoxy adhesive composition may further include a coupling agent. The coupling agent may be any one or a mixture of two or more selected from epoxysilane, aminosilane, and alkylsilane, but is not limited thereto. In addition, the content of the coupling agent may be included in an amount of 0.001 to 1 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the base epoxy resin, but is not limited thereto.

According to an embodiment of the present invention, the curing agent in the second agent of the two-part epoxy adhesive composition is for curing the adhesive composition of the present invention, and may be reacted with the first agent to prepare a cured product. As the curing agent, both a solid curing agent and a liquid curing agent commonly used may be used, and the curing agent may directly participate in crosslinking of the composition or may be used in the form of a catalyst.

According to an embodiment of the present invention, the curing agent may be an amine-based curing agent, an acid anhydride-based curing agent, or a phenol-based curing agent. These may be used independently and may mix and use 2 or more types. Preferably, an amine-based curing agent may be used.

Examples of the amine-based curing agent include dimethyldisican, dicyandiamide, isophoronediamine, diethylenetriamine, triethylenetetramine, triethylenepentamine, bis(p-aminocyclohexyl)methane, methylenedianiline (eg , 4,4'-methylenedianiline, etc.), 4,7,10-trioxatridecane-1,13-diamine, polyetheramine (eg, Jeffamine D-230, Jeffamine D-400, etc.), diaminodi Phenylmethane, diaminodiphenylsulfone, 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 selected may be used.

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, methyl and any one or two or more selected from hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride.

Examples of the phenol-based curing agent include phenol resins such as formaldehyde condensed resol type phenol resin, non-formaldehyde condensed phenol resin, novolak type phenol resin, novolak type phenol formaldehyde resin, and polyhydroxystyrene resin; resol-type phenol resins such as aniline-modified resol resins and melamine-modified resol resins; novolak-type phenolic resins such as phenol novolac resin, cresol novolac resin, tert-butylphenol novolac resin, nonylphenol novolak resin and naphthol novolak resin; 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 polyhydroxystyrene resins such as poly(p-hydroxystyrene).

According to an embodiment of the present invention, in the two-part epoxy adhesive composition, the weight ratio of the base epoxy resin of the first agent and the curing agent of the second agent may be 1 to 9: 9 to 1. Specifically, it may have a weight ratio of 1 to 5: 5 to 1, more specifically 1 to 3: 3 to 1, but is not limited thereto.

According to an embodiment of the present invention, the second agent of the two-part epoxy adhesive composition may further include a filler. Specific examples of the filler are the same as described above, and the content of the filler is 0.01 to 100 parts by weight, specifically 1 to 50 parts by weight, more specifically 1 to 30 parts by weight of the filler based on 100 parts by weight of the curing agent of the second agent. It may include parts by weight, but is not limited thereto.

The second agent of the two-part epoxy adhesive composition may further include a curing accelerator. The curing accelerator is used together with the curing agent to control the curing rate, and may be any one or two or more selected from a tertiary amine-based curing accelerator, an imidazole-based curing accelerator, and a urea-based curing accelerator, but is not limited thereto .

Examples of the tertiary amine-based curing accelerator include any one or two or more selected from benzyldimethylamine, triethanolamine, triethylenediamine, dimethylaminoethanol or tri(dimethylaminomethyl)phenol.

Examples of the imidazole-based curing 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 any one or two or more selected from 1-cyanoethyl-2-undecylimidazole and the like.

Examples of the urea-based curing accelerator include any one selected from p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, and 3,4-dichlorophenyl-N,N-dimethylurea; Two or more may be mentioned.

The curing accelerator may be used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the epoxy resin, more preferably 0.01 to 5 parts by weight, and still more preferably 0.5 to 3 parts by weight. Although it is good that sufficient hardening acceleration effect can be expressed in the said range, if the physical property described by this invention is not impaired, it is not restrict|limited in particular.

In addition to this, one or more other additives may be optionally added to the two-part epoxy adhesive composition according to an embodiment of the present invention. For example, optional additives include 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, UV stabilizers, antioxidants, mold release agents, and mixtures thereof may be further included. The optional additive may be used in a range that does not impair the physical properties of the adhesive composition of the present invention.

A cured product obtained by curing the two-part epoxy adhesive composition according to an embodiment of the present invention may be provided. Specifically, the curing may be room temperature curing or thermal curing, and more specifically, in the thermal curing process, the curing temperature and curing time of the process may be variously set according to the conditions of the curing agent, the curing accelerator, and the specimen, but for example 80 to 150 It may be dried at a temperature of ℃ for 30 minutes or more, but is not particularly limited thereto. In addition, the two-component epoxy adhesive composition of the present invention can be cured at room temperature, so it does not require handling and heating equipment, so the curing process is simple. . As such, the composition of the present invention can be cured using the method of the curing process commonly used, and the curing process of the two-component epoxy adhesive composition is not particularly limited as long as the physical properties for the purpose of the present invention are not impaired.

The present invention may provide an acid anhydride-based epoxy compound represented by the following formula (5).

[Formula 5]

In Formula 5, 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, Y is hydrocarbylene or heterohydrocarbylene, and k may be an integer of 1 or more. .

The epoxy adhesive composition according to an embodiment of the present invention includes the acid anhydride-based epoxy compound represented by Chemical Formula 5, so that the toughness is effectively improved compared to the conventional epoxy resin, and the durability is surprisingly improved. In terms of having more improved durability, preferably in Formula 5 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, Y in Formula 5 according to an embodiment of the present invention 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, in Formula 5, 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.

More preferably, the acid anhydride-based epoxy compound of Formula 5 according to an embodiment of the present invention may be represented by Formula 6 below.

[Formula 6]

In Formula 6, R ₁ may be C _1-7 alkyl, R ₃ to R ₆ may be each independently hydrogen or C _1-7 alkyl, Y is hydrocarbylene or heterohydrocarbylene, and k is It may be an integer of 1 or more. Preferably, in Formula 6 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 6, 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 5 and 6 may be an organic group derived from an epoxy compound, and examples of descriptions and specific compounds may be the same as or different from Y in Formula 1 above.

More preferably, the acid anhydride-based epoxy compound of Chemical Formula 5 according to an embodiment of the present invention may be represented by the following Chemical Formulas 7 to 8.

[Formula 7]

[Formula 8]

In Formulas 7 to 8, R ₁ may be C _1-7 alkyl, A is -CO-, -SO-, -SO ₂ - or -C(R ₁₃ )(R ₁₄ )-, and R ₁₃ to R ₁₄ may be each independently hydrogen, C _1-7 alkyl, C _1-7 haloalkyl or C _6-12 aryl, or R ₁₃ to R ₁₄ may be connected to each other to form a C _3-10 alicyclic ring, m may be greater than or equal to 0.1 or a real number from 0.1 to 5.

Preferably, in Formulas 7 to 8, R ₁ may be C _1-5 alkyl, A is -CO-, -SO-, -SO ₂ - or -C(R ₁₃ )(R ₁₄ )-, and R ₁₃ to R ₁₄ may be each independently hydrogen, C _1-7 alkyl, C _1-7 haloalkyl or C _6-12 aryl, or R ₁₃ to R ₁₄ may be connected to each other to form a C _3-10 alicyclic ring, n may be an integer from 1 to 10. More preferably, R ₁ may be C _1-3 alkyl, A may be —SO ₂ — or —C(R ₁₃ )(R ₁₄ )-, and R ₁₃ to R ₁₄ are each independently hydrogen, C _{1 -7} alkyl or C _1-7 haloalkyl, or R ₁₃ to R ₁₄ may be connected to each other to form a C _3-10 alicyclic ring, and n may be a real number of 0.1 or more.

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 present invention may provide an epoxy adhesive composition comprising an acid anhydride-based epoxy compound according to an embodiment of the present invention, specifically active energy ray curing type, moisture curing type, thermosetting type or room temperature curing type, etc., preferably It may be 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.

Specifically, the epoxy adhesive composition 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, and specific examples of the compound are the same as described above.

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, and specific examples of the compound are the same as described above. 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.

In addition, the present invention provides a cured product of the epoxy adhesive composition according to an embodiment of the present invention. The cured product is very good because it can exhibit excellent elongation, T-peel strength and shear strength.

The present invention may provide a fatty acid-modified acid anhydride-based epoxy compound represented by the following formula (1).

[Formula 1]

는 단일결합 또는 이중결합이다. 바람직하게, 상기 화학식 1는 하기 화학식 3 내지 4로 표시되는 것일 수 있다. In Formula 1, R ₁ , R ₆ are Y, Z and k are the same as described above,

is a single bond or a double bond. Preferably, Chemical Formula 1 may be represented by the following Chemical Formulas 3 to 4.

[Formula 3]

[Formula 4]

상기 화학식 3 내지 4에서, R₁₁, R₁₂, A, Z₁ 내지 Z₄ 및 k는 상기 서술한 바와 동일하다.

In Formulas 3 to 4, R ₁₁ , R ₁₂ , A, Z ₁ to Z ₄ and k are the same as described above.

Hereinafter, a two-part epoxy adhesive composition comprising a fatty acid-modified 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.

[Method for evaluating physical properties]

1. Epoxy equivalent weight [g/eq.]

The epoxy equivalent weight was measured according to ASTM D 1652-04.

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] and tensile strain [%]

Tensile strength and tensile strain were measured according to ASTM D 638 using a universal testing machine (UTM 5982, INSTRON). When measuring the tensile strain, the specimen was prepared by curing at 100° C. for 30 minutes, and it was judged that the higher the tensile strain, the better the elongation.

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/min in a temperature range of -80 to 250 °C.

6. Shear strength [MPa]

*For the shear strength test piece, a 25 x 12.7 mm adhesive part is formed on two metal steel plates (SPRC440, 25 x 100 x 1.6 mm), overlapped with each other, and the thickness of the adhesive part is adjusted with a glass bead, and then cured at 100 ° C for 20 minutes. produced. Shear strength was measured by pulling the adherend at a speed of 1.3 mm/min according to ASTM D-1002 standard with a universal testing machine (UTM, universal testing machine).

7. T-peel strength [N/25㎜]

The T-peel strength test piece was prepared according to ISO 11339 standard using two metal steel plates (SPRC440, 25 x 305 mm). The thickness of the bonding site was controlled with a glass bead of 2 mm, and the specimen was prepared by curing at 100° C. for 20 minutes. T-peel strength was measured by pulling the adherend at a speed of 50 mm/min with a universal testing machine (UTM, universal testing machine).

[Preparation Example 1] Preparation of acid anhydride-based epoxy compound (MHPA-MFE)

Preparation of -MHPA-ME

After putting 168.0 g (0.76 mol) of 4-methylhexahydrophthalic anhydride (4-MHHPA) and 59.0 g (0.76 mol) of glycidol in a round flask, the reaction mixture was stirred at 60° C. for 3 hours. was sampled and the reaction was terminated at the point where the epoxy equivalent weight became 242 g/eq. to obtain an acid anhydride-based compound (MHPA-ME).

-Preparation of MHPA-MFE

Bisphenol F diglycidyl ether having an epoxy group at the end of a round flask and The compound of Example 1 (MHPA-ME) was added in a molar ratio of 1:1, and the reaction mixture was sampled while stirring at 110° C. for 2 hours, and the reaction was terminated at the point where the epoxy equivalent weight became 277 g/eq.

The MHPA-MFE obtained by the above method was analyzed by FT-IR and is shown in FIG. 1 . It was confirmed that MHPA-MFE was prepared by confirming that an ester peak and an epoxy peak corresponding to each epoxy were generated.

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

- Preparation of 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 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. It was confirmed that the acid anhydride ring was opened as the peak of 1875 cm ^-1 , the peak of the symmetric anhydride, disappeared, and the production of the target product MTPA-ME was confirmed by confirming that the epoxy structure was added as a newly generated peak in the 910 cm ^-1 region. did.

- Manufacture of 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 at a molar ratio of 1:1, and the reaction mixture was sampled while stirring at 110° C. for 2 hours, and the epoxy equivalent weight measured by ASTM D1652 was 302.8 g/eq. The reaction was terminated in

MTPA-MFE obtained by the above method was analyzed by FT-IR, and it was confirmed that MTPA-MFE was prepared by confirming that an ester peak and an epoxy peak corresponding to each epoxy were generated.

[Preparation Example 3] Preparation of fatty acid-modified acid anhydride-based epoxy compound (MHFA)

In a 1L round flask, the MHPA-MFE and dimer acids (dimer acids, CRODA, Pripol 1013-LQ-(GD)) were prepared in a molar ratio of 2:1, and triphenylphosphate was added to the dimer fatty acids. 0.1 mol% of was added and the reaction mixture was sampled while stirring at 105° C. for 3 hours or more, and the reaction was terminated at the point where the epoxy equivalent weight became 813 g/eq.

The MHFA obtained by the above method was analyzed through FT-IR, which is shown in FIG. 1 . As shown in Fig. 1 (a), the structure of the target product MHFA was confirmed by the movement of the ester peak, the generation and movement of the epoxy peak, and the generation of 2852-2922 cm ^-1 , the peak of the dimer fatty acid repeating unit, in MHPA-MFE. .

[Preparation Example 4] Preparation of fatty acid-modified acid anhydride-based epoxy compound (MHJA)

-Manufacturing of MHPA-MJE

In the preparation of MHPA-MFE of Preparation Example 1, JRE-320 (Ductile epoxy, m is 0.8 to 1) instead of bisphenol F diglycidyl ether was used in the same manner as in Preparation Example 1, except that MHPA- MJE was obtained.

The MHPA-MJE obtained by the above method was analyzed through FT-IR, and the results are shown in FIG. 1(b). The structure of the target product MHPA-MJE was confirmed by the generation of an ester peak and an epoxy peak corresponding to each epoxy.

-Manufactured by MHJA

In a 1L round flask, the MHPA-MJE and dimer acids (CRODA, Pripol 1013-LQ-(GD)) were prepared in a molar ratio of 2:1, and triphenylphosphate was added to the dimer fatty acids. 0.1 mol% of was added and the reaction mixture was sampled while stirring at 105° C. for 3 hours or more, and the reaction was terminated at the point where the epoxy equivalent weight became 1008 g/eq.

MHJA obtained by the above method was analyzed through FT-IR, which is shown in FIG. 1 . As shown in Fig. 1 (b), the structure of the target product MHJA was confirmed by the movement of the ester peak in MHPA-MJE, the generation and movement of the epoxy peak, and the generation of 2852-2922 cm ^-1 , the peak of the dimer fatty acid repeating unit. .

[Examples 1 to 6]

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 base epoxy resin and the acid anhydride-based epoxy compounds of Preparation Examples 1 and 2 (MHPA-MFE, MTPA- MHPA-MFE and MTPA-MFE were added so that the molar ratio of MFE) was 9: 1, 8: 2, 7.5: 2.5, respectively, to prepare epoxy adhesive compositions, respectively. As a curing agent, dicyandiamide (DICY, AIR PRODUCTS) was used, and the epoxy equivalent weight of the base epoxy resin included in the composition and the active hydrogen equivalent weight (AHEW) of dicyandiamide were added in a 1:1 ratio. 0.2 parts by weight of 2-methylimidazole as a curing accelerator was added based on 100 parts by weight of the base epoxy resin.

The epoxy adhesive composition prepared in each was heat-cured in a curing oven to prepare a cured product, and each cured product contained the base epoxy resin and the acid anhydride-based epoxy compound of Preparation Examples 1 and 2 in a molar ratio of 9: 1. The cured product prepared with the composition was MHPA-MFE 10 or MTPA-MFE 10, and the cured product prepared with the composition included in a molar ratio of 8: 2 was MHPA-MFE 20 or MTPA-MFE 20, and the molar ratio was 7.5: 2.5. A cured product prepared with the included composition was denoted as MHPA-MFE 25 or 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 1, except that MHPA-MFE, an acid anhydride-based epoxy compound of Preparation Example 1 of the present invention, was not added in Example 1.

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 1
(MHPA-MFE 10) MHPA-MFE One 9 Example 2
(MHPA-MFE 20) MHPA-MFE 2 8 Example 3
(MHPA-MFE 25) MHPA-MFE 2.5 7.5 Example 4
(MTPA-MFE 10) MTPA-MFE One 9 Example 5
(MTPA-MFE 20) MTPA-MFE 2 8 Example 6
(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 1
(MHPA-MFE 10) 169.55 156.91 79.23 (±5.27) 59.17 (±6.11) 150.6 (±11.1) Example 2
(MHPA-MFE 20) 176.75 165.47 81.41 (±5.26) 61.62 (±3.17) 139.1 (±15.8) Example 3
(MHPA-MFE 25) 179.36 167.56 77.38 (±8.03) 50.42 (±2.34) 131.9 (±11.0) Example 4
(MTPA-MFE 10) 176.67 160.29 81.30 (±7.1) 65.10 (±5.16) 120.3 (±2.34) Example 5
(MTPA-MFE 20) 177.18 160.37 93.34 (±2.33) 55.70 (±5.76) 116.1 (±5.70) Example 6
(MTPA-MFE 25) 178.62 160.47 80.41 (±3.94) 52.20 (±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 (MHPA/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. 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 resin of the present invention and the acid anhydride-based epoxy compound have a molar ratio of 7.5 to 9: 　 1 to 2.5. It can be seen that when it is included, it has 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.

[Examples 7 to 9]

A first agent consisting of 24.1 g of a base epoxy resin, 24.9 g of a toughening agent, 3 g of a filler, 0.3 g of a coupling agent, and the fatty acid-modified acid anhydride-based epoxy compound (MHFA) of Preparation Example 3, 36 g of a curing agent, and 4.25 g of a filler Two preparations were prepared. The content of the fatty acid-modified acid anhydride-based epoxy compound (MHFA) of Preparation Example 3 was added according to Table 3 below. The epoxy adhesive composition in which the first agent and the second agent were mixed was added to a planetary mixer and stirred at room temperature for 30 minutes under vacuum conditions to prepare an epoxy adhesive composition.

As the base epoxy resin, MOMENTIVE's EPIKOTE 828 (epoxy equivalent weight: 187 g/eq) was used. It was mixed and used. As the curing agent, an amine-based curing agent (Kukdo Chemical, Jeffamine D-230) was used, and as the filler, a mixture of calcium carbonate, aluminum hydroxide, and calcium oxide in a 1:1:1 weight ratio was used, and the coupling agent was epoxy. A mixture of silane and alkylsilane in a weight ratio of 1:1 was used.

[Examples 10 to 12]

Example 7 was carried out in the same manner as in Example 7, except that the fatty acid-modified acid anhydride-based epoxy compound (MHJA) of Preparation Example 4 was used instead of the fatty acid-modified acid anhydride-based epoxy compound (MHFA) of Preparation Example 3 . The content of the fatty acid-modified acid anhydride-based epoxy compound (MHJA) of Preparation Example 4 was added according to Table 3 below.

A cured product was prepared by curing the epoxy adhesive composition prepared in each, and each cured product contained 10, 20 and 25 parts by weight of a fatty acid-modified acid anhydride-based epoxy compound (MHFA) with respect to 100 parts by weight of the base epoxy resin. MHFA 10, 20, and 25 for cured products prepared with the composition indicated.

In addition, the prepared cured product was measured for physical properties through the evaluation method described above, and the measured results are shown in Table 3 below.

[Comparative Example 2]

A cured product was prepared in the same manner as in Example 7, except that in Example 7, the fatty acid-modified acid anhydride-based epoxy compound (MHFA) of Preparation Example 3 of the present invention was not added. The prepared cured product was measured for physical properties by the evaluation method described above, and the measured results are shown in Table 3 below.

Fatty acid modified acid anhydride based epoxy compound tensile strain
(Tensile strain) shear strength
(Shear strength) T-peel strength
(T-peel strength) type content
(g) phr % MPa N/25mm Example 7
(MHFA 10) MHFA 2.41 10 44.01 24.40 267.8 Example 8
(MHFA 20) MHFA 4.82 20 47.51 22.48 280.8 Example 9
(MHFA 25) MHFA 6.02 25 49.09 22.65 257.3 Example 10
(MHJA 10) MHJA 2.41 10 45.88 23.20 255.0 Example 11
(MHJA 20) MHJA 4.82 20 46.16 22.40 260.7 Example 12
(MHJA 25) MHJA 6.02 25 48.99 22.02 244.5 Comparative Example 2
(MHJA 0, MHJA 0) - 29.51 20.97 210.9

As shown in Table 3, it was confirmed that the two-component epoxy adhesive composition comprising the fatty acid-modified acid anhydride-based epoxy compound according to the present invention exhibited improved tensile strain and shear strength as well as T-peel strength. Specifically, it was confirmed that In the case of Example 7 in which the content of MHFA was 10phr, 16.4% improved shear strength and 27.0% improved T-peel strength compared to Comparative Example 1, and in Example 8, in which the content of MHFA was 20phr, 7.2% compared to Comparative Example 2 It showed improved shear strength and 33.1% improved T-peel strength. In addition, in the case of Example 10, in which the content of MHJA was 10 phr, 10.6% improved shear strength and 20.9% improved T-peel strength compared to Comparative Example 2, and Example 11 in which the content of MHJA was 20 phr compared to Comparative Example 2 It showed 6.8% improved shear strength and 23.6% improved T-peel strength. The two-part epoxy adhesive composition of the present invention has more improved physical properties compared to the comparative example in shear strength and T-peel strength, and the fatty acid-modified acid anhydride-based epoxy compound of the present invention is 5 parts by weight based on 100 parts by weight of the base epoxy resin. It can be seen that when included in an amount of from 25 parts by weight to 25 parts by weight, it has extremely excellent physical properties.

In addition, it was confirmed that the tensile strain also increased as the content of the fatty acid-modified acid anhydride-based epoxy compound increased. Specifically, in the case of Example 1, it was confirmed that the tensile strain, ie, elongation, was increased by 49.1% compared to Comparative Example 2, thereby confirming the high elongation characteristics of the two-component epoxy adhesive composition of the present invention.

Through this, the epoxy adhesive composition comprising the fatty acid-modified acid anhydride-based epoxy compound according to the present invention can provide a cured product having excellent elongation, shear strength and T-peel strength, and prevent structural deformation due to external impact By doing so, it was confirmed that durability significantly superior to that of the existing epoxy composition can be expressed. Specifically, it can be used in various ways as a lightweight, heterogeneous material bonding and coating material for automobiles.

As described above, the present invention has been described with specific matters and limited examples and comparative examples, 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 described below, 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 (32)

A two-part epoxy adhesive composition comprising a base epoxy resin, a fatty acid-modified acid anhydride-based epoxy compound represented by the following Chemical Formula 1, a toughening agent, and a filler.
[Formula 1]

In Formula 1,
R ₁ to R ₆ are each independently hydrogen or C _1-10 alkyl;
Y is hydrocarbylene or heterohydrocarbylene;
Z is hydrocarbylene;
k is an integer greater than or equal to 1;

is a single bond or a double bond. The method of claim 1,
The two-part epoxy adhesive composition is
a first agent comprising a base epoxy resin, a fatty acid-modified acid anhydride-based epoxy compound represented by Formula 1, a toughening agent, and a filler; and
A two-part epoxy adhesive composition comprising; a second agent including a curing agent. 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 two-part epoxy adhesive composition. The method of claim 1,
Y of Formula 1 is a two-part epoxy adhesive composition derived from an epoxy compound having a bifunctional group. The method of claim 1,
Z of Formula 1 is a two-part epoxy adhesive composition derived from an unsaturated fatty acid. 6. The method of claim 5,
Z of Formula 1 is a branched type including one or more side chains (branched chain), and a two-part epoxy adhesive composition derived from a dimer fatty acid. 7. The method of claim 6,
Z of Formula 1 is a two-part epoxy adhesive composition that satisfies the following structure.
[rescue]

In the above structure,
Z ₁ and Z ₃ are saturated or unsaturated C _3-30 alkylene or C _3-30 alkenylene;
Z ₂ and Z ₄ are saturated or unsaturated C _3-30 alkenyl or C _3-30 alkyl. 8. The method of claim 7,
A two-part epoxy adhesive composition wherein the total number of double bonds contained in Z ₁ to Z ₄ of the structure is 1 to 10. The method of claim 1,
The formula (1) is a two-part epoxy adhesive composition represented by the following formula (2).
[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 is C _6-50 hydrocarbylene or heterohydrocarbylene;
Z is hydrocarbylene derived from C _4-50 unsaturated fatty acids;
k is an integer greater than or equal to 1;

is a single bond or a double bond. 10. The method of claim 9,
Y in Formula 2 is a two-part epoxy adhesive composition derived from an epoxy compound having a bifunctional group. 10. The method of claim 9,
Z of Formula 2 is a branched type including at least one side chain (branched chain), and a two-part epoxy adhesive composition derived from a dimer fatty acid. 10. The method of claim 9,
The formula 2 is a two-part epoxy adhesive composition represented by the following formulas 3 to 4.
[Formula 3]

[Formula 4]

In Formulas 3 to 4,
R ₁₁ to R ₁₂ are each independently hydrogen or C _1-7 alkyl;
A is -CO-, -SO-, -SO ₂ - or -C(R ₁₃ )(R ₁₄ )-, and R ₁₃ to R ₁₄ are each independently hydrogen, C _1-7 alkyl, C _1-7 halo alkyl or C _6-12 aryl, or R ₁₃ to R ₁₄ may be linked to each other to form a C _3-10 alicyclic ring;
Z ₁ and Z ₃ are saturated or unsaturated C _3-30 alkylene or C _3-30 alkenylene;
Z ₂ and Z ₄ are saturated or unsaturated C _3-30 alkenyl or C _3-30 alkyl;
k is an integer greater than or equal to 1. The method of claim 1,
The toughening agent is a urethane-based toughening agent, a rubber-based toughening agent, or a mixture thereof. 3. The method of claim 2,
The first agent of the two-part epoxy adhesive composition is
Based on 100 parts by weight of the base epoxy resin, 0.1 to 30 parts by weight of the fatty acid-modified acid anhydride-based epoxy compound represented by Formula 1, 10 to 150 parts by weight of a toughening agent, and 0.1 to 50 parts by weight of a filler A two-part epoxy adhesive composition comprising . 3. The method of claim 2,
The weight ratio of the base epoxy resin and the curing agent of the two-part epoxy adhesive composition is 1 to 9: 9 to 1 of the two-part epoxy adhesive composition. 3. The method of claim 2,
The first agent of the two-part epoxy adhesive composition is a two-part epoxy adhesive composition further comprising a coupling agent. 3. The method of claim 2,
The second agent of the two-part epoxy adhesive composition is a two-part epoxy adhesive composition further comprising a filler. 18. The method of claim 17,
The second agent of the two-part epoxy adhesive composition
A two-part epoxy adhesive composition comprising 0.01 to 100 parts by weight of a filler based on 100 parts by weight of a curing agent. A cured product obtained by curing the two-part epoxy adhesive composition of any one of claims 1 to 18. 20. The method of claim 19,
The cured product is a cured product obtained by thermosetting or room temperature curing of a two-part epoxy adhesive composition. An acid anhydride-based epoxy compound represented by the following formula (5).
[Formula 5]

In Formula 5,
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;
k is an integer greater than or equal to 1. 22. The method of claim 21,
In Formula 5, 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 an acid anhydride-based epoxy compound. 22. The method of claim 21,
In Formula 5, 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, an acid anhydride-based epoxy compound. 22. The method of claim 21,
The acid anhydride-based epoxy compound of Formula 5 is an acid anhydride-based epoxy compound represented by the following Formula 6.
[Formula 6]

In the formula (6),
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;
k is an integer greater than or equal to 1. 25. The method of claim 24,
In Formula 6, 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, an acid anhydride-based epoxy compound. 25. The method of claim 24,
The acid anhydride-based epoxy compound of Formula 6 is an acid anhydride-based epoxy compound represented by the following Chemical Formulas 7 to 8.
[Formula 7]

[Formula 8]

In Formulas 7 to 8,
R ₁ is C _1-7 alkyl;
A is -CO-, -SO-, -SO ₂ - or -C(R ₁₃ )(R ₁₄ )-, and R ₁₃ to R ₁₄ are each independently hydrogen, C _1-7 alkyl, C _1-7 halo alkyl or C _6-12 aryl, or R ₁₃ to R ₁₄ may be linked to each other to form a C _3-10 alicyclic ring;
m is a real number greater than or equal to 0.1. An epoxy adhesive composition comprising the acid anhydride-based epoxy compound of any one of claims 21 to 26. 28. The method of claim 27,
The epoxy adhesive composition is an epoxy adhesive composition further comprising a base epoxy resin, a curing agent and a curing accelerator. 29. The method of claim 28,
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 obtained by curing the epoxy adhesive composition of claim 27. A fatty acid-modified 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;
Y is hydrocarbylene or heterohydrocarbylene;
Z is hydrocarbylene;
k is an integer greater than or equal to 1;

is a single bond or a double bond. 32. The method of claim 31,
The formula 1 is a fatty acid-modified acid anhydride-based epoxy compound represented by the following formulas 3 to 4
[Formula 3]

[Formula 4]

In Formulas 3 to 4,
R ₁₁ to R ₁₂ are each independently hydrogen or C _1-7 alkyl;
A is -CO-, -SO-, -SO ₂ - or -C(R ₁₃ )(R ₁₄ )-, and R ₁₃ to R ₁₄ are each independently hydrogen, C _1-7 alkyl, C _1-7 halo alkyl or C _6-12 aryl, or R ₁₃ to R ₁₄ may be linked to each other to form a C _3-10 alicyclic ring;
Z ₁ and Z ₃ are saturated or unsaturated C _3-30 alkylene or C _3-30 alkenylene;
Z ₂ and Z ₄ are saturated or unsaturated C _3-30 alkenyl or C _3-30 alkyl;
k is an integer greater than or equal to 1.

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