KR102578045B1 - Novel glycidyl acid anhydride-based polyol compound, modified polyurethane copolymer prepared therefrom and adhesive composition containing the copolymer, and cured product prepared therefrom - Google Patents

Abstract

The present invention relates to a novel glycidyl acid anhydride-based polyol compound, a modified polyurethane copolymer prepared therefrom, an adhesive composition containing the same, and a cured product prepared therefrom. The modified polyurethane copolymer according to the present invention contains an epoxy group in the repeating unit, so when added to an adhesive composition, it has excellent compatibility with the base epoxy resin and effectively increases the mechanical properties and impact resistance of the cured product when cured. It has an effect.
Accordingly, the adhesive composition containing the modified polyurethane copolymer of the present invention complements the shortcomings of the conventional epoxy resin and has the desired mechanical properties, so that it can be widely applied not only to adhesives but also to molding agents, insulators, composite materials, coating agents, etc. Specifically, it can be applied to automobiles, aircraft, spacecraft, railways, ships, and sports equipment that require excellent mechanical properties to effectively improve mechanical properties such as tensile strength, impact strength, and flexural strength of the product and impact resistance.

Description

Novel glycidyl acid anhydride-based polyol compound, modified polyurethane copolymer prepared therefrom, adhesive composition containing the same, and cured product prepared therefrom adhesive composition containing the copolymer, and cured product prepared therefrom}

The present invention relates to a modified polyurethane copolymer prepared by synthesizing a novel glycidyl acid anhydride-based polyol compound, an adhesive composition containing the same, and a cured product prepared therefrom.

Epoxy resin is a thermosetting plastic that resists climate change well, hardens quickly, has excellent mechanical properties and chemical resistance, and has strong adhesion. Based on these advantages, it is mainly applied in various industrial fields such as adhesives, coatings, fiber-reinforced composite materials, and automobiles. In general, an epoxy adhesive composition containing an epoxy base material, a curing agent, and a curing accelerator is prepared and cured to produce an epoxy resin. Specifically, it is hardened by reacting the epoxy group of the epoxy base with the amine group or carboxylic acid anhydride of the hardener.

Cured epoxy resins have the disadvantage of having high static strengths, such as high tensile and shear strengths, while their dynamic strengths, such as impact and flexural strengths, are insufficient. To solve this problem, a toughening agent is generally added to the epoxy adhesive composition to improve impact strength and flexural strength. However, these tougheners have a low bonding force with the epoxy base, causing phase separation. In other words, when a toughener is added to the adhesive composition, impact resistance can be improved by the toughener absorbing shock received from the outside, but the epoxy, which is the mattress, and the toughener cause phase separation, resulting in a decrease in mechanical strength such as tensile strength. I do it.

Therefore, it contains a toughening agent that has excellent compatibility with the epoxy base and does not cause phase separation, and has excellent static strength such as tensile strength while also having excellent dynamic strength such as impact strength and flexural strength, which can effectively improve impact resistance. Research and development on adhesive compositions is urgently needed.

KR 10-2018-0136724 A (2018.12.26)

The present invention provides novel glycidyl acid anhydride-based polyol compounds.

Additionally, the present invention provides a modified polyurethane copolymer prepared from the glycidyl acid anhydride-based polyol compound and having excellent compatibility with an epoxy base.

In addition, the present invention provides an adhesive composition that includes the modified polyurethane copolymer as a toughening agent and has excellent static strength such as tensile strength and dynamic strength such as impact strength and flexural strength, thereby effectively improving impact resistance, and A cured product prepared therefrom is provided.

In order to achieve the above object, the present inventors included a toughening agent that has excellent compatibility with the epoxy base and does not cause phase separation, and has excellent static strength such as tensile strength and at the same time excellent dynamic strength such as impact strength and bending strength. After continuous research to develop an adhesive composition that can effectively improve resistance, surprisingly, an adhesive composition containing a modified polyurethane copolymer of a specific structure has excellent compatibility with the epoxy base and does not cause phase separation. The invention was completed by discovering that not only impact and bending strength but also tensile strength was effectively improved, resulting in excellent impact resistance.

The present invention can provide a glycidyl acid anhydride-based polyol compound containing a functional group represented by the following formula (1).

[Formula 1]

(In Formula 1 above,

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

is a single bond or double bond.)

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

More preferably, according to an embodiment of the present invention, the glycidyl acid anhydride-based polyol compound may be represented by the following formula (2).

[Formula 2]

(In Formula 2 above,

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

Y is s radical;

s is an integer from 1 to 4;

is a single bond or double bond.)

According to an embodiment of the present invention, Formula 2 may be expressed as Formula 3 below.

[Formula 3]

(In Formula 3 above,

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

Y is hydrocarbylene or heterohydrocarbylene;

is a single bond or double bond.)

Specifically, Formula 3 may be expressed as Formula 4 below.

[Formula 4]

(In Formula 4 above,

R ₁ is hydrogen or methyl;

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

Y is C _2-30 hydrocarbylene or heterohydrocarbylene;

is a single bond or double bond.)

The present invention can provide a modified polyurethane copolymer that is a reaction product between a glycidyl acid anhydride-based polyol compound, a polyol compound, and a diisocyanate compound according to an embodiment of the present invention.

According to one embodiment of the present invention, the polyol compound may be diol or triol.

According to one embodiment of the present invention, the diisocyanate compound may be aliphatic diisocyanate or aromatic diisocyanate.

According to one embodiment of the present invention, the modified polyurethane copolymer has an equivalent ratio of the hydroxy group of the glycidyl acid anhydride-based polyol compound represented by Formula 1 to the hydroxy group of the polyol compound of 1 to 9:9 to 9. is 1; The equivalent ratio of the hydroxyl group of the glycidyl acid anhydride-based polyol compound represented by Formula 1 and the isocyanate group of the diisocyanate compound may satisfy 1:1 to 10.

According to one embodiment of the present invention, the modified polyurethane copolymer may be represented by the following formula (5).

[Formula 5]

(In Formula 5 above,

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

X, Y and Z are hydrocarbylene or heterohydrocarbylene;

x and y are integers greater than or equal to 1;

is a single bond or double bond.)

Preferably, in Formula 5, R ₁ to R ₂ are independently hydrogen or methyl; R ₃ to R ₆ are independently hydrogen or C _1-7 alkyl; X and Y may be C _2-30 hydrocarbylene or heterohydrocarbylene.

According to an embodiment of the present invention, in Formula 5, x:y may be 1 to 9:9 to 1.

According to one embodiment of the present invention, the number average molecular weight of the modified polyurethane copolymer may be 2,000 to 50,000 g/mol.

According to one embodiment of the present invention, the weight average molecular weight of the modified polyurethane copolymer may be 5,000 to 80,000 g/mol.

According to one embodiment of the present invention, the polydispersity index (PDI) of the modified polyurethane copolymer may be 1 to 5.

An adhesive composition containing a modified polyurethane copolymer according to an embodiment of the present invention can be provided.

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

According to one embodiment of the present invention, the modified polyurethane copolymer can be used as a toughening agent.

According to one embodiment of the present invention, the modified polyurethane copolymer may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the base epoxy resin.

A cured product obtained by curing the adhesive composition according to an embodiment of the present invention can be provided.

The modified polyurethane copolymer according to the present invention contains an epoxy group in the repeating unit, so when added to an adhesive composition, it has excellent compatibility with the base epoxy resin and effectively increases the mechanical properties and impact resistance of the cured product when cured. You can do it.

Specifically, the adhesive composition containing this can exhibit excellent tensile strength, flexural strength, and impact strength, and can exhibit significantly superior impact resistance compared to conventional adhesive compositions by effectively preventing structural deformation due to external impact.

Accordingly, the adhesive composition containing the modified polyurethane copolymer of the present invention complements the shortcomings of the conventional epoxy resin and has the desired mechanical properties, so that it can be widely applied not only as an adhesive, but also as a coating agent, molding agent, insulator, and composite material. . Specifically, it can be applied to automobiles, aircraft, spacecraft, railways, ships, and sports equipment that require excellent mechanical properties to effectively improve mechanical properties such as tensile strength, impact strength, and flexural strength of the product and impact resistance.

Figure 1 is a graph showing Fourier Transform-Infrared spectroscopy (FT-IR) results of the MOCA compound of Example 1 of the present invention.
Figure 2 is a graph showing the results of Fouray transform nuclear magnetic resonance spectroscopy (FT-NMR) of the glycidyl acid anhydride-based polyol compound (HHOD) of Example 1 of the present invention.
Figure 3 is a graph showing Fouray transform infrared spectroscopy (FT-IR) results of the modified polyurethane copolymer (MEPU) of Example 2 of the present invention.
Figure 4 is a graph showing the results of GPC analysis of the modified polyurethane copolymer (MEPU) of Example 2 of the present invention.
Figure 5 shows the fracture surface of the fractured specimen after measuring the impact strength of the cured product prepared in Comparative Example 1 and Examples 3 to 5 of the present invention, observed with a Field Emission Scanning Electron Microscope (FE-SEM). It is one image.

Hereinafter, the modified polyurethane copolymer according to the present invention, the adhesive composition containing it, and the cured product prepared therefrom will be described in detail. At this time, if there is no other definition in the technical and scientific terms used, they have meanings commonly understood by those skilled in the art to which this invention pertains, and the following description will not unnecessarily obscure the gist of the present invention. Descriptions of possible notification functions and configurations are omitted.

As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly dictates otherwise.

In addition, units used without special mention in this specification are based on weight, and as an example, the unit of % or ratio means weight % or weight ratio, and weight % refers to the amount of any one component of the entire composition unless otherwise defined. It refers to the weight percent occupied in the composition.

In addition, the numerical range used in this specification includes the lower limit and upper limit and all values within the range, increments logically derived from the shape and width of the defined range, all double-defined values, and the upper limit of the numerical range defined in different forms. and all possible combinations of the lower bounds. Unless otherwise specified in the specification of the present invention, values outside the numerical range that may occur due to experimental error or rounding of values are also included in the defined numerical range.

As used in the present invention, “comprises” is an open description with the same meaning as expressions such as “comprises,” “contains,” “has,” or “features,” and includes elements and materials that are not additionally listed. or does not exclude the process.

As used herein, “substituted” means that the hydrogen atom of the portion to be substituted is replaced with a substituent. In one embodiment, each carbon atom of a substituted group is not substituted with more than two substituents. In other embodiments, each carbon atom of a substituted group is not substituted with more than one substituent. In the case of a keto substituent, two hydrogen atoms are replaced by oxygen, which is attached to the carbon by a double bond. The substituent may be used without limitation as long as it is a known substituent.

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

“Hydrocarbylene” or “heterohydrocarbylene” as used in the present invention refers to a radical having two bonding positions derived from hydrocarbon or heterohydrocarbon, and hetero means that carbon is B, O, N, or C. It means substituted with one or more heteroatoms selected from (=O), P, P(=O), S, S(=O) ₂ and Si atoms.

“Alicyclic” as used in the present invention refers to a cycloalkyl, non-aromatic monocyclic or multicyclic ring system having 3 to 10 carbon atoms, and may have an unsaturated bond within the ring.

As used herein, “alkyl” refers to a straight-chain or branched saturated hydrocarbon radical having one bonding position consisting of only carbon and hydrogen atoms.

“Alkylene” or “heteroalkylene” as used in the present invention refers to a radical having two bonding positions derived from alkyl or heteroalkyl, and hetero means that carbon is B, O, N, C (=O) , P, P(=O), S, S(=O) ₂ and Si atoms.

As used herein, "hydroxy" means -OH, "amino" means -NH ₂ and "carboxyl" or "carboxyl" means -COOH.

“Polyol” as used herein means a compound containing two or more hydroxy groups. The polyol can be divided into aliphatic, cycloaliphatic and aromatic polyol compounds, or can be divided into polyester polyol and polyester polyol compounds. Among the above polyols, a polyol containing two hydroxys is called a diol, a polyol containing three hydroxys is called a triol, and a polyol containing four hydroxys is called a tetraol. It is said. When the hydroxy and diisocyanate of the polyol react, a urethane group is formed to produce polyurethane.

The "epoxy resin" described in the present invention refers to a cured plastic that has completed a reaction with a curing agent in academic terms, but as commonly used in the technical field, it is a raw material for an epoxy composition and is an epoxy resin that has an epoxy group and can react with a curing agent. It can mean a compound.

Additionally, the “cured product” described in the present invention may be a cured product of an adhesive composition in a general sense. Additionally, the cured product may include a semi-cured product.

Hereinafter, the present invention will be described in detail.

The present invention can provide a glycidyl acid anhydride-based polyol compound containing a functional group represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ to R ₆ are independently hydrogen or C _1-10 alkyl, is a single bond or a double bond. Preferably, in Formula 1, R ₁ to R ₂ may be independently hydrogen or methyl, and R ₃ to R ₆ may be independently hydrogen or C _1-7 alkyl. Specifically, the glycidyl acid anhydride-based polyol compound may contain 1 to 10 functional groups represented by Formula 1, preferably 1 to 3 functional groups, but is not limited thereto.

Specifically, Chemical Formula 1 may be expressed as Chemical Formula 6 below.

[Formula 6]

In Formula 6, R ₁ , R ₃ to R ₆ and is the same as described in Formula 1 above.

More specifically, Formula 6 may be selected from the following compounds.

More preferably, according to an embodiment of the present invention, the glycidyl acid anhydride-based polyol compound may be represented by the following formula (2).

In Formula 2, R ₁ to R ₆ are independently hydrogen or C _1-10 alkyl, Y is a s radical, and s is an integer of 1 to 4, is a single bond or a double bond. The fact that s in Y of Formula 2 is a radical means that when Y of the glycidyl acid anhydride-based polyol compound represented by Formula 2 contains s structures of Formula 1, s of Y becomes a radical. means that

Specifically, according to one embodiment of the present invention, Formula 2 may be expressed as Formula 7 below.

[Formula 7]

In Formula 7, R ₁ , R ₃ to R ₆ , Y, s and is the same as described in Formula 2 above.

According to an embodiment of the present invention, Formula 2 may be expressed as Formula 3 below.

[Formula 3]

In Formula 3, R ₁ to R ₆ are independently hydrogen or C _1-10 alkyl, Y is hydrocarbylene or heterohydrocarbylene, is a single bond or a double bond. Preferably, in Formula 3, R ₁ to R ₂ may be independently hydrogen or methyl, and R ₃ to R ₆ may be independently hydrogen or C _1-7 alkyl.

Additionally, in Formula 3, Y may be C _2-30 hydrocarbylene or heterohydrocarbylene, preferably Y may be C _2-30 hydrocarbylene, more preferably C _2-30 alkylene, but is not limited thereto. No. Depending on the hydrocarbon length of Y, properties such as molecular weight of the glycidyl acid anhydride-based polyol compound represented by Formula 3 may be adjusted, which may affect the physical properties of the modified polyurethane copolymer.

In addition, Y in Formula 3 may be included in Y in Formula 2, and descriptions and examples of specific compounds may also be included, but are not limited thereto.

The glycidyl acid anhydride-based polyol compound represented by Formula 3 can be prepared by any method recognized by those skilled in the art. For example, an acid anhydride-based compound is prepared from acid anhydride and glycidol as shown in Scheme 1 below, It can be produced by reacting it again with an epoxy compound. The acid anhydride and glycidol may react at an equivalent ratio of 0.1 to 2:1. In addition, the reaction may be performed by adding the acid anhydride-based compound and the epoxy compound so that the hydroxyl group of the acid anhydride-based compound and the epoxy group of the epoxy compound satisfy an equivalence ratio of 0.1 to 5:1, preferably 0.5 to 3:1. There is no particular limitation. In addition, in the above production method, the equivalence ratio of the input raw materials can be adjusted to prepare a glycidylic acid anhydride-based polyol compound represented by the formula (2). For this, a compound containing 2 to 4 epoxy groups of the epoxy compound is used. can be used.

[Scheme 1]

(In Scheme 1, Y and R ₁ to R ₆ are the same as described in Formula 3.)

The acid anhydride may be used without particular limitation as long as it is commonly used, but preferably methyltetrahydrophthalic anhydride (MTHPA) or 4-methylhexahydrophthalic anhydride (4-MHHPA) can be used. Additionally, the epoxy compound has two or more functional groups and may be an aliphatic epoxy compound, a cycloaliphatic epoxy compound, or an aromatic epoxy compound, and may specifically be triglycidyl ether or diglycidyl ether, but is not limited thereto. Depending on the type of the epoxy compound, the properties of the glycidyl acid anhydride-based polyol compound represented by Formula 3 may be adjusted, which may affect the physical properties of the modified polyurethane copolymer.

Specifically, examples of the aliphatic epoxy compounds include diglycidyl ether of 1,4-butanediol, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and diglycidyl ether of propylene glycol. , a polyether polyol obtained by adding one or two or more types of alkylene oxide (ethylene oxide or propylene oxide) to dimethyloltricyclodecane diglycidyl ether and aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, or glycerin. Glycidyl ether, etc. may be mentioned, and specific examples of the cycloaliphatic epoxy compound may be hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, etc. Specific examples of the aromatic epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, and brominated bisphenol F diglycidyl ether. dil ether, brominated bisphenol S diglycidyl ether, novolac type epoxy resin (e.g. phenol/novolak type epoxy resin, cresol/novolak type epoxy resin, brominated phenol/novolak type epoxy resin), etc. However, it is not limited thereto, and Y in Formula 1 may be derived from the epoxy compound. Preferably, but not limited to, aliphatic epoxy compounds, specifically diglycidyl ether, more specifically 1,6-hexanediol diglycidyl ether, can be used to prepare adhesive compositions with better impact resistance. no.

The epoxy equivalent weight of the glycidyl acid anhydride-based polyol compound according to an embodiment of the present invention is 100 to 1000 g/eq. It may be, specifically 100 to 500 g/eq. It may satisfy the range, but is not limited thereto. As shown in Scheme 1, the epoxy equivalent weight can be adjusted depending on the type of acid anhydride and epoxy compound, and a polyurethane copolymer can be prepared using a glycidylic acid anhydride-based polyol compound that satisfies the above range. In this case, it is possible to further improve the physical properties of the adhesive composition containing it, such as tensile strength, impact strength, and flexural strength.

According to an embodiment of the present invention, Chemical Formula 3 may be expressed as Chemical Formula 4 below.

[Formula 4]

In Formula 4, R ₁ is hydrogen or methyl, R ₃ to R ₆ are independently hydrogen or C _1-7 alkyl, Y is C _2-30 hydrocarbylene or heterohydrocarbylene, is a single bond or a double bond. Preferably, R ₁ is methyl, R ₃ to R ₆ are hydrogen, and Y may be C _2-20 alkylene. Y is the same as Y in Chemical Formula 3 and Scheme 1, and the description and examples of specific compounds are the same as those described above.

More specifically, Formula 4 may be selected from the following compounds.

(In the above compound, k is an integer of 1 or more.)

The present invention can provide a modified polyurethane copolymer that is a reaction product between a glycidyl acid anhydride-based polyol compound, a polyol compound, and a diisocyanate compound according to an embodiment of the present invention.

The glycidyl acid anhydride-based polyol compounds represented by Formulas 1 to 4 contain both an epoxy group and a hydroxy group, and the hydroxy group can be reacted with diisocyanate to produce a modified polyurethane copolymer, and the epoxy group is In the adhesive composition, the base epoxy resin may react with the curing agent to form an epoxy resin. These structural features enable the modified polyurethane copolymer to have excellent compatibility with the epoxy resin base material, which allows the adhesive composition of the present invention to exhibit further improved impact resistance.

According to one embodiment of the present invention, the polyol compound is not greatly limited as long as it is a commonly used polyol, but may specifically be one or more selected from polyester, polyol, polyester polyol, etc., or a mixture thereof. Alternatively, the polyol compound may be an aliphatic polyol, cycloaliphatic polyol, or aromatic polyol.

Preferably, the polyol compound may be diol or triol, and a mixture of the two may be used. More preferably, it may be a diol, and the diol may be a dihydric alcohol, polyesterdiol, or polyesterdiol. Specifically, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentane. Diol, neopentyl glycol, bis(hydroxymethyl)cyclohexane, 2-methyl-1,3-propanediol, methylpentanediol; Also include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, polytetrahydrofuran, polycarbonate diol and polycaprolactone diol. It may be possible, but it is not limited to this. The polyol compound may preferably be polytetrahydrofuran, but is not limited thereto, and the polyol compound may be selected in various ways to obtain the desired physical properties of the adhesive composition.

According to one embodiment of the present invention, the diisocyanate compound is not greatly limited as long as it is a commonly used diisocyanate, but may specifically be an aliphatic diisocyanate or an aromatic diisocyanate. More specifically, the aliphatic diisocyanate is tri, tetra-, penta-, hexa-, hepta- or octa-methylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethyltetra methylene 1,4-diisocyanate , hexamethylene 1,6-diisocyanate (HDI), pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, trimethylhexamethylene 1,6-diisocyanate, 1-isocyanate-3,3,5 -trimethyl-5-isocyanate methylcyclohexane (isophorone diisocyanate, IPDI), 1,4- or 1,3-bis(methyl isocyanate) cyclohexane (HXDI), cyclohexane 1,4-diisocyanate, 1-methyl It may be, but is not limited to, cyclohexane 2,4- or 2,6-diisocyanate and methylene dicyclohexyl (4,4'-, 2,4'- or 2,2'-)diisocyanate (H12MDI). , the aromatic diisocyanate is naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- or 2,6-diisocyanate (TDI), 3,3'-dimethyl-4,4'-diisocyanate di Phenyl (TODI), p-phenylene diisocyanate (PDI), diphenylethane 4,4'-diisocyanate (EDI), diphenylmethane diisocyanate, dimethyldiphenyl 3,3'-diisocyanate, diphenylethane 1, It may be, but is not limited to, 2-diisocyanate and diphenylmethane diisocyanate (MDI). Preferably tri, tetra-, penta-, hexa-, hepta- or octa-methylene diisocyanate can be used, more preferably hexamethylene diisocyanate. In order to obtain the desired physical properties of the adhesive composition, the diisocyanate compound may be selected in various ways.

Preferably, the polyol compound may be represented as Structure 1 below, and the diisocyanate compound may be represented as Structure 2 below.

[Structure 1]

[Structure 2]

In structures 1 and 2 above,

X and Z may be hydrocarbylene or heterohydrocarbylene. _{Specifically , _ _ -100} heterohydrocarbylene, but is not limited thereto. The physical properties of the polyurethane copolymer of the present invention can be adjusted depending on the type of the polyol compound and diisocyanate compound, and it is preferable to select a compound that satisfies the above range in order to express the impact resistance targeted by the present invention. .

The polyol compound represented by Structure 1 and the diisocyanate compound represented by Structure 2 can be directly synthesized and used, or commercially available products may be used, and are not particularly limited as long as they do not impair the physical properties targeted in the present invention. For example, the polyol compound may be polytetrahydrofuran, and the average molecular weight may be 5,000 g/mol or less, preferably 2,000 g/mol or less, and more preferably 1,000 g/mol or less.

According to one embodiment of the present invention, the modified polyurethane copolymer may be represented by the following formula (5).

[Formula 5]

In Formula 5, R ₁ to R ₆ are independently hydrogen or C _1-10 alkyl, may be a single bond or a double bond. Preferably, in Formula 5, R ₁ to R ₂ are independently hydrogen or methyl, R ₃ to R ₆ are independently hydrogen or C _1-7 alkyl, and X and Y are C _2-30 hydrocarbons. It may be bilene or heterohydrocarbylene, specifically C _2-30 hydrocarbylene, and more specifically C _2-30 alkylene. Z may be C _2-200 heterohydrocarbylene, more specifically Z may be C _2-70 heterohydrocarbylene, but is not limited thereto. In addition, as in Y of Formula 2, s of Y of Formula 5 may be a radical, and s may be an integer of 1 to 4, and the specific description thereof is the same as that described in Formula 2.

Additionally, in Formula 5, x and y may each represent the mole percent of the corresponding repeating unit, and x+y=1, and x:y is 1 to 9:9 to 1, preferably 1 to 5: It may be 5 to 1.

Specifically, as shown in Scheme 2 below, a glycidyl acid anhydride-based compound according to an embodiment of the present invention, a polyol compound represented by Structure 1, and a diisocyanate compound represented by Structure 2 are reacted to produce a modified poly Urethane copolymers can be prepared.

[Scheme 2]

(In Scheme 2 _, x, y, _Y ,

In addition, a method for producing a modified polyurethane copolymer according to an embodiment of the present invention includes the steps of stirring a glycidyl acid anhydride-based polyol compound and a polyol compound; removing moisture; Adding a diisocyanate compound; And it may include the step of adding a capping agent. Specifically, the glycidyl acid anhydride-based polyol compound and the polyol compound were added to the reactor, stirred at 100 to 200 rpm at 50 to 100 ° C., moisture was removed, and then the diisocyanate compound and catalyst were added and reacted for 20 minutes to 2. Gives a time response. Next, a capping agent is added and the temperature is raised to 100 to 150° C. to complete the reaction, thereby obtaining the modified polyurethane copolymer.

In addition, in the present invention, the capping agent for capping the terminal isocyanate of the modified polyurethane copolymer has a terminal group or side chain group that can react with isocyanate, such as a hydroxy group (-OH), a thiol group (-SH), an amine group, etc. There is no limitation as long as it has one reactor. Preferably, a reactive capping agent having the above-mentioned reactive group and an allyl or vinyl group can be used. Such reactive capping agents include, for example, aromatic, aliphatic, and alicyclic compounds such as 2-allylphenol, allyloxybisphenol A, Reactive alcohols such as the like may be used, but are not limited thereto. In the case of an adhesive composition containing polyurethane using a capping agent having a reactive group such as an allyl or vinyl group, it is better because physical properties such as impact strength and flexural strength can be further improved.

According to one embodiment of the present invention, the modified polyurethane copolymer has an equivalent ratio of the hydroxy group of the glycidyl acid anhydride-based polyol compound represented by Formula 1 to the hydroxy group of the polyol compound of 1 to 9:9 to 9. 1, specifically 1 to 5: 5 to 1, more specifically 1 to 3: 3 to 1, and the hydroxy group of the glycidyl acid anhydride-based polyol compound represented by the formula (1) and the isocyanate group of the diisocyanate compound The equivalence ratio may satisfy 1:1 to 10, specifically 1:1 to 8, and more specifically 1:1 to 5. That is, the modified polyurethane copolymer according to an embodiment of the present invention is prepared by adding the glycidyl acid anhydride-based polyol compound, polyol compound, and diisocyanate compound represented by Formula 1 to satisfy the equivalence ratio in the above range. You can. The ratio of x and y in Chemical Formula 5 and Scheme 2 can be determined according to the equivalence ratio.

According to one embodiment of the present invention, the number average molecular weight of the modified polyurethane copolymer may be 2,000 to 50,000 g/mol, preferably 5,000 to 30,000 g/mol. Additionally, the weight average molecular weight of the modified polyurethane copolymer may be 5,000 to 80,000 g/mol, preferably 10,000 to 50,000 g/mol. When an adhesive composition is manufactured including a modified polyurethane copolymer that satisfies the above range, impact resistance is effectively improved, and the average molecular weight can be adjusted according to desired physical properties. Additionally, the polydispersity index (PDI) of the modified polyurethane copolymer may be 1 to 5, preferably 1 to 3.

An adhesive composition containing a modified polyurethane copolymer according to an embodiment of the present invention can be provided. Preferably, the modified polyurethane copolymer may be used as a toughening agent, and the modified polyurethane copolymer may be included in an amount of 1 to 30% by weight in the adhesive composition.

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

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

Additionally, 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 a polyurethane copolymer modified by satisfying the above range, the mechanical properties such as impact strength and flexural strength of the adhesive composition can be improved.

The modified polyurethane copolymer may be used as a toughening agent for the adhesive composition. The modified polyurethane copolymer contains an epoxy group and can react with the base epoxy resin and the curing agent, which can serve to improve compatibility with the base epoxy resin. By using the modified polyurethane copolymer as a toughening agent, the impact resistance and mechanical properties of the adhesive composition can be greatly improved, and specifically, the tensile strength, impact strength, and flexural strength can be greatly improved, which is very good.

The adhesive composition according to an embodiment of the present invention may contain 1 to 50 parts by weight of the modified polyurethane copolymer, preferably 1 to 30 parts by weight, based on 100 parts by weight of the base epoxy resin. When satisfying the above range, the adhesive composition of the present invention exhibits superior tensile strength, impact strength, and flexural strength, thereby preventing structural deformation due to external impact, thereby compensating for the shortcomings of the conventional epoxy adhesive composition and providing superior impact resistance. It's even better because it can manifest.

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 the base epoxy resin, and commonly used curing agents can be appropriately selected and used, for example, acid anhydride-based curing agents, phenol-based curing agents, and amino-based curing agents. It may be selected from a curing agent, etc. The curing agent can 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, One or two or more selected from methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride may be included, but are not limited thereto.

Examples of the phenol-based curing agent include phenol resins such as formaldehyde-condensed resol-type phenol resins, non-formaldehyde-condensed phenol resins, novolac-type phenol resins, novolak-type phenol formaldehyde resins, and polyhydroxystyrene resins. profit; resol-type phenolic resins such as aniline-modified resol resins and melamine-modified resol resins; novolak-type phenolic resins such as phenol novolak resin, cresol novolak resin, tert-butylphenol novolak resin, nonylphenol novolak resin and naphthol novolak resin; Special phenolic resins such as dicyclopentadiene-modified phenol resin, terpene-modified phenol resin, triphenolmethane-type resin, phenolaralkyl resin having a phenylene skeleton or diphenylene skeleton, and naphtholaralkyl resin; and polyhydroxystyrene resins such as poly(p-hydroxystyrene), but are not limited thereto.

Examples of the amino curing agent include dimethyl Dicykan (DMDC), dicyandiamide (DICY), isophorone diamine (IPDA), diethylenetriamine (DETA), triethylenetetramine (TETA), and bis( p-aminocyclohexyl)methane (PACM), methylenedianiline (e.g. 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-diaminobenzene 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 are not limited thereto.

In addition, the content of the curing agent is such that the equivalent ratio of the epoxy equivalent weight (EEW) of the base epoxy resin contained in the adhesive composition of the present invention and the activated hydrogen equivalent weight (AHEW) of the curing agent is 1:0.8 to 1.5, preferably 1:0.9 to 1:0.9. It may be desirable to determine and add the hardener content to satisfy 1.2.

The curing accelerator according to an embodiment of the present invention is used to control the curing speed, and may be selected from imidazole-based accelerators and urea-based accelerators. The curing accelerator can be used alone or in combination.

Examples of the imidazole-based 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 may be mentioned, but are not limited thereto.

An example of the urea-based accelerator is any one selected from p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, and 3,4-dichlorophenyl-N,N-dimethylurea, etc. Two or more may be included, 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 base epoxy resin included in the adhesive composition, but is not limited thereto.

In addition to this, one or more other additives may optionally be added to the 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, anti-foaming agents, wetting agents, colorants, thermoplastics, processing aids, ultraviolet (UV) blockers, and fluorescent compounds. , UV stabilizers, antioxidants, mold release agents, and mixtures thereof may be further included. The additive may be used in a range that does not impair the physical properties of the adhesive composition of the present invention.

The adhesive composition according to an embodiment of the present invention may be a curable adhesive composition, and may specifically be an active energy ray-curable type, moisture-curable type, heat-curable type, or room temperature-curable type, and preferably may be a heat-curable 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 components and content of the adhesive composition. Specifically, it can be heat-cured at a temperature of 80 to 250°C, or can be heat-cured at a temperature of 100 to 200°C for 3 hours or more, or 1 hour at 120°C, 1 hour at 150°C, or 1 hour at 180°C. The heat curing process can be carried out sequentially. Additionally, the adhesive composition according to an embodiment of the present invention may be one-component or two-component, but may be appropriately adjusted in consideration of the working environment, application, and target physical properties.

In addition, the adhesive composition containing the modified polyurethane copolymer of the present invention has the desired mechanical properties by complementing the shortcomings of the conventional epoxy resin, so that it can be widely applied not only as an adhesive, but also as a coating agent, molding agent, insulator, and composite material. there is. Specifically, it can be applied to automobiles, aircraft, spacecraft, railways, ships, and sports equipment that require excellent mechanical properties to effectively improve mechanical properties such as tensile strength, impact strength, and flexural strength of the product and impact resistance.

A cured product obtained by curing the adhesive composition according to an embodiment of the present invention can be provided. The cured product can exhibit excellent tensile strength, impact strength, and flexural strength, and can have significantly superior impact resistance compared to conventional adhesive compositions by effectively preventing structural deformation due to external impact.

The adhesive composition containing the modified polyurethane copolymer according to the present invention will be described in more detail through examples below. However, the following examples are only a reference for explaining the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms. Additionally, 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 the present invention pertains. Additionally, the terms used in the description in the present invention are only intended to effectively describe specific embodiments and are not intended to limit the present invention.

[Physical property evaluation method]

1. Epoxy equivalent weight [g/eq.]

Epoxy equivalent weight was measured according to ASTM D1652-04. After dissolving 0.4 mg of the sample to be measured in 15 ml of Chloroform, 10 ml of TEAB (Triethylamonium bicarbonat) solution was added and titrated with 0.1 N HClO ₄ to measure the epoxy equivalent.

2. Average molecular weight (Mw, Mn) [g/mol] and polydispersity index (PDI)

Measurements were made using Gel Permeation Chromatography (GPC, Agilent Technologies, 1260 infinity±). The column was used by connecting two PLgel 5㎛ MIXED-D 300 x 7.5 mm and one PLgel 5㎛ 50 x 7.5 mm column, and THF was used as a solvent. Number average molecular weight, weight average molecular weight, and polydispersity index were measured using the above method.

3. Tensile strength

It was measured using a universal testing machine (UTM 5982, INSTRON), and tensile strength, Young's Modulus, and Tensile Strain were measured according to ASTM D 638.

4. Flexural strength [MPa]

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

5. Impact strength [J/m]

Impact strength was measured according to ASTM D 256-10 using an Izod type impact tester (JJHBT-6501, JJ-test). In addition, after measuring the impact strength, the fracture surface of the specimen was observed using FE-SEM and is shown in Figure 5.

[Example 1] Preparation of glycidyl acid anhydride-based polyol compound (HHOD)

- Manufacturing of MOCA

Add 4-methylhexahydrophthalic anhydride (4-MHHPA) (50.0 g) and glycidol (21.1 g) in an equivalent ratio of 1:1 into a round flask, then stir at 60°C for 4 hours. The reaction mixture was sampled every hour and the reaction was terminated at the point where the epoxy equivalent weight was 280 g/eq., and the compound 4-methyl-2-((oxiran-2-ylmethoxy)carbonyl)cyclohexane-1-carboxylic acid ( MOCA) was obtained.

The compounds obtained by the above method were analyzed through FT-IR, which is shown in Figure 1. As shown in Figure 1, the acid anhydride peak at 1856 cm ^-1 disappeared due to the reaction, and the C=O peak of the ester group and carboxylic acid was generated in the 1780 cm ^-1 and 1731 cm ^-1 regions, indicating that the MOCA compound was produced. Confirmed.

-Manufacture of HHOD

The prepared MOCA (71.1 g) and 1,6-HDGE (1,6-hexanediol diglycidyl ether) (33.2 g) were added to the round flask, stirred at 110°C for 2 hours, and the reaction mixture was sampled every hour to epoxy The reaction is terminated at the point where the equivalent weight is 320 g/eq. to produce compound O'1,O1-((hexane-1,6-diylbis(oxy)) bis(1-hydroxyethane-2,1-diyl)) 2 ,2'-bis(oxiran-2-ylmethyl) bis(4-methylcyclohexane -1,2-dicarboxylate)(HHOD) was synthesized.

The compounds obtained by the above method were analyzed through Automatic Potentiometric Titrando, FT-IR, and FT-NMR, and are shown in Figure 2. As shown in Figure 2, it was confirmed that the HHOD compound was produced by confirming that the carboxylic acid (O=C-OH) peak disappeared around 12 ppm.

[Example 2] Preparation of modified polyurethane copolymer (MEPU)

The HHOD compound (80 g) of Example 1 and PTHF (Polytetrahydrofuran, Sigma-aldrich) (80 g) were placed in a reactor and stirred at 150 rpm at 80°C, then a vacuum was applied to remove moisture and create a nitrogen atmosphere. Add 26 ml of HMDI (Hexamethylene Diisocyanate) and a catalyst (dibutyltin dilaurate) and proceed with the reaction while stirring at 80°C for 40 minutes. Then, 2-AP (2-allyl phenol), a capping agent, was added and the temperature was raised to 110°C to dissolve the compound. The ends were capped with -NCO. In the FT-IR data, the reaction was terminated at the point where the N=C=O isocyanate peak disappeared at 2267 cm ^-1 to obtain a modified polyurethane copolymer (MEPU).

(In the reaction formula of Example 2, m and n are integers of 1 or more.)

The compounds obtained by the above method were analyzed through FT-IR and GPC, and are shown in Figures 3 and 4. As shown in Figure 3, after adding the capping agent, the hydroxy (-OH) of the capping agent reacts with the isocyanate (-NCO) of the polyurethane being synthesized, confirming that the -NCO peak around 2267 cm ^-1 disappears. It was confirmed that this was completed and the MEPU compound was produced. In addition, as shown in Figure 4, the GPC measurement results showed that the modified polyurethane copolymer (MEPU) had a number average molecular weight (Mn) of 11,169 g/mol, a weight average molecular weight (Mw) of 29,965 g/mol, and a polydispersity index (PDI) of 2.7. ) was confirmed to have been synthesized.

[Examples 3 to 5] Preparation of adhesive composition

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

Specifically, the modified polyurethane copolymer used MEPU of Example 2, bisphenol A diglycidyl ether (DGEBA, Momentive, EPIKOTE 828) was used as the base epoxy resin, and dicyandiamide was used as the curing agent. (DICY, AIR PRODUCTS) was used, and 2-methylimidazole was used as a curing accelerator. The epoxy equivalent weight of the base epoxy resin contained in the composition and the active hydrogen equivalent weight (AHEW) of dicyandiamide, a curing agent, were added in a ratio of 1:1, and the curing accelerator was added in an amount of 0.2 parts by weight based on 100 parts by weight of the base epoxy resin. did.

The adhesive composition prepared in each case was heat-cured in a curing oven to prepare a cured product, and the adhesive composition contained 10, 20, and 30 parts by weight of modified polyurethane copolymer (MEPU) based on 100 parts by weight of the base epoxy resin. The cured products were designated as MEPU 10, 20, and 30, respectively. In addition, the 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 the modified polyurethane copolymer (MEPU) of Example 2 of the present invention was not added. The physical properties of the prepared cured product were measured using the evaluation method described above, and the measured results are shown in Table 2 below.

Modified polyurethane copolymer (MEPU) Base
epoxy resin hardener Hardening accelerator phr content
(g) EPIKOTE 828
(g) DICY
(g) 2-MI
(g) Example 3
(MEPU 10) 10 16 160 18.0 0.34 Example 4
(MEPU 20) 20 32 160 18.0 0.34 Example 5
(MEPU 30) 30 48 160 18.0 0.34 Comparative Example 1
(MEPU 0) - - 160 18.0 0.34

Tensile strength measurement Flexural strength
(MPa) impact strength
(J/m) tensile strength
(MPa) Young's modulus
(MPa) Tensile strain
(%) Example 3
(MEPU 10) 64.72 2879.0 2.79 120.91 59.36 Example 4
(MEPU 20) 71.71 2743.8 3.76 119.90 72.82 Example 5
(MEPU 30) 71.81 2676.4 3.81 112.81 54.82 Comparative Example 1
(MEPU 0) 63.69 2947.2 3.04 108.05 47.03

As shown in Table 2, the adhesive composition containing the modified polyurethane copolymer (MEPU) of the present invention exhibited superior tensile strength, flexural strength, and impact strength than Comparative Example 1. Specifically, Example 3 showed 11.9% improved flexural strength and 26.2% improved impact strength compared to Comparative Example 1, and Example 4 showed 12.6% improved tensile strength, 11.0% improved flexural strength, and 54.8% compared to Comparative Example 1. It showed improved impact strength, and in the case of Example 5, it showed 12.8% improved tensile strength and 16.6% improved impact strength compared to Comparative Example 1, so that the adhesive composition containing the modified polyurethane copolymer (MEPU) of the present invention was compared to the conventional adhesive composition. It was confirmed that it had the effect of significantly increasing impact resistance compared to the adhesive composition of . In addition, as shown in Figure 5, the fractured surface of Comparative Example 1 (a) to which MEPU was not added showed a smooth surface, while the fractured surface of Examples 3 to 5 to which (b) to (d) MEPU was added showed a rough surface. As holes were observed, it was confirmed that the polyurethane of the present invention, which has a spherical particle shape, appeared to be fractured due to a phase transition in the process of absorbing shock, and as a result, the impact resistance of the cured adhesive was improved. As described above, the present invention has been described with specific details and limited examples and comparative examples, but these are provided only to facilitate a more general understanding of the present invention, and the present invention is not limited to the above-mentioned examples. Those skilled in the art can make various modifications and variations from this description.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and the scope of the patent claims described below as well as all modifications that are equivalent or equivalent to the scope of this patent claim shall fall within the scope of the spirit of the present invention. .

Claims (20)

A glycidyl acid anhydride-based polyol compound represented by the following formula (2).
[Formula 2]

In Formula 2,
R ₁ to R ₆ are independently hydrogen or C _1-10 alkyl;
Y is C _2-30 alkylene;
s is an integer from 2 to 4;
is a single bond or a double bond. According to clause 1,
In Formula 2, R ₁ to R ₂ are independently hydrogen or methyl;
R ₃ to R ₆ are each independently hydrogen or C _1-7 alkyl. A glycidyl acid anhydride-based polyol compound. delete According to clause 1,
The formula 2 is a glycidyl acid anhydride-based polyol compound represented by the formula 3 below.
[Formula 3]

In Formula 3 above,
R ₁ to R ₆ are independently hydrogen or C _1-10 alkyl;
Y is C _2-30 alkylene;
is a single bond or a double bond. According to clause 4,
The formula (3) is a glycidyl acid anhydride-based polyol compound represented by the following formula (4).
[Formula 4]

In Formula 4 above,
R ₁ is hydrogen or methyl;
R ₃ to R ₆ are independently hydrogen or C _1-7 alkyl;
Y is C _2-20 alkylene;
is a single bond or a double bond. A modified polyurethane copolymer that is a reaction product between a glycidyl acid anhydride-based polyol compound, a polyol compound, and a diisocyanate compound selected from claims 1, 2, and 4 to 5. According to clause 6,
The polyol compound is a modified polyurethane copolymer that is diol or triol. According to clause 6,
The diisocyanate compound is a modified polyurethane copolymer that is aliphatic diisocyanate or aromatic diisocyanate. According to clause 6,
The modified polyurethane copolymer has an equivalent ratio of the hydroxyl group of the glycidyl acid anhydride-based polyol compound represented by Formula 2 to the hydroxyl group of the polyol compound of 1 to 9:9 to 1;
A modified polyurethane copolymer wherein the equivalence ratio of the hydroxy group of the glycidyl acid anhydride-based polyol compound represented by Formula 2 and the isocyanate group of the diisocyanate compound satisfies 1:1 to 10. According to clause 6,
The modified polyurethane copolymer is a modified polyurethane copolymer represented by the following formula (5).
[Formula 5]

In Formula 5 above,
R ₁ to R ₆ are independently hydrogen or C _1-10 alkyl;
X and Z are hydrocarbylene or heterohydrocarbylene;
Y is C _2-30 alkylene;
x and y are integers greater than or equal to 1;
is a single bond or a double bond. According to clause 10,
In Formula 5, R ₁ to R ₂ are independently hydrogen or methyl;
R ₃ to R ₆ are independently hydrogen or C _1-7 alkyl;
X is C _2-30 hydrocarbylene or heterohydrocarbylene;
Y is a modified polyurethane copolymer wherein C _2-20 alkylene. According to clause 10,
In Formula 5, x:y is a modified polyurethane copolymer of 1 to 9:9 to 1. According to clause 6,
The modified polyurethane copolymer has a number average molecular weight of 2,000 to 50,000 g/mol. According to clause 6,
The modified polyurethane copolymer has a weight average molecular weight of 5,000 to 80,000 g/mol. According to clause 6,
The modified polyurethane copolymer has a polydispersity index (PDI) of 1 to 5. An adhesive composition comprising the modified polyurethane copolymer of claim 6. According to clause 16,
The adhesive composition further includes a base epoxy resin, a curing agent, and a curing accelerator. According to clause 16,
An adhesive composition wherein the modified polyurethane copolymer is used as a toughening agent. According to clause 17,
The adhesive composition includes 1 to 30 parts by weight of the modified polyurethane copolymer based on 100 parts by weight of the base epoxy resin. Cured product obtained by curing the adhesive composition of claim 16