KR102600560B1 - epoxy resin composition, and one-component epoxy adhesive composition comprising the same - Google Patents

Abstract

The present invention relates to an epoxy resin composition and a one-component epoxy adhesive composition containing the same. The epoxy resin composition of the present invention has at least three or more urethane functional groups introduced, so that, unlike conventional polyurethane-based tougheners, it is compatible with the base epoxy resin. Not only is it excellent in handling, it satisfies strength requirements such as high shear strength and shear deformation.

Description

Epoxy resin composition and one-component epoxy adhesive composition comprising the same {epoxy resin composition, and one-component epoxy adhesive composition comprising the same}

The present invention relates to an epoxy resin composition and a one-component epoxy adhesive composition containing the same, and more specifically, to a specific epoxy resin composition derived from a polyurethane prepolymer into which at least three or more urethane groups are introduced, and a one-component epoxy adhesive composition containing the same. It's about.

In general, epoxy resins have excellent properties compared to other resins, such as adhesion to various substrates, heat resistance, chemical resistance, electrical properties, and mechanical properties.

Therefore, it is used in a wide range of industrial fields such as sealing agents and adhesives.

Epoxy resin compositions are known as a two-component type consisting of a polyol-based compound and an isocyanate-based compound, and a one-component type composition that hardens by moisture in the air, etc. However, it is unnecessary to adjust the mixing of the composition during field construction and has various advantages such as ease of handling. Due to these advantages, one-component epoxy base compositions are widely used.

In particular, epoxy resins used in adhesives are widely used in the adhesive, molding, and coating industries due to their high mechanical properties and thermal and insulating properties. Despite the good mechanical properties of epoxy resin, it is pointed out as a major disadvantage in industrial fields that require high resistance to impact due to its brittleness, like glass, which is prone to breakage upon impact.

That is, epoxy resins that lack toughness can compromise important strength requirements, such as impact strength and flexural strength. To meet these strength requirements, recent epoxy adhesive compositions use additives such as toughening agents.

However, these additives are difficult to handle because they increase the viscosity of the adhesive or have low compatibility with epoxy resin, and the adhesive performance deteriorates due to impact or compression shear at the adhesive site, so the effect is still minimal. am.

Therefore, there is still a need for an adhesive that is easy to handle and can provide excellent adhesive performance even after impact or high compression shear.

Korean Patent Publication No. 10-2020-0048601

The present invention provides an epoxy resin composition that can be used as an adhesive and realize improved physical properties, a one-component epoxy adhesive composition containing the same, and a cured product thereof.

The present invention provides an epoxy resin composition that is used as a toughening agent for a one-component epoxy adhesive composition and has surprisingly improved physical properties. The epoxy resin composition of the present invention has

A repeating unit represented by Formula 1 below and

It contains functional groups represented by the following formula (2) at both terminals.

[Formula 1]

(In Formula 1 above,

A is a functional group derived from a polyisocyanate compound;

Z is a functional group derived from difunctional polyetheramine;

R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₂ aryl;

R _a is hydrogen or methyl.)

[Formula 2]

Preferably, the epoxy resin composition according to an embodiment of the present invention may be represented by the following formula (3).

[Formula 3]

(In Formula 3 above,

A is a functional group derived from a polyisocyanate compound;

Z is a functional group derived from difunctional polyetheramine;

R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₂ aryl;

R _a is hydrogen or methyl;

The above m is a real number excluding integers greater than or equal to 1.)

Preferably, in Formula 1 or 3 according to an embodiment of the present invention, Z may be represented by Formula 4 below.

[Formula 4]

(In Formula 4 above,

R ₁ or R ₂ are independently hydrogen or methyl;

l is one or more real numbers.)

Preferably, the polyisocyanate compound in Formula 1 or 3 according to an embodiment of the present invention may be an alicyclic polyisocyanate compound.

Preferably, Chemical Formula 3 according to an embodiment of the present invention may be expressed as Chemical Formula 5 below.

[Formula 5]

(In Formula 5 above,

A is a functional group derived from a polyisocyanate compound;

R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₂ aryl;

n is one or more real numbers;

m is a real number excluding integers greater than 1.)

In terms of having improved physical properties as an adhesive or toughening agent, preferably, in Formula 5 according to an embodiment of the present invention, A is a functional group derived from an aliphatic polyisocyanate compound; R is hydrogen or C1-C5alkyl; n is a real number of 2 or more, and m can be any real number excluding an integer of 1 or more.

The epoxy compound according to an embodiment of the present invention may be derived from a polyol derived from a reaction product of a difunctional polyetheramine and a cyclic carbonate, and a polyurethane prepolymer prepared by reacting the polyol with a polyisocyanate compound.

Preferably, the polyurethane prepolymer according to an embodiment of the present invention may be represented by the following formula (6).

[Formula 6]

(In Formula 6 above,

A is a functional group derived from a polyisocyanate compound;

R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₂ aryl;

R ₁ to R ₃ are independently hydrogen or methyl;

l is a real number greater than or equal to 1, and m is a real number excluding integers greater than or equal to 1.)

Specifically, the bifunctional polyetheramine according to an embodiment of the present invention is Jeffamine D-230 (Huntsman), D-400. Any one or a mixture of two or more selected from D-2000, ED-600, ED-900, ED-2003, etc.;

The cyclic carbonate may be ethylene carbonate, propylene carbonate, or a mixture thereof.

Additionally, the present invention provides a one-component epoxy adhesive composition containing the epoxy resin composition of the present invention and a cured product thereof.

Preferably, the one-component epoxy adhesive composition of the present invention may further include a base epoxy resin, a curing agent, and a curing accelerator.

The one-component epoxy adhesive composition of the present invention may contain 5 to 30% by weight of the epoxy resin composition based on the total weight of the base epoxy resin and the epoxy resin composition.

Additionally, the present invention provides a polyurethane prepolymer for producing the epoxy resin composition of the present invention, and the polyurethane prepolymer of the present invention may be represented by the following formula (6).

[Formula 6]

(In Formula 6 above,

A is a functional group derived from a polyisocyanate compound;

R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₂ aryl;

R ₁ to R ₃ are independently hydrogen or methyl;

n is a real number greater than or equal to 1, and m is a real number excluding one or more integers.)

The epoxy resin composition of the present invention contains a plurality of urethane groups, at least 3 or more, preferably 4 or more, and is used as a main agent or toughening agent for an epoxy adhesive composition to have improved curing behavior, impact strength, toughness and shear strength. .

In addition, the epoxy resin composition of the present invention has excellent miscibility with the base epoxy resin and can be used with various base epoxy resins, making it highly compatible and easy to handle.

Therefore, the epoxy resin composition of the present invention has improved mechanical strength and physical properties by including three or more, and four or more, urethane functional groups.

In addition, the one-component epoxy adhesive composition containing the epoxy resin composition of the present invention also has greatly improved shear strength, shear stress, tensile strength, toughness, and impact strength, making it possible to implement improved adhesive performance and mechanical properties as an adhesive.

Furthermore, the epoxy resin composition of the present invention enables the production of a one-component epoxy adhesive composition having desired physical properties by controlling the urethane group.

In addition, the polyurethane prepolymer of the present invention is a novel compound, and has at least 3 or more, preferably 4 or more urethane groups, and the epoxy resin composition of the present invention prepared therefrom has 3 or more, preferably 4 or more urethane groups introduced. Has improved physical properties.

Accordingly, the one-component epoxy adhesive composition of the present invention can be very usefully used in various materials in various fields, such as aircraft members, spacecraft members, automobile members, railroad car members, ship members, sports equipment members, and computer members.

Hereinafter, the epoxy resin composition of the present invention and the one-component epoxy adhesive composition containing the same 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, the term “comprises” is an open description with the same meaning as expressions such as “comprising,” “contains,” “has,” or “characterized by” and is not additionally listed. No element, material or process is excluded.

Additionally, the term “cured product” used in the present invention has a general meaning and may be a cured product of an epoxy adhesive composition. Additionally, the cured product may include a semi-cured product.

As used herein, the term “alkyl” refers to an aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. The alkyl may be straight-chain or branched alkyl, respectively, when used alone or in combination. Straight-chain or branched alkyl is specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neo-pentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl. , normal decyl, etc. may be included.

The term “alkoxy” used in this specification includes -OCH ₃ , -OCH ₂ CH ₃ , -O(CH ₂ ) ₂ CH ₃ , -O(CH ₂ ) ₃ CH ₃ , -O(CH ₂ ) ₄ CH ₃ , means -O-(alkyl), including -O(CH ₂ ) ₅ CH ₃ , and the like, where alkyl is as defined above.

As used herein, the term “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 this. The carbocyclic aromatic group may be optionally substituted.

As used herein, the term "functional group derived from a polyisocyanate compound" refers to a radical excluding the urethane functional group, etc. formed by the reaction of one or more isocyanate groups present in the polyisocyanate compound, and the radical is the isocyanate participating in the reaction, etc. It may be due to the number of groups.

The present invention provides an epoxy resin composition and a one-component epoxy adhesive composition containing the same. The epoxy resin composition of the present invention includes a repeating unit represented by the following formula (1) and a functional group represented by the following formula (2) at both ends.

[Formula 1]

(In Formula 1 above,

A is a functional group derived from a polyisocyanate compound;

Z is a functional group derived from difunctional polyetheramine;

R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₂ aryl;

R _a is hydrogen or methyl.)

[Formula 2]

The epoxy resin composition of the present invention has at least 3, preferably 4 or more urethane functional groups, and thus, unlike conventional epoxy resin compositions, the epoxy resin produced therefrom has excellent impact strength, toughness and tensile strength, and has excellent curing behavior and curing behavior. The shear strength is very excellent.

Specifically, the epoxy resin composition of the present invention, unlike conventional epoxy compounds, is manufactured with diisocyanate derived from a polyurethane prepolymer prepared by reacting a polyol derived from a difunctional polyetheramine and a cyclic carbonate reaction product with polyisocyanate, thereby producing a number of By introducing a urethane functional group, toughness was greatly improved.

Furthermore, the epoxy resin composition of the present invention is not only easy to handle in a wide temperature range, including temperatures lower than room temperature, but also has extremely improved physical properties, and has excellent adhesive performance even under impact or high compression shear.

Additionally, the epoxy resin composition of the present invention can itself be used as an epoxy adhesive agent, and can preferably be used as a polyurethane-based toughening agent.

When the epoxy resin composition of the present invention is used as a polyurethane-based toughening agent, it increases compatibility with the base epoxy resin and allows the toughening agent to directly participate in the curing reaction, thereby securing mutual bonding force and having improved adhesion and toughness.

In addition, the epoxy resin composition of the present invention has the advantage of being able to easily adjust the shear strength by adjusting the epoxy content.

Preferably, the epoxy resin composition according to one embodiment of the present invention may be represented by the following formula (3).

［Chemical Formula 3］

(In Formula 3 above,

A is a functional group derived from a polyisocyanate compound;

Z is a functional group derived from difunctional polyetheramine;

R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₂ aryl;

R _a is hydrogen or methyl;

The m above is a real number excluding integers greater than or equal to 1.)

In Chemical Formula 1 or Chemical Formula 3 of the present invention according to one embodiment of the present invention, Z may be represented by the following Chemical Formula 4:

[Formula 4]

(In Formula 4 above,

R ₁ or R ₂ are independently hydrogen or methyl;

ｎis 1 or more real numbers.）

The polyisocyanate compound in Formula 1 according to an embodiment of the present invention is not particularly limited as long as it has at least two isocyanate groups in the molecule. Polyisocyanate compounds include aliphatic polyisocyanate compounds, cycloaliphatic polyisocyanate compounds, aromatic polyisocyanate compounds, heterocyclic polyisocyanate compounds, aliphatic polyisothiocyanate compounds, cycloaliphatic polyisothiocyanate compounds, and aromatic polyisothiocyanate compounds. and sulfur-containing heterothiocyanate compounds, and modified forms thereof.

For example, polyisocyanate compounds include pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, α, α, α',α'-tetramethylxylylene diisocyanate, bis(isocyanatomethyl)naphthalene, mesityrylene triisocyanate, bis(isocyanate) Natomethyl)sulfide, bis(isocyanatoethyl)sulfide, bis(isocyanatomethyl)disulfide, bis(isocyanatoethyl)disulfide, bis(isocyanatomethylthio)methane, bis(isocyanate) Aliphatic polyisocyanate compounds such as nattoethylthio)methane, bis(isocyanatoethylthio)ethane, and bis(isocyanatomethylthio)ethane; Isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, 2,5 -bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isocyanato Methyl)tricyclodecane, 3,9-bis(isocyanatomethyl)tricyclodecane, 4,8-bis(isocyanatomethyl)tricyclodecane, 4,9-bis(isocyanatomethyl)tricyclodecane Alicyclic polyisocyanate compounds such as; Aromatic polyisocyanates such as phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and diphenyl sulfide-4,4-diisocyanate. compound; 2,5-diisocyanatothiophene, 2,5-bis(isocyanatomethyl)thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis(isocyanatomethyl)tetrahydrothiophene ophene, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis(isocyanatomethyl)-1,4-dithiane Heterocyclic polyisocyanate compounds such as 4,5-diisocyanato-1,3-dithiolane and 4,5-bis(isocyanatomethyl)-1,3-dithiolane; etc. can be mentioned.

Examples of isothiocyanate compounds include hexamethylene diisothiocyanate, lysine diisothiocyanate methyl ester, lysine triisothiocyanate, m-xylene diisothiocyanate, and bis(isothiocyanatomethyl ) Aliphatic polyisothiocyanate compounds such as sulfide, bis(isothiocyanatoethyl)sulfide, and bis(isothiocyanatoethyl)disulfide; Isophorone diisothiocyanate, bis(isothiocyanatomethyl)cyclohexane, dicyclohexylmethane diisothiocyanate, cyclohexane diisothiocyanate, methylcyclohexane diisothiocyanate, 2,5- Bis(isothiocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isothiocyanatomethyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isothio Cyanatomethyl)tricyclodecane, 3,9-bis(isothiocyanatomethyl)tricyclodecane, 4,8-bis(isothiocyanatomethyl)tricyclodecane, 4,9-bis(isothiocyanato) Alicyclic polyisothiocyanate compounds such as methyl)tricyclodecane; aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate, 4,4-diphenylmethane diisothiocyanate, and diphenyl disulfide-4,4-diisothiocyanate; 2,5-Diisothiocyanatothiophene, 2,5-bis(isothiocyanatomethyl)thiophene, 2,5-isothiocyanatotetrahydrothiophene, 2,5-bis(isothiocyanato) Methyl)tetrahydrothiophene, 3,4-bis(isothiocyanatomethyl)tetrahydrothiophene, 2,5-diisothiocyanato-1,4-dithiane, 2,5-bis(isothiocyanate) Sulfur-containing products such as natomethyl)-1,4-dithiane, 4,5-diisothiocyanato1,3-dithiolane, and 4,5-bis(isothiocyanatomethyl)-1,3-dithiolane. Heterocyclic polyisothiocyanate compounds; etc. can be mentioned.

The above polyisocyanate compounds can be used individually or in combination of two or more types. Among these, aromatic polyisocyanate or cycloaliphatic polyisocyanate is preferable, and cycloaliphatic polyisocyanate is preferred in that the shear modulus of the epoxy adhesive composition using the epoxy compound produced is superior and has improved adhesiveness even under high temperature and high humidity. desirable. More preferred examples of cycloaliphatic polyisocyanates may be trans-cyclohexane 1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(methylisocyanate)cyclohexane (H6XDI), and dicyclohexylmethane diisocyanate (H12MDI). .

Preferably, the above chemical formula 3 according to one embodiment of the present invention can be expressed as the following chemical formula 5.

[Formula 5]

(In Formula 5 above,

A is a functional group derived from a polyisocyanate compound;

R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₂ aryl;

n is a real number greater than or equal to 1; m is a real number excluding integers greater than or equal to 1.)

Preferably, in Formula 5 according to one embodiment of the present invention, R is hydrogen, C _1- C ₅ alkyl, or C _6- C ₁₂ aryl; n may be a real number of 2 or more, and m may be a real number excluding an integer of 1 or more. More preferably, R is hydrogen, C _1- C ₅ alkyl; n is a real number of 5 or more, m can be any real number other than an integer of 1 or more, and R is hydrogen, C _1- C ₃ alkyl; n may be a real number between 10 and 100, and m may be a real number excluding integers between 1 and 2.

In another embodiment, the epoxy resin composition according to one embodiment of the present invention may include an epoxy resin compound represented by the following chemical formula: 5-1.

[Formula ５－１]

(In the above formula 5-1,

A is a functional group derived from a polyisocyanate compound;

R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₂ aryl;

l is a real number greater than 1, and m is a real number less than 2.)

Preferably, in Formula 5-1 according to an embodiment of the present invention, R is hydrogen, C _1- C ₅ alkyl, or C _6- C ₁₂ aryl; n may be a real number of 2 or more, m may be a real number of less than 2, and more preferably R is hydrogen, C _1- C ₅ alkyl; n can be a real number of 5 or more, m can be a real number of less than 2, R is hydrogen, C _1- C ₃ alkyl; n may be a real number from 5 to 100, and m may be a real number from 0.1 to less than 2.

Preferably, in Formula 5 and Formula 5-1 according to an embodiment of the present invention, A is a functional group derived from an alicyclic polyisocyanate compound; R is hydrogen or C _1- C ₅ alkyl; n may be a real number of 5 or more, m may be a real number of less than 2, and more preferably, A is trans-cyclohexane 1,4-diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane, and dicyclohexylmethane. It is a functional group derived from one or two or more selected from diisocyanate; R is hydrogen or methyl; n is a real number of 6 or more, m is a real number of less than 2, more preferably, n is a real number of 6 to 100, and m may be a real number of 0.1 to less than 2.

The epoxy resin composition according to an embodiment of the present invention may have a weight average molecular weight measured by gel permeation chromatography (GPC) of 1,000 to 20,000 g/mol, preferably 2,000 to 10,000 g/mol.

An epoxy resin composition according to an embodiment of the present invention includes a polyol derived from the reaction of a difunctional polyetheramine and a cyclic carbonate, and

It may be derived from a polyurethane prepolymer prepared by reacting the polyol with a polyisocyanate compound.

Specifically, the epoxy resin composition according to an embodiment of the present invention is first prepared from a polyol derived from the reaction of a difunctional polyetheramine and a cyclic carbonate through a non-isocyanate urethane reaction to incorporate a urethane functional group, and then to form a polyisocyanate compound. It is manufactured from a polyurethane prepolymer into which at least three or more urethane groups are introduced by reacting again with .

Accordingly, the epoxy resin composition of the present invention has at least 3 or more urethane groups, preferably at least 4 or more, and has improved curing behavior, impact strength, toughness and shear strength.

The bifunctional polyetheramine according to an embodiment of the present invention is not particularly limited as long as it is commonly used in the art, but preferably has a weight average molecular weight of 200 to 10,000 g/mol, more preferably 300 to 5,000 g/mol. mol may be polyetheramine. As a more specific example, it may be one or more commercially available products selected from Huntsman's JEFFAMINE D-400, D-2000, ED-600, ED-900, ED-2003, etc., preferably Huntsman. It may be one or more selected from D-2000 and ED-2003 of JEFFAMINE.

The cyclic carbonate according to an embodiment of the present invention may be preferably C ₁ -C ₁₀ alkylene carbonate, preferably C ₁ -C ₅ alkylene carbonate, and as a specific example, may be ethylene carbonate or propylene carbonate. , the alkylene carbonate may be further substituted with one or more substituents selected from C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy, and C _6- C ₁₂ aryl.

In terms of producing a polyurethane prepolymer with desirable physical properties according to an embodiment of the present invention, the difunctional polyetheramine is D-2000 or ED-2003 of Zefamine, and the cyclic carbonate is a combination of ethylene carbonate or propylene carbonate. It can be.

Specifically, the polyurethane prepolymer according to an embodiment of the present invention may be represented by the following formula (6).

[Formula 6]

(In the above formula 6,

A is a functional group derived from a polyisocyanate compound;

R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₂ aryl;

R ₁ to R ₃ are independently hydrogen or methyl;

n is a real number greater than or equal to 1, and m is a real number excluding integers greater than or equal to 1.)

Preferably, in Formula 6 according to an embodiment of the present invention, A is a functional group derived from an alicyclic polyisocyanate compound or an aromatic polyisocyanate compound; R is hydrogen or C _1- C ₁₀ alkyl; R ₁ and R ₃ are methyl; R ₂ may be hydrogen, n may be a real number greater than or equal to 2, and m may be a real number excluding an integer less than 2. More preferably, A is a functional group derived from an alicyclic polyisocyanate compound; R is hydrogen or methyl; R ₁ and R ₃ are methyl; R ₂ may be hydrogen, n may be a real number between 5 and 100, m may be a real number excluding integers less than 2, n may be a real number between 6 and 50, and m may be a real number excluding integers less than 0.1 to 2. It can be.

Preferably, the polyurethane prepolymer of the present invention is a bifunctional polyetheramine, such as D-2000 or ED-2003 from JEFFAMINE, and the cyclic carbonate may be prepared from the reaction of ethylene carbonate or propylene carbonate.

The epoxy resin composition according to an embodiment of the present invention may correspond to a mixture of compounds having a repeating unit represented by the above Chemical Formula 1.

In other words, the epoxy resin composition according to one embodiment of the present invention is a mixture of compounds having x (an integer of 1 or more) repeating units represented by the above chemical formula 1. In the above chemical formula 3, m is represented by the above chemical formula 1. The sum of each compound containing x repeating units and their numbers is divided by the total number of compounds containing x repeating units represented by the above chemical formula 1. It corresponds to the average value of these.

Essentially, the epoxy resin composition of the present invention may be a mixture of epoxy compounds containing a repeating unit represented by the above chemical formula 1.

The present invention also includes a one-component epoxy adhesive composition containing the epoxy resin composition of the present invention.

The one-component epoxy adhesive composition of the present invention has improved mechanical properties and excellent adhesive performance by including the epoxy resin composition of the present invention containing at least 3 or more, preferably 4 or more urethane functional groups as a main agent and a toughening agent.

The one-component epoxy adhesive composition of the present invention may further include a base epoxy resin, a curing agent, and a curing accelerator.

The one-component epoxy adhesive composition according to an embodiment of the present invention contains 5 to 30% by weight of the epoxy compound, preferably less than 5 to 25% by weight, more preferably 10 to 25% by weight, based on the total weight of the epoxy resin composition and the base epoxy resin. It may be less than %, and more preferably 10 to 20% by weight.

The base epoxy resin according to an embodiment of the present invention is a compound capable of producing an epoxy resin and may have two or more epoxy groups in the molecule, and may be saturated, unsaturated, cyclic or acyclic, aliphatic, or cycloaliphatic. , aromatic and heterocyclic polyepoxy compounds, etc. may be selected.

Non-limiting examples of the base epoxy resin include one or more bisphenol-type epoxy resins selected from bisphenol A, bisphenol E, bisphenol F, bisphenol M, bisphenol S, and bisphenol H, and glycidyl ether. One or a mixture of two or more selected from the group consisting of epoxy resins, glycidyl amine-based epoxy resins, phenol novolak-type epoxy resins, and cresol novolak-type epoxy resins can be mentioned. Preferably, one or more of two or more selected from bisphenol A-based epoxy resins and bisphenol F-based epoxy resins may be used in terms of maintaining excellent adhesive performance, flexural strength, and impact strength.

In addition, the base epoxy resin according to an embodiment of the present invention 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. If the above range is satisfied, it has more advantageous characteristics in improving mechanical properties such as impact strength and bending strength at the adhesive area, as well as the above-described effects.

The curing agent according to one embodiment of the present invention may directly participate in crosslinking of the composition or may act in the form of a catalyst. The curing agent is a curing agent for the main epoxy resin, and can be used without limitation as long as it is known in the art, and may be selected from acid anhydride-based curing agents, phenol-based curing agents, and amino-based curing agents.

Non-limiting 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, and glutar. Any one or two or more selected from acid anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride may be mentioned.

Non-limiting examples of the phenol-based curing agent include formaldehyde condensation type resol type phenol resin, non-formaldehyde condensation type phenol resin, novolac-type phenol resin, novolac-type phenol formaldehyde resin, and polyhydroxystyrene resin. Phenolic resins such as; 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).

Non-limiting examples of the amino curing agent include dimethyl Dicykan (DMDC), dicyandiamide (DICY), isophorone diamine (IPDA), diethylenetriamine (DETA), and triethylenetetramine (TETA). , 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-methylcyclo Hexane, 2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene, 1,2-diaminobenzene, 1,3-diaminobenzene, 1, 4-diaminobenzene, diaminodiphenyl oxide, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl and 3,3'-dimethyl-4,4'-diamino Any one or two or more selected from diphenyl and the like may be mentioned.

In addition, the curing agent may include 3 to 15 parts by weight, preferably 3 to 10 parts by weight, based on the total of 100 parts by weight of the epoxy resin composition and the base epoxy resin included in the one-component epoxy adhesive composition, but is limited thereto. It doesn't work. In the above range, curing proceeds in a short time and productivity can be secured, so it is preferable.

In addition, the curing accelerator is used to control the curing speed, and may be selected from imidazole-based accelerators and urea-based accelerators.

Non-limiting examples of the imidazole-based accelerator include 2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenyl. Midazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tri Azine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2-undecylimidazole, 3-heptadecylimidazole, 2-phenylimidazole, 2-phenylimidazoline, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Any one or two or more selected from midazole and 1-cyanoethyl-2-undecylimidazole may be mentioned.

Non-limiting examples of the urea-based accelerator include p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3,3'-(4-methyl-1,3-phenylene) ) Any one or two or more selected from bis(1,1-dimethylurea) and 3,4-dichlorophenyl-N,N-dimethylurea.

In addition, the curing accelerator may be included in an amount of 0.01 to 1 part by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the epoxy resin composition and the base epoxy resin included in the one-component epoxy adhesive composition, but is limited thereto. That is not the case.

In addition, in the one-component epoxy adhesive composition according to an embodiment of the present invention, additives selected from inorganic fillers, pigments, coupling agents, antioxidants, radical absorption/formation inhibitors, dispersants, and flame retardants are appropriately selected according to the purpose. More may be added, but it is not limited thereto.

The one-component epoxy adhesive composition according to an embodiment of the present invention has the advantage of requiring no mixing adjustment of the composition during on-site construction and being easy to handle.

Additionally, the present invention provides a cured product of the one-component epoxy adhesive composition described above.

The cured product according to an embodiment of the present invention is the one-component epoxy adhesive composition, which contains 5 to 30% by weight of the epoxy resin composition of the present invention based on the total amount of the base epoxy resin and the epoxy compound, so that the curing temperature is 150 to 180%. It can be carried out at ℃ for 30 minutes to 2 hours, and the shear strength according to ASTM D 1002 can be satisfied at least 17.00 MPa. It may also be 18.00 MPa or more, and may be 20.00 MPa or more, and the shear strain may be 5.00% or more, preferably 5.50% or more, and more preferably 6.00% or more.

The one-component epoxy adhesive composition of the present invention can be used as a structural adhesive. Specifically, it can be used as a structural adhesive in the assembly of structures such as civil engineering buildings as well as transportation vehicles such as automobiles, aircraft, and ships. It has excellent adhesion properties between the same or different materials such as metal to metal, metal to glass, and metal to carbon fiber, so it can be used in a variety of industries, including structural adhesives.

The epoxy resin composition of the present invention and the one-component epoxy adhesive composition containing the same 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.

(Assessment Methods)

1. Hardening behavior

It was measured using a differential scanning calorimeter (DSC Q2000, TA instruments), and the temperature rise test was analyzed at a temperature increase rate of 10 ^o C/min in the temperature range of 50 to 250 ^o C, and was analyzed by curing at 160 o C for 90 minutes ( Purging conditions: N ₂ , 40 ml/min).

2.Shear strength [MPa]

Using the single lap shear test method, the shear strength test piece is formed by forming an adhesive part of 12.5 Х 25 ㎜ (thickness: 200 um) on two metal steel plates (CR340, 25 Х 100 Х 1.6 ㎜) and overlapping them 2 times. It was manufactured by adjusting the thickness of the adhesive area using mm glass beads and then curing it at 160°C for 90 minutes. 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) at 25°C.

3. Impact strength [J/m]

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

Curing conditions: 120℃ 1hr, 150℃ 1hr, 180℃ 1hr

Shape: Notched

Measurement speed: 3.5m/s

Pendulum energy: 5.5J

Measurement temperature: room temperature (25℃)

4. Tensile strength [MPa]

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

Curing conditions: 120℃ 1hr, 150℃ 1hr, 180℃ 1hr

Measurement speed: 1.3mm/min

Measurement temperature: room temperature (25℃)

1. Epoxy equivalent weight [g/eq.]

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

[Preparation Example 1] Preparation of polyol

71.42 g of propylene carbonate was mixed with 350 g of Jeffamine D-2000 (Huntsman) and stirred at 100°C for 6 days. Unreacted propylene carbonate and Jeffamine D-2000 were removed from the obtained reaction mixture using dichloromethane and water. Trace amounts of remaining water were removed using MgSO ₄ , and dichloromethane contained in the purified polyol was removed using a vacuum distillation rotary concentrator to obtain the final compound.

The synthesis of the prepared polyol was confirmed by ¹ H-NMR (CDCl ₃ ). CDCl ₃ was used as the measurement solvent. The conversion rate of polyol was measured using the CH ₃ peak located at the end of Jeffamine D-2000 and the CH ₃ peak of propylene carbonate, and it was confirmed that polyol was synthesized with a conversion rate of 92%.

[Example 1] Preparation of polyurethane prepolymer and epoxy resin composition

120 g of the polyol prepared in Preparation Example 1 was placed in a double jacket reactor including a stirrer, reflux condenser, and thermometer, and 24.33 g of isophorone diisocyanate (IPDI) and 144.33 g of EAc, a diluting solvent, were added. When the temperature inside the reactor reaches 60°C, DBTDL (Dibutyltin dilaurate) catalyst is added and the urethane reaction begins. The conversion rate is confirmed through the NCO peak through FT-IR. When the peak of NCO reached a state where there was no change, 8.51 g of glycidol, an end capping agent, was reacted with the remaining NCO to obtain an epoxy resin composition whose ends were terminated with epoxy.

The synthesis of polyurethane prepolymer and epoxy resin composition was confirmed by FT-IR and ¹ H-NMR. In FT-IR, it was confirmed that the NCO peak corresponding to 2270 cm ^-1 was consumed at a certain level (1eq) and became constant after 5 hours of reaction. After that, glycidol was added and reacted with the remaining NCO for 3 hours, and the NCO completely disappeared. was confirmed by FT-IR. ¹ H-NMR measurement used CDCl ₃ as a solvent and was measured at room temperature. When comparing the CH ₂ peak of glycidol and the epoxy CH ₂ peak of the synthesized epoxy compound, it was confirmed that the peak of glycidol shifted due to the urethane bond, indicating that the epoxy resin composition was successfully synthesized. The weight average molecular weight of the epoxy resin composition synthesized in this way was measured by GPC (calibrated with PMMA (methyl methacrylate)), and it was confirmed that Mn = 6,442 g/mol and Mw = 9,926 g/mol. In addition, it was confirmed that the calculated molecular weight measured by EEW (Epoxy equivalent weight) was 4,329.46 g/mol. Accordingly, the molecular weight used in the evaluation of the physical properties below was evaluated based on the molecular weight obtained from the EEW value.

(Examples 2 to 4 and Comparative Example 1)

A one-component epoxy adhesive composition was prepared by mixing the epoxy resin composition, the base epoxy resin, the curing agent, and the curing accelerator described below with the materials and contents as shown in Table 1 below.

That is, the base epoxy resin and the epoxy resin composition are mixed in weight percent as shown in Table 1 below, the total weight of the base epoxy resin and epoxy resin composition is 100 parts by weight, and the curing agent and curing accelerator as shown in Table 1 are added in parts by weight. A one-component epoxy adhesive composition was prepared by mixing.

The one-component epoxy adhesive composition was cured at 160°C for 90 minutes using a mold to prepare a cured product.

In addition, the physical property results through the above evaluation method are shown in Tables 2 to 4 below.

Base epoxy resin (% by weight) Epoxy resin composition
(weight%) Hardener (parts by weight) Curing accelerator (parts by weight) Example 3 (U-5) 95 5 6.597 0.415 Example 4 (U-10) 90 10 6.287 0.395 Example 5 (U-15) 85 15 5.950 0.373 Example 6 (U-20) 80 20 5.666 0.356 Example 7 (U-25) 75 25 5.355 0.337 Example 8 (U-30) 70 30 5.019 0.316 Example 9 (U-50) 50 50 4.295 0.270 Comparative Example 1 100 - 6.907 0.434

Base epoxy resin: diglycidyl ether bisphenol A (DGEAB; Kukdo Chem)

Hardener: Dicyandiamide (Dyhard 100S, DICY)

Curing accelerator: 3,3'-(4-methyl-1,3-phenylene)bis(1,1-dimethylurea)(Dyhard UR 500:

Example 4
(U-10) Example 8
(U-30) Example 9
(U-50) Comparative Example 1
(U-0) T _peak (℃) 159.36 169.19 184.38 157.48 T _onset (℃) 146.81 150.99 151.32 145.49 T _g (°C) 126.13 122.97 110.57 134.72

As shown in Table 2 above, in the one-component epoxy adhesive composition according to the present invention, a tendency for the glass transition temperature (Tg) to decrease as the proportion of the epoxy resin composition of the present invention increased was observed. Therefore, it can be seen that the curing temperature of the one-component epoxy adhesive composition containing the epoxy resin composition of the present invention may be 159 to 185°C, and is preferably 160 to 170°C.

shear strength
(MPa) shear stress
(MPa) tensile strength
(MPa) toughness
(J/m³) Young's modulus
(MPa) impact strength
(KJ/m²) Comparative Example 1 (U-0) 16.41±0.51 4.35±0.85 64.00±0.53 4.15±0.58 2456.465±205.48 5.32±0.27 Example 3 (U-5) 17.04±0.88 5.55±0.35 59.15±1.83 4.44±0.87 2228.38±163.97 5.59±0.18 Example 4 (U-10) 20.13±0.11 6.7±0.78 57.99±2.02 4.63±0.39 2050.631±65.18 6.44±0.20 Example 5 (U-15) 21.77±0.81 7.85±0.7 57.07±1.35 4.93±0.29 1941.54±32.28 7.04±0.25 Example 6 (U-20) 23.99±0.58 9.35±1.01 52.86±0.31 5.42±0.55 1616.531±99.58 8.09±0.50

As shown in Table 3, the one-component epoxy adhesive composition of the present invention has improved adhesion compared to the one-component epoxy adhesive composition of the comparative example that does not contain the epoxy resin composition of the present invention by introducing at least four or more urethane groups. there is.

In particular, the epoxy resin composition of the present invention is contained in an amount of 10 to 20% by weight, preferably less than 10 to 25% by weight, more preferably, based on the total weight of the base epoxy resin contained in the one-part epoxy adhesive composition of the present invention and the epoxy resin composition of the present invention. At 10 to 20% by weight, it shows surprisingly improved values in all physical properties.

Furthermore, the cured product made from the one-component epoxy adhesive composition according to the present invention has excellent shear strength, shear stress, tensile strength, and impact strength, and can provide excellent durability by preventing structural deformation due to external impact. Therefore, according to the present invention, improved rigidity can be provided by compensating for the brittleness of the conventional epoxy resin.

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 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 (14)

An epoxy resin composition represented by the following formula (3).
[Formula 3]

In Formula 3 above,
A is a functional group derived from a polyisocyanate compound;
Z is a functional group derived from difunctional polyetheramine;
R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₂ aryl;
R _a is hydrogen or methyl;
The m is a real number excluding integers greater than or equal to 1. delete According to clause 1,
In the above Chemical Formula 3, Z is represented by the following Chemical Formula 4, an epoxy resin composition.
[Formula 4]

In Formula 4 above,
R ₁ or R ₂ are independently hydrogen or methyl;
The above n is one or more real numbers. According to clause 1,
An epoxy resin composition wherein the polyisocyanate compound is an alicyclic polyisocyanate compound. According to clause 1,
The above formula (3) is an epoxy resin composition represented by the following formula (5).
[Formula 5]

In Formula 5 above,
A is a functional group derived from a polyisocyanate compound;
R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₂ aryl;
n is a real number greater than 1, and m is a real number excluding integers greater than 1. According to clause 5,
In Formula 5, A is a functional group derived from an aliphatic polyisocyanate compound;
R is hydrogen or C _1- C ₅ alkyl;
An epoxy resin composition where n is a real number of 1 or more, and m is a real number excluding an integer of 2 or more. According to clause 1,
The epoxy resin composition is
A polyol derived from the reaction of a difunctional polyetheramine and a cyclic carbonate, and
An epoxy resin composition derived from a polyurethane prepolymer prepared by reacting the polyol and a polyisocyanate compound. According to clause 7,
The polyurethane prepolymer is an epoxy resin composition represented by the following formula (6).
[Formula 6]

In Formula 6 above,
A is a functional group derived from a polyisocyanate compound;
R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₂ aryl;
R ₁ to R ₃ are independently hydrogen or methyl;
n is a real number greater than or equal to 1, and m is a real number excluding integers greater than or equal to 1. According to clause 7,
The bifunctional polyetheramine is any one or a mixture of two or more selected from Jeffamine D-230, D-400, D-2000, ED-600, ED-900 and ED-2003 (from Huntsman);
The cyclic carbonate is an epoxy resin composition wherein the cyclic carbonate is ethylene carbonate, propylene carbonate, or a mixture thereof. A one-component epoxy adhesive composition comprising the epoxy resin composition of claim 1. According to clause 10,
The one-component epoxy adhesive composition further includes a base epoxy resin, a curing agent, and a curing accelerator. According to clause 11,
The one-component epoxy adhesive composition is a one-component epoxy adhesive composition that contains 5 to 30% by weight of the epoxy resin composition based on the total weight of the base epoxy resin and the epoxy resin composition. A cured product of the one-component epoxy adhesive composition of claim 10. A polyurethane prepolymer represented by the following formula (6).
[Formula 6]

In Formula 6 above,
A is a functional group derived from a polyisocyanate compound;
R is hydrogen, C _1- C ₁₀ alkyl, C _1- C ₁₀ alkoxy or C _6- C ₁₀ aryl;
R ₁ to R ₃ are independently hydrogen or methyl;
n is a real number greater than 1, and m is a real number excluding integers greater than 1.