KR20220109975A - Epoxy compound, epoxy resin composition containing the same, and one-component epoxy adhesive composition comprising the same - Google Patents

Abstract

The present invention relates to an epoxy compound, an epoxy resin composition comprising the same, and a one-component epoxy adhesive composition comprising the same. The epoxy compound of the present invention has at least three or more urethane functional groups introduced therein, and thus has excellent compatibility with an epoxy resin, unlike a conventional polyurethane-based toughening agent. Therefore, the epoxy compound is easy to handle and satisfies strength requirements such as high shear strength and shear deformation.

Description

An epoxy compound, an epoxy resin composition comprising the same, and a one-component epoxy adhesive composition comprising the same

The present invention relates to an epoxy compound, an epoxy resin composition comprising the same, and a one-component epoxy adhesive composition comprising the same, and more particularly, an epoxy compound derived from a polyurethane prepolymer in which at least three or more urethane groups are introduced, an epoxy comprising the same It relates to a resin composition and a one-part epoxy adhesive composition comprising the same.

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 two-component compositions composed of a polyol-based compound and an isocyanate-based compound and one-component compositions that are cured by moisture in the air. Because of the various advantages of the one-component epoxy main composition is widely used.

In particular, epoxy resins used in adhesives are widely used in the bonding, molding, and coating industries due to their high mechanical properties and thermal and insulating properties. Despite the good mechanical properties of the epoxy resin, it is pointed out as a major disadvantage in the industrial field requiring high resistance to impact due to brittleness, which is easy to break from impact, such as glass.

In other words, an epoxy resin that lacks toughness can compromise important strength requirements, such as impact strength and flexural strength. In order to meet such strength requirements, recent epoxy adhesive compositions use additives such as toughening agents.

However, these additives increase the viscosity of the adhesive or have low compatibility with the epoxy resin, making it difficult to handle, and the adhesive performance is deteriorated due to impact or compression shear at the bonding site, so the effect is still insignificant. to be.

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

Korean Patent Publication No. 10-2020-0048601

The present invention provides an epoxy compound that can be used as an adhesive to have improved impact strength and flexural strength.

In addition, the present invention provides an epoxy resin composition comprising the epoxy compound of the present invention and a cured product thereof.

In addition, the present invention provides a one-component epoxy adhesive composition comprising the epoxy compound of the present invention and a cured product thereof.

It also provides a polyurethane prepolymer for preparing the epoxy compound of the present invention.

The present invention is to provide an epoxy compound having surprisingly improved physical properties used as an adhesive agent or a toughening agent of an epoxy adhesive composition,

The epoxy compound of the present invention is represented by the following formula (1).

[Formula 1]

(In Formula 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 ₁₀ aryl;

R ₁ to R ₃ are each independently hydrogen or methyl;

n and m are each independently an integer of 2 or more.)

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

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

[Formula 2]

(In Formula 2,

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;

n and m are each independently an integer of 2 or more.)

Preferably, in terms of having more improved physical properties as a subject or toughening agent of an adhesive, in Formula 2 according to an embodiment of the present invention, A is a functional group derived from an aliphatic polyisocyanate compound; R is hydrogen or C 1 -C 5 alkyl; n and m may each independently be an integer of 2 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 bifunctional 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 (3).

[Formula 3]

(In Formula 3,

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 each independently hydrogen or methyl;

n and m are each independently an integer of 2 or more.)

Specifically, the bifunctional polyetheramine according to an embodiment of the present invention is Jeffamine D-230, D-400. any one or a mixture of two or more selected from D-2000, ED-600, ED-900, ED-2003, T-403 and T-3000; The cyclic carbonate may be ethylene carbonate, propylene carbonate, or a mixture thereof.

The epoxy compound according to an embodiment of the present invention may be used for an epoxy resin adhesive or an epoxy resin toughening agent.

In addition, the present invention provides an epoxy resin composition comprising the epoxy compound of the present invention and a cured product thereof.

Preferably, the epoxy resin composition according to an embodiment of the present invention may contain 1 to 99% by weight of the epoxy compound of the present invention based on the total weight of the epoxy resin composition.

In addition, the present invention provides a one-component epoxy adhesive composition comprising the epoxy compound of the present invention and a cured product thereof.

Preferably, the one-part 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 include a base epoxy resin and an epoxy resin compound in a weight ratio of 1 to 9: 9 to 10.

In addition, the present invention to provide a polyurethane prepolymer for preparing the epoxy compound of the present invention, the polyurethane prepolymer of the present invention may be represented by the following formula (3).

[Formula 3]

(In Formula 3,

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 each independently hydrogen or methyl;

n and m are each independently an integer of 2 or more.)

The epoxy compound of the present invention includes at least three or more urethane groups, so that it is used as a main agent or toughener of an epoxy adhesive composition and has improved curing behavior and shear strength.

In addition, the epoxy compound of the present invention has very good compatibility with the base epoxy resin, so it can be used with various base epoxy resins, so the compatibility is very high and handling is easy.

Therefore, the one-component epoxy adhesive composition containing the epoxy compound of the present invention satisfies the strength requirements such as high impact strength and flexural strength, and has excellent adhesive performance even in impact or high compressive shear.

In addition, the polyurethane prepolymer of the present invention is a novel compound, and the epoxy compound of the present invention prepared therefrom having at least three or more urethane groups has improved physical properties by introducing three or more urethane groups.

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

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

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

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

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

As used herein, the term "comprises" is an open-ended description having an equivalent meaning to expressions such as "comprises", "contains", "has" or "characterized by", and is not listed further. It does not exclude elements, materials or processes.

In addition, as used herein, the term “cured product” may be a cured product of an epoxy adhesive composition in a general sense. In addition, the cured product may include a semi-cured material.

As used herein, the term "alkyl" means an aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms. The alkyls may be straight-chain or branched alkyl, respectively, when used alone or in combination. The straight-chain or branched alkyl is specifically methyl, ethyl, normalpropyl, isopropyl, normalbutyl, isobutyl, tert-butyl, normalpentyl, neo-pentyl, normalhexyl, isohexyl, normalheptyl, normaloctyl, normalnonyl , normal decyl, and the like may be included.

As used herein, the term "alkoxy" means -OCH ₃ , -OCH ₂ CH ₃ , -O(CH ₂ ) ₂ CH ₃ , -O(CH ₂ ) ₃ CH ₃ , -O(CH ₂ ) ₄ CH ₃ , -O-(alkyl), including -O(CH ₂ ) ₅ CH ₃ , and the like, wherein 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. Carbocyclic aromatic groups may be optionally substituted.

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

The present invention provides an epoxy compound, an epoxy resin composition comprising the same, and a one-component epoxy adhesive composition comprising the same, wherein the epoxy compound of the present invention is represented by the following formula (1).

[Formula 1]

(In Formula 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 ₁₀ aryl;

R ₁ to R ₃ are each independently hydrogen or methyl;

n and m are each independently an integer of 2 or more.)

As at least three or more urethane functional groups are introduced, the epoxy compound of the present invention has excellent mechanical properties and excellent curing behavior and shear strength, unlike conventional epoxy compounds.

Furthermore, the epoxy compound of the present invention is not only easy to handle in a wide temperature range, including lower than room temperature, but also has excellent strength requirements such as impact strength and flexural strength, and has excellent adhesive performance even in impact or high compressive shear.

In addition, the epoxy compound of the present invention can be used as an epoxy adhesive agent itself, and preferably used as a polyurethane-based toughening agent.

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

In addition, the epoxy compound of the present invention has the advantage that the shear strength can be easily controlled by adjusting the epoxy content.

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. The polyisocyanate compound is an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, an aromatic polyisocyanate compound, a heterocyclic polyisocyanate compound, an aliphatic polyisothiocyanate compound, an alicyclic polyisothiocyanate compound, an aromatic polyisothiocyanate compound. and sulfur-containing heterocyclic polyisothiocyanate compounds, and modified products 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-xylene diisocyanate, α,α,α′,α′-tetramethylxylylenediisocyanate, bis(isocyanatomethyl)naphthalene, mesityrylenetriisocyanate, bis(isocya) Natomethyl)sulfide, bis(isocyanatoethyl)sulfide, bis(isocyanatomethyl)disulfide, bis(isocyanatoethyl)disulfide, bis(isocyanatomethylthio)methane, bis(isocyana aliphatic polyisocyanate compounds such as natoethylthio)methane, bis(isocyanatoethylthio)ethane, and bis(isocyanatomethylthio)ethane; Isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, cyclohexanediisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethylmethaneisocyanate, 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 Opene, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis(isocyanatomethyl)-1,4-dithione Heterocyclic polyisocyanate compounds, such as an ant, 4,5-diisocyanato-1,3-dithiolane, and 4,5-bis(isocyanatomethyl)-1,3-dithiolane; and the like.

As the isothiocyanate compound, for example, hexamethylene diisothiocyanate, lysine diisothiocyanate methyl ester, lysine triisothiocyanate, m-xylene diisothiocyanate, bis(isothiocyanatomethyl) ) aliphatic polyisothiocyanate compounds such as sulfide, bis(isothiocyanatoethyl)sulfide, and bis(isothiocyanatoethyl)disulfide; Isophorone diisothiocyanate, bis(isothiocyanatomethyl)cyclohexane, dicyclohexylmethane diisothiocyanate, cyclohexanediisothiocyanate, methylcyclohexanediisothiocyanate, 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)tricyclodecane alicyclic polyisothiocyanate compounds such as methyl)tricyclodecane; aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate, 4,4-diphenylmethane diisothiocyanate, and diphenyldisulfide-4,4-diisothiocyanate; 2,5-diisothiocyanatothiophene, 2,5-bis(isothiocyanatomethyl)thiophene, 2,5-isothiocyanatotetrahydrothiophene, 2,5-bis(isothiocyanatomethyl)thiophene Methyl) tetrahydrothiophene, 3,4-bis (isothiocyanatomethyl) tetrahydrothiophene, 2,5-diisothiocyanato-1,4-dithiane, 2,5-bis (isothiocyana) Contains sulfur such as natomethyl)-1,4-dithiane, 4,5-diisothiocyanato1,3-dithiolane, 4,5-bis(isothiocyanatomethyl)-1,3-dithiolane heterocyclic polyisothiocyanate compounds; and the like.

The above polyisocyanate compounds can be used individually or in combination of 2 or more types, respectively. An aromatic polyisocyanate or an alicyclic polyisocyanate is preferable in terms of having better shear modulus of an epoxy adhesive composition using an epoxy compound prepared among them, and having improved adhesion even under high temperature and high humidity, and an alicyclic polyisocyanate is more desirable. More preferred examples of the cycloaliphatic polyisocyanate may be transcyclohexane 1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(isocyanatemethyl)cyclohexane (H6XDI), dicyclohexylmethane diisocyanate (H12MDI). .

Preferably, in Formula 1 according to an embodiment of the present invention, A is a functional group derived from an aromatic or cycloaliphatic polyisocyanate compound; R is hydrogen, C ₁ -C ₅ alkyl or C ₁ -C ₅ alkoxy; R ₁ to R ₃ are each independently hydrogen or methyl; n and m may be each independently an integer of 2 or more, and more preferably, A in Formula 1 is a functional group derived from an alicyclic polyisocyanate compound; R is hydrogen or C ₁ -C ₃ alkyl; R ₁ and R ₃ are independently of each other methyl; R ₂ is hydrogen; n and m may be each independently an integer of 2 to 30.

Formula 1 according to an embodiment of the present invention preferably in terms of being included in the epoxy adhesive composition to have improved physical properties may be represented by Formula 2 below.

[Formula 2]

(In Formula 2,

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;

n and m are each independently an integer of 2 or more.)

Preferably, in Formula 2 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 and m may independently be an integer of 2 or more, and more preferably, A is in trans cyclohexane 1,4-diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane and dicyclohexylmethane diisocyanate. a functional group derived from one or two or more selected; R is hydrogen or methyl; n and m are each independently an integer of 2 to 30, more preferably n is an integer of 3 to 23, and m may be an integer of 2 to 10.

The epoxy compound according to an embodiment of the present invention may have a weight average molecular weight of 2,000 to 4,000 g/mol, preferably 2,400 to 3,700 g/mol, measured by gel permeation chromatography (GPC).

The epoxy compound according to an embodiment of the present invention is a polyol derived from a reaction product 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 compound according to an embodiment of the present invention is first prepared from a polyol derived from a reaction product of a bifunctional polyetheramine and a cyclic carbonate through a non-isocyanate urethane reaction, and a urethane functional group is introduced thereto, and the polyisocyanate compound and It is prepared from a polyurethane prepolymer into which at least three or more urethane groups are introduced by reacting again.

Accordingly, the epoxy compound of the present invention has at least three or more, preferably, at least four or more urethane groups to have improved curing behavior and shear strength.

The difunctional 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 3,000 g/mol, more preferably 300 to 1,500 g/mol. mol of polyetheramine. As a more specific example, any one selected from Huntsman's JEFFAMINE's D-400, D-2000, ED-600, ED-900, ED-2003, T-403 and T-3000, or two or more commercially available commercial products It can be a product.

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, ethylene carbonate or propylene carbonate, , 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 ₁₀ aryl.

In terms of preparing a polyurethane prepolymer having desirable physical properties according to an embodiment of the present invention, the bifunctional polyetheramine is D-400, D-2000 or T-403 of Jeffamine, and the cyclic carbonate is ethylene carbonate or It may be a combination of propylene carbonate.

Specifically, the polyurethane prepolymer according to an embodiment of the present invention may be represented by the following formula (3).

[Formula 3]

(In Formula 3,

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 each independently hydrogen or methyl;

n and m are each independently an integer of 2 or more.)

Preferably, in Formula 3 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 and m may be each independently an integer of 2 or more, 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 and m may be each independently an integer of 2 or more, n may be an integer of 3 to 23, and m may be an integer of 2 to 10.

Preferably, the polyurethane prepolymer of the present invention is D-400 or T-403 of JEFFAMINE as a difunctional polyetheramine, and the cyclic carbonate may be prepared from the reaction of ethylene carbonate or propylene carbonate.

The present invention also provides an epoxy resin composition comprising the epoxy compound of the present invention.

The epoxy resin composition according to an embodiment of the present invention essentially contains the epoxy compound of the present invention, specifically 1 to 99% by weight, preferably 5 to 60% by weight, more preferably 30% by weight based on the total weight of the epoxy resin composition to 50% by weight.

The present invention also includes a one-part epoxy adhesive composition comprising the epoxy compound of the present invention.

The one-component epoxy adhesive composition of the present invention has improved mechanical properties by including the epoxy compound of the present invention including at least three or more, preferably four or more urethane functional groups as a main agent and a toughening agent, and at the same time has excellent adhesive performance.

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 has a base epoxy resin and an epoxy compound in a weight ratio of 1 to 9: 9 to 1, preferably 3 to 7: A weight ratio of 7 to 3, more preferably 4 to 6: It may be included in a weight ratio of 6 to 4.

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

As a non-limiting example of the base epoxy resin, any one or more bisphenol-type epoxy resins selected from bisphenol A-based, bisphenol E-based, bisphenol F-based, bisphenol M-based, bisphenol S-based and bisphenol H-based, glycidyl ether and any one or a mixture of two or more selected from a type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolak type epoxy resin, and a cresol novolak type epoxy resin. Preferably, any one or two or more selected from the bisphenol A-based epoxy resin and the bisphenol F-based epoxy resin may be used in terms of 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 a liquid at room temperature, and may have an epoxy equivalent weight of 100 to 600 g/eq, or 150 to 550 g/eq. When the above range is satisfied, mechanical properties such as impact strength and flexural strength to the bonding site as well as the above-described effects are improved, and it has more advantageous properties.

The curing agent according to an embodiment of the present invention may directly participate in the crosslinking of the composition or may act in the form of a catalyst. The curing agent is a curing agent of the epoxy resin, which is the main subject, and may be used without limitation as long as it is known in the art, and may be selected from an acid anhydride curing agent, a phenolic curing agent, an amino curing agent, and the like.

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, glutaric acid and any one or two or more selected from acid anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

Non-limiting examples of the phenol-based curing agent include formaldehyde condensed resol phenolic resins, non-formaldehyde condensed phenolic resins, novolac-type phenolic resins, novolac-type phenol formaldehyde resins, and polyhydroxystyrene resins. phenolic resins such as; resol-type phenolic resins such as aniline-modified resol resins and melamine-modified resol resins; novolac-type phenolic resins such as phenol novolac resins, cresol novolac resins, tert-butylphenol novolac resins, nonylphenol novolac resins and naphthol novolac resins; special phenolic resins such as dicyclopentadiene-modified phenolic resins, terpene-modified phenolic resins, triphenolmethane-type resins, phenolaralkyl resins having a phenylene skeleton or diphenylene skeleton, and naphtholaralkyl resins; and any one or two or more selected from polyhydroxystyrene resins such as poly(p-hydroxystyrene).

Non-limiting examples of the amino curing agent include dimethyl dicykan (DMDC), dicyandiamide (DICY), isophoronediamine (IPDA), diethylenetriamine (DETA), triethylenetetramine (TETA) , bis(p-aminocyclohexyl)methane (PACM), methylenedianiline (eg 4,4'-methylenedianiline), polyetheramines such as polyetheramine D230, diaminodiphenylmethane ( DDM), diaminodiphenylsulfone (DDS), 2,4-toluenediamine, 2,6-toluenediamine, 2,4-diamino-1-methylcyclohexane, 2,6-diamino-1-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.

In addition, the curing agent may include 3 to 15 parts by weight, preferably 3 to 10 parts by weight, of the curing agent based on 100 parts by weight of the total of the epoxy compound and the base epoxy resin included in the one-component epoxy adhesive composition, but is limited thereto it is not In the case of the above range, it is preferable that the curing proceeds in a short time to secure productivity.

In addition, the curing accelerator is for controlling the curing rate, and may be selected from imidazole-based accelerators and urea-based accelerators.

Non-limiting examples of the imidazole accelerator include 2-methylimidazole, 2-heptadecyl imidazole, 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 midazole and 1-cyanoethyl-2-undecylimidazole, and any one or two or more selected from the group.

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) ) bis(1,1-dimethylurea) and 3,4-dichlorophenyl-N,N-dimethylurea, and the like, may be selected from any one or two or more.

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 total of the compound and the base epoxy resin included in the one-component epoxy adhesive composition, but is not limited thereto. .

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

The one-component epoxy adhesive composition according to an embodiment of the present invention has advantages in that it is unnecessary to adjust the mixing of the composition in local construction, and it is easy to handle.

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

The cured product according to an embodiment of the present invention is cured by including the epoxy compound of the present invention and the base epoxy resin in a weight ratio of 1 to 9: 9 to 1 as the one-component epoxy adhesive composition. It can be carried out for 2 hours, and the shear strength according to ASTM D 1002 can satisfy 17.00 MPa or more. In addition, 18.00 MPa or more, it may be 20.00 MPa, and the shear strain may satisfy 5.00%, preferably 6.00% rather than 5.50%.

The one-part 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 vehicles, such as automobiles, aircraft, ships, etc., as well as structures such as civil buildings. It has excellent adhesion performance between the same or different materials such as metal and metal, metal and glass, and metal and carbon fiber, so it can be used in a variety of industries including structural adhesives.

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

(Assessment Methods)

1. Shear strength and shear deformation:

Shear strength and shear strain were measured according to ASTM D 1002 using a universal testing machine (UTM).

2. Hardening behavior test:

Samples of 5 mg or less were collected in a DSC pan to prepare a specimen, and the temperature range was 50° C. to 250° C. using a differential scanning calorimeter (DSC), and the temperature was increased at a rate of 10° C./min.

[Preparation Example 1] Preparation of polyol

373.71 g of propylene carbonate was mixed with 750 g of Jeffamine D-400 (Huntsman) and stirred at 100° C. for 72 hours. From the obtained reaction mixture, dichloromethane and water were used to remove unreacted propylene carbonate and Jeffamine D-400. A trace amount of water was removed using MgSO ₄ , and dichloromethane contained in the purified polyol was removed by vacuum distillation using a rotary concentrator to obtain a final compound.

The synthesis of the prepared polyol was confirmed by ¹ H-NMR (CDCl ₃ ). The measurement solvent was CDCl ₃ . The conversion of the polyol was measured using the peak of CH3 located at the end of Jeffamine D _- 400 and the peak of CH3 of propylene carbonate, and it was confirmed that the polyol was synthesized with a conversion rate of 97%.

[Example 1] Preparation of polyurethane prepolymer and epoxy compound

106.16 g of the polyol prepared in Preparation Example 1 was placed in a double-jacketed reactor including a stirrer, a reflux condenser, and a thermometer, and 74.45 g of IPDI, which is isophorone diisocyanate, was added thereto. When the reaction temperature reaches 60° C., a DBTDL (Dibutyltin dilaurate) catalyst is added to initiate the urethane reaction. Check the conversion rate through the NCO peak through FT-IR. When the peak of NCO reached a state in which there was no change, 26.04 g of glycidol, a terminal blocker, was reacted with residual NCO to obtain an epoxy compound terminated with epoxy.

The synthesis of the polyurethane prepolymer and the epoxy compound was confirmed by FT-IR and ¹ H-NMR. In FT-IR, it was confirmed that the NCO peak corresponding to 2270cm ^-1 was consumed at a certain level (1eq) and became constant after 5 hours of reaction. was confirmed by FT-IR. ¹ H-NMR measurement was performed using the solvent CDCl ₃ , and was measured at room temperature. When the CH ₂ peak of glycidol and the epoxy CH ₂ peak of the synthesized epoxy compound were compared, it was confirmed that the peak of glycidol was shifted due to the urethane bond, indicating that the epoxy compound was successfully synthesized. As a result of measuring the weight average molecular weight of the synthesized epoxy compound by GPC (calibrated with PMMA (methyl methacrylate)), it was confirmed that Mw was 3,603 g/mol.

(Examples 2 to 4 and Comparative Example 1)

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

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

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 results of the physical properties through the evaluation method are shown in Table 2 below.

Example 3 Example 4 Example 5 Comparative Example 1 Base epoxy resin (wt%) 90 70 50 100 Epoxy compound (wt%) 10 30 50 not included Hardener (parts by weight) 6.34 5.252 4.165 6.97 Curing accelerator (parts by weight) 0.4 0.33 0.26 0.43

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

Hardener: dicyandiamide (Dyhard 100S, DICY)

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

Example 3 Example 4 Example 5 Comparative Example 1 T _peak (℃) 158.25 169.13 182.28 157.48 T _onset (℃) 144.22 140.22 137.08 145.49 Shear strength (MPa) 17.93 20.75 23.45 16.26 shear deformation 5.91 6.97 7.69 3.57

As shown in Table 2, in the one-part epoxy adhesive composition according to the present invention, as the ratio of the epoxy resin of the present invention increased, a tendency to decrease the glass transition temperature (Tg) was observed. In addition, it can be seen that the cured product prepared using the adhesive composition containing the epoxy resin compound of the present invention has surprisingly improved shear strength and shear strain value compared to Comparative Examples not including the same.

Therefore, it can be seen that the one-component epoxy adhesive composition of the present invention has excellent adhesion compared to the conventional one-component epoxy adhesive composition by introducing at least four or more urethane groups.

Furthermore, the cured product by the one-component epoxy adhesive composition according to the present invention has excellent impact strength and shear strength, and thus can provide excellent durability by preventing structural deformation due to external impact. That is, according to the present invention, it is possible to provide improved rigidity by supplementing the brittleness of the conventional epoxy resin.

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

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

Claims (16)

Epoxy compound represented by Formula 1 below:
[Formula 1]

In Formula 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 ₁₀ aryl;
R ₁ to R ₃ are each independently hydrogen or methyl;
n and m are each independently an integer of 2 or more. The method of claim 1,
In Formula 1, the polyisocyanate compound is an epoxy compound that is an alicyclic polyisocyanate compound. The method of claim 1,
Formula 1 is an epoxy compound represented by Formula 2 below.
[Formula 2]

In Formula 2,
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;
n and m are each independently an integer of 2 or more. According to the third
In Formula 2, A is a functional group derived from an aliphatic polyisocyanate compound;
R is hydrogen or C ₁ -C ₅ alkyl;
n and m are independently of each other an integer of 2 or more epoxy compound. The method of claim 1,
The epoxy compound is
a polyol derived from the reaction of a difunctional polyetheramine with a cyclic carbonate, and
A compound derived from a polyurethane prepolymer prepared by reacting the polyol with a polyisocyanate compound. 6. The method of claim 5,
The polyurethane prepolymer is an epoxy compound represented by the following formula (3).
[Formula 3]

In Formula 3,
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 each independently hydrogen or methyl;
n and m are each independently an integer of 2 or more. 7. The method of claim 6,
The bifunctional polyetheramine is Jeffamine D-230, D-400. any one or a mixture of two or more selected from D-2000, ED-600, ED-900, ED-2003, T-403 and T-3000;
The cyclic carbonate is an epoxy compound of ethylene carbonate, propylene carbonate, or a mixture thereof. According to any one of claims 1 to 7 selected from,
The epoxy compound is an epoxy compound for an epoxy resin adhesive or an epoxy resin toughening agent. An epoxy resin composition comprising the epoxy resin compound of any one of claims 1 to 7. The method of claim 9,
The epoxy compound is an epoxy resin composition comprising 1 to 99% by weight based on the total weight of the epoxy resin composition. A one-component epoxy adhesive composition comprising the epoxy compound of any one of claims 1 to 7. The method of claim 11,
The one-component epoxy adhesive composition further comprises an epoxy resin, a curing agent and a curing accelerator. 12. The method of claim 11,
The one-component epoxy adhesive composition is a one-component epoxy adhesive composition comprising a base epoxy resin and an epoxy compound in a weight ratio of 1 to 9: 9 to 1. A cured product of the epoxy resin composition of claim 9 . A cured product of the one-component epoxy adhesive composition of claim 11. A polyurethane prepolymer represented by the following formula (3).
[Formula 3]

In Formula 3,
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 each independently hydrogen or methyl;
n and m are each independently an integer of 2 or more.