KR102566314B1 - 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 containing the same, and a one-component epoxy adhesive composition containing the same. The epoxy compound of the present invention is introduced with at least three or more urethane functional groups, so unlike conventional polyurethane tougheners, the epoxy resin It is easy to handle due to its excellent compatibility with and satisfies strength requirements such as high shear strength and shear deformation.

Description

Epoxy compound, epoxy resin composition containing the same, and one-component epoxy adhesive composition containing the same

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

As for the epoxy resin composition, a two-component type composed of a polyol-based compound and an isocyanate-based compound and a one-component type that is cured by moisture in the air are known. Due to the various advantages of the one-component type epoxy based 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 such an epoxy resin, it is pointed out as a major disadvantage in industries requiring high resistance to impact due to its brittleness, such as glass.

That is, epoxy resins that lack toughness may 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 not easy to handle because they increase the viscosity of the adhesive or have low compatibility with the epoxy resin, and the adhesive performance deteriorates due to impact or compression shear at the bonding site, so the effect is still insignificant. am.

Therefore, there is still a need for an adhesive that is easy to handle and can realize excellent adhesive performance even in the event of impact 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 containing the epoxy compound of the present invention and a cured product thereof.

In addition, the present invention provides a one-component epoxy adhesive composition containing 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 by being 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 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 each independently hydrogen or methyl;

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

Preferably, the polyisocyanate compound in Chemical 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 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;

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

In terms of having more improved physical properties as a main agent or toughening agent of an adhesive, A in Formula 2 according to an embodiment of the present invention is preferably a functional group derived from an aliphatic polyisocyanate compound; R is hydrogen or C1-C5 alkyl; n and m may be an integer of 2 or more independently of each other.

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 and a polyisocyanate compound.

Preferably, the polyurethane prepolymer according to an embodiment of the present invention may be represented by Formula 3 below.

[Formula 3]

(In Chemical 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 independently of each other 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.

An 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 containing the epoxy compound of the present invention and a cured product thereof.

Preferably, the epoxy resin composition according to one embodiment of the present invention may include 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 containing the epoxy compound 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 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 provides 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 Chemical 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 independently of each other an integer of 2 or more.)

The epoxy compound of the present invention includes at least three or more urethane groups and is used as a main agent or a toughening agent of an epoxy adhesive composition to have improved curing behavior and shear strength.

In addition, the epoxy compound of the present invention has very good miscibility with the base epoxy resin and 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 strength requirements such as high impact strength and flexural strength, and thus has excellent adhesive performance even under impact or high compression shear.

In addition, the polyurethane prepolymer of the present invention is a novel compound, and has at least three or more urethane groups, and the epoxy compound of the present invention prepared therefrom 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 useful for various materials in various fields, such as aircraft members, spaceship 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 containing the same, and a 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 terms and scientific terms used, they have meanings commonly understood by those of ordinary skill in the art to which this invention belongs, and will unnecessarily obscure the gist of the present invention in the following description. Descriptions of possible known functions and configurations are omitted.

The singular form used herein may be intended to include the plural form as well, unless the context dictates otherwise.

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

Further, as used herein, numerical ranges include lower and upper limits and all values within that range, increments logically derived from the shape and breadth of the defined range, all values defined therebetween, and the upper limit of the numerical range defined in a different form. and all possible combinations of lower bounds. Unless otherwise specifically 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 in the present invention, the term "comprises" is an open description having the same meaning as the expression "includes", "includes", "has" or "characterized by", and is not further listed. It does not exclude any element, material or process.

In addition, the term "cured product" used in the present invention may be a cured product of an epoxy adhesive composition as a general meaning. In addition, 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 alkyls, when used alone or in combination, may be straight-chain or branched-chain alkyls, respectively. 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, etc. 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, and the like. 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 the reaction of one or more isocyanate groups present in the polyisocyanate compound, etc. It may be according to the number of groups.

The present invention provides an epoxy compound, an epoxy resin composition containing the same, and a one-component epoxy adhesive composition containing the same. The epoxy compound of the present invention is represented by Formula 1 below.

[Formula 1]

(In Formula 1 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 each independently hydrogen or methyl;

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

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

Furthermore, the epoxy compound of the present invention is easy to handle in a wide temperature range, including temperatures lower than room temperature, and has excellent strength requirements such as impact strength and flexural strength, so it has excellent adhesion performance even in impact or high compression shear.

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

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

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

The polyisocyanate compound in Chemical 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 its molecule. Polyisocyanate compounds include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, heterocyclic polyisocyanate compounds, aliphatic polyisothiocyanate compounds, alicyclic polyisothiocyanate compounds, and aromatic polyisothiocyanate compounds. and sulfur-containing heterocyclic polyisothiocyanate compounds, and modified products thereof.

For example, the polyisocyanate compound is 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 natoethylthio)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 the like; Aromatic polyisocyanates such as phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and diphenylsulfide-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-dithiophene An, 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 the isothiocyanate compound include 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, 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 Contains sulfur, such as natomethyl)-1,4-dithiane, 4,5-diisothiocyanato 1,3-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, respectively. Aromatic polyisocyanate or alicyclic polyisocyanate is preferable, and alicyclic polyisocyanate is more preferable in terms of having a more excellent shear modulus of the epoxy adhesive composition using the epoxy compound prepared from these and improved adhesiveness even under high temperature and high humidity. desirable. A more preferred example of the alicyclic polyisocyanate may be trans cyclohexane 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 alicyclic 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 independently integers from 2 to 30.

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

[Formula 2]

(In Formula 2 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;

n and m are independently of each other 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 be independently of each other an integer of 2 or more, more preferably A is trans cyclohexane 1,4-diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane and dicyclohexylmethane diisocyanate a functional group derived from one or more selected groups; 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, 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, as measured by gel permeation chromatography (GPC).

An epoxy compound according to an embodiment of the present invention is a polyol derived from a reaction product of a bifunctional 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 to incorporate a urethane functional group, and a polyisocyanate compound and It is prepared from a polyurethane prepolymer in which at least three or more urethane groups are introduced by reacting again.

Accordingly, the epoxy compound of the present invention has improved curing behavior and shear strength by having at least three, preferably at least four, urethane groups.

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

[Formula 3]

(In Chemical 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 independently of each other 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 is 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 bifunctional polyetheramine, and the cyclic carbonate may be prepared from the reaction of ethylene carbonate or propylene carbonate.

In addition, the present invention provides an epoxy resin composition containing the epoxy compound of the present invention.

The epoxy resin composition according to one 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.

In addition, the present invention includes a one-component 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 and excellent adhesive performance by including the epoxy compound of the present invention including at least three, preferably four 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.

In the one-component epoxy adhesive composition according to an embodiment of the present invention, the base epoxy resin and the epoxy compound have a weight ratio of 1 to 9:9 to 1, preferably 3 to 7:7 to 3, more preferably 4 to 9. 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 have two or more epoxy groups in a molecule, and may be saturated, unsaturated, cyclic or acyclic, aliphatic, or alicyclic. , It may be one selected from aromatic and heterocyclic polyepoxy compounds.

A non-limiting example of the base epoxy resin is any one or more bisphenol-type epoxy resins selected from bisphenol A, bisphenol E, bisphenol F, bisphenol M, bisphenol S, and bisphenol H, glycidyl ether and any one or a mixture of two or more selected from among epoxy resins, glycidyl amine epoxy resins, phenol novolak type epoxy resins, and cresol novolak type epoxy resins. Preferably, any one or two or more selected from bisphenol A-based epoxy resins and bisphenol F-based epoxy resins may be used in terms of having 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. When the above range is satisfied, it has more advantageous characteristics in improving mechanical properties such as impact strength and flexural strength to the bonding site, as well as the above-mentioned effects.

The curing agent according to an embodiment of the present invention may directly participate in crosslinking of the composition or act as a catalyst. The curing agent may 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 glutaric acid. and any one or two or more selected from acid anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

Non-limiting examples of the phenolic curing agent include formaldehyde condensation-type resol-type phenolic resins, non-formaldehyde condensation-type phenolic resins, novolac-type phenolic resins, novolac-type phenolic 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 novolak 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 and naphtholaralkyl resins having a phenylene skeleton or diphenylene skeleton; and 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 sum 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 curing proceeds in a short time to secure productivity.

In addition, the curing accelerator is for controlling 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.

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, or any one or two or more selected from the like.

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

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 is not limited thereto.

The one-component epoxy adhesive composition according to one embodiment of the present invention has the advantage of not requiring mixing and adjustment of the composition in field construction and easy handling.

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 includes 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, so that the curing time is 30 minutes to 120 to 180 ° C. It can be carried out for 2 hours, and the shear strength according to ASTM D 1002 can satisfy more than 17.00 MPa. In addition, it may be 18.00 MPa or more, and also 20.00 MPa, and the shear strain may satisfy 5.00%, preferably 6.00% more than 5.50%.

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 assembling vehicles such as automobiles, aircraft, and ships as well as structures such as civil engineering buildings. It has excellent adhesive performance 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 various industries including structural adhesives.

The epoxy compound of the present invention, the epoxy resin composition including the same, and the one-component epoxy adhesive composition including the same will be described in more detail through the following examples. However, the following examples are only one reference for explaining the present invention in detail, but the present invention is not limited thereto, and may be implemented in various forms. Also, unless defined otherwise, 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, terms used in description in the present invention are only for effectively describing specific embodiments, and are not intended to limit the present invention.

(Assessment Methods)

1. Shear strength and shear strain:

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

2. Hardening behavior experiment:

A sample of less than 5 mg was collected in a DSC pan to prepare a specimen and measured by raising the temperature at a rate of 10 ° C / min in the temperature range of 50 ° C to 250 ° C using a differential scanning calorimeter (DSC).

[Production Example 1] Production of polyol

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

Synthesis of the prepared polyol was confirmed by ¹ H-NMR (CDCl ₃ ). CDCl ₃ was used as the measurement solvent. The polyol conversion was measured using the CH3 peak located at the terminal of Jeffamine D-400 and the CH ₃ peak 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 jacket reactor including a stirrer, a reflux condenser, and a thermometer, and 74.45 g of IPDI, which is isophorone diisocyanate, was added. When the reaction temperature reaches 60°C, a dibutyltin dilaurate (DBTDL) catalyst is added to initiate the urethane reaction. Confirm the conversion rate through the NCO peak through FT-IR. When the peak of NCO reached a state where there was no change, 26.04 g of glycidol, an end blocker, and residual NCO were reacted to obtain an epoxy compound terminated with epoxy.

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 2270 cm ^-1 was consumed at a certain level (1eq) and became constant after 5 hours of reaction, and then glycidol was added and reacted with the remaining NCO for 3 hours to completely disappear NCO was confirmed by FT-IR. ¹ H-NMR measurement was performed at room temperature using CDCl ₃ as a solvent. 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 shifted due to the urethane bond, indicating that the epoxy compound was successfully synthesized. The weight average molecular weight of the epoxy compound thus synthesized was measured by GPC (calibrated with PMMA (methyl methacrylate)), and 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, a curing agent, and a curing accelerator described below in the materials and contents shown in Table 1 below.

That is, as shown in Table 1 below, the base epoxy resin and the epoxy compound are mixed in % by weight, and the total weight of the base epoxy resin and the epoxy compound is 100 parts by weight, and the curing agent and the curing accelerator as shown in Table 1 are mixed in parts by weight A one component 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 physical property results through the evaluation method are shown in Table 2 below.

Example 3 Example 4 Example 5 Comparative Example 1 Base epoxy resin (% by weight) 90 70 50 100 Epoxy compound (% by weight) 10 30 50 not include Curing agent (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)

Hardener: 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-component epoxy adhesive composition according to the present invention, as the ratio of the epoxy resin of the present invention increases, the glass transition temperature (Tg) tends to decrease. 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 the comparative example without the epoxy resin compound.

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

Furthermore, the cured product made of the one-component epoxy adhesive composition according to the present invention has excellent impact strength and shear strength, and thus can impart 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, the present invention has been described by specific details, limited examples and comparative examples, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the present invention Those skilled in the art can make various modifications and variations from these descriptions.

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

Claims (16)

An 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. According to claim 1,
In Formula 1, the polyisocyanate compound is an alicyclic polyisocyanate compound. According to 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. In 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 each independently an integer of 2 or more epoxy compound. According to claim 1,
The epoxy compound is
polyols derived from the reaction product of a bifunctional polyetheramine and a cyclic carbonate, and
An epoxy compound derived from a polyurethane prepolymer prepared by reacting the polyol with a polyisocyanate compound. According to claim 5,
The polyurethane prepolymer is an epoxy compound represented by Formula 3 below.
[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. According to claim 5,
The cyclic carbonate is an epoxy compound of ethylene carbonate, propylene carbonate or a mixture thereof. According to any one selected from claims 1 to 7,
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. According to claim 9,
The epoxy compound is an epoxy resin composition contained in 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. According to claim 11,
The one-component epoxy adhesive composition further comprises an epoxy resin, a curing agent and a curing accelerator, the one-component epoxy adhesive composition. According to claim 11,
The one-component epoxy adhesive composition includes 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 Formula 3 below.
[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.