KR20250115072A - Amine compound with low viscosity and low mild irritation, curative composition comprsing the same, coating composition comprsing the same, and product comprsing the same - Google Patents

Abstract

The present invention relates to an amine compound having an active hydrogen equivalent of 44 to 120, a curing composition comprising the same, a coating composition comprising the same, and an article manufactured from the coating composition. The amine compound has at least one terminal modified with a heteroaryl, and has the above-described active hydrogen equivalent, thereby exhibiting low skin permeability, low irritation, and low corrosion, and can be applied to a solvent-free curing composition to exhibit low viscosity characteristics.

Description

Amine compound with low viscosity and low mild irritation properties, curing agent composition containing the same, coating composition containing the same, and article containing the same {AMINE COMPOUND WITH LOW VISCOSITY AND LOW MILD IRRITATION, CURATIVE COMPOSITION COMPRSING THE SAME, COATING COMPOSITION COMPRSING THE SAME, AND PRODUCT COMPRSING THE SAME}

The present invention relates to an amine compound having low viscosity and skin-irritating properties, a curing agent composition comprising the same, a coating composition comprising the same, and an article comprising the same.

Epoxy resins have excellent adhesive properties and chemical resistance, and are used in a variety of applications, including coatings, adhesives, paints, and composite formulations. Epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, multifunctional epoxy resins, and novolac epoxy resins. Epoxy resins can be cured or crosslinked using amine-based curing agent compositions.

Conventionally, solvent-based curing agent compositions have been primarily used. However, due to environmental regulations on volatile organic compounds (VOCs), various attempts have been made to replace organic solvents or reduce their usage, including high-solid curing agent compositions, aqueous curing agent compositions, and solvent-free curing agent compositions. However, these curing agent compositions have had the problem of difficulty in controlling viscosity or pot life when used with epoxy resins. Therefore, recently, methods have been developed to control the viscosity of the curing agent composition by adjusting the content of free amines in solvent-free curing agent compositions or by using low-molecular-weight compounds such as benzyl alcohol as diluents. However, low-molecular-weight compounds such as free amines and benzyl alcohol are irritating and corrosive to the skin of workers during painting, so caution is required when handling them.

The present invention aims to provide an amine compound having low irritation or corrosiveness to the skin, a low-viscosity curing agent composition containing the same, a coating composition containing the same, and an article containing the same.

One aspect of the present invention provides an amine compound having a structure represented by the following chemical formula 1 and having an active hydrogen equivalent (A.H.E.W.) of 44 to 120.

[Chemical Formula 1]

Among the foods,

R ₁ , R ₂ and R ₃ are each independently a C ₂ -C ₁₀ alkyl group or a C ₂ -C ₁₀ alkylene group,

A and B are each independently a substituted or unsubstituted C ₆ -C ₁₄ aryl group, or a substituted or unsubstituted C ₃ -C ₁₄ heteroaryl group, wherein at least one of A and B is a substituted or unsubstituted C ₃ -C ₁₄ heteroaryl group,

X ₁ , X ₂ , X ₃ and X ₄ are each independently A, B or a hydrogen atom,

n is 0, 1, 2, 3, 4, 5, 6, or 7.

The above amine compound may be a reaction product of a reactant comprising one or more polyalkylene amines and one or more substituted or unsubstituted heteroaryl aldehydes.

The above polyalkylene amine may be a multifunctional amine having three or more active amine hydrogens.

The above polyalkylene amine may be at least one selected from the group consisting of diethylenetriamine, triethylenetetramine, N-3-aminopropyl ethylenediamine, N,N'-bis(3-aminopropyl)ethylenediamine, N,N-bis(3-aminopropyl)ethylenediamine, N,N,N'-tris(3-aminopropyl) ethylenediamine, N,N,N',N'-tetrakis(3-aminopropyl) ethylenediamine, N-3-aminopropyl-1,3-propanediamine, N,N'-bis(3-aminopropyl)-1,3-propanediamine, N,N-bis(3-aminopropyl)-1,3-propanediamine, N,N,N'-tris(3-aminopropyl)-1,3-propanediamine, and N,N,N',N'-tetrakis(3-aminopropyl)-1,3-propanediamine.

The molar ratio of the polyalkylene amine and the substituted or unsubstituted heteroaryl aldehyde may be 1:1 to 1:2.5.

The above reactants may further comprise one or more substituted or unsubstituted aryl aldehydes.

The molar ratio of the substituted or unsubstituted heteroaryl aldehyde may be greater than the molar ratio of the substituted or unsubstituted aryl aldehyde.

The molar ratio of the substituted or unsubstituted heteroaryl aldehyde and the substituted or unsubstituted aryl aldehyde may be 100:0 to 51:49.

The above heteroaryl may include one or more selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur and selenium.

When the above A or B has a substituent, the substituent is at least one selected from the group consisting of CH ₂ OH, CH ₂ Y, CHOR ₄ , R ₄ , CHO and COOH, wherein Y is a halogen atom and R ₄ may be a C ₁ -C ₁₀ alkyl group.

One aspect of the present invention provides a curing agent composition comprising an amine compound according to the above aspect.

The above reactant contains two or more kinds of polyalkylene amines and may have a viscosity of 500 cps or less at 25°C.

One aspect of the present invention provides a coating composition comprising an amine compound and an epoxy resin according to the above aspect.

One aspect of the present invention provides an article manufactured using a coating composition according to the above aspect.

The above article may be an adhesive, a coating, a primer, a sealant, a binder, a building product, a floor product, or a combination thereof.

The amine compound according to the present invention can be applied to a solvent-free curing agent composition. The solvent-free curing agent composition is safe due to its low skin irritation and corrosiveness, has low viscosity, allows spray coating, and has easy control of working time.

Figure 1 is a graph showing the change in contact angle of synthetic product droplets obtained in examples and comparative examples of the present invention according to ASTM D 5946.

Hereinafter, each component of the present invention will be described in more detail so that a person having ordinary skill in the art to which the present invention pertains can easily practice it; however, this is only an example, and the scope of the rights of the present invention is not limited by the following contents.

The term "comprises" as used herein is used to list materials, compositions, devices, and methods useful in the present invention, but is not limited to the listed examples.

As used herein, the terms "about" and "substantially" are used to mean a range or approximation of a numerical value or degree, taking into account inherent manufacturing and material tolerances, and are used to prevent infringers from unfairly exploiting the disclosure, which includes precise or absolute numerical values provided to aid understanding of the present invention.

The terms "skin irritation" and "skin corrosion" used herein can be evaluated by the Primary Irritation Index (PII) based on the skin irritation test method according to OECD guideline TG 404. When the skin irritation index is 5 or higher, it can be evaluated as having strong skin irritation and corrosion.

One embodiment of the present invention is an amine compound having a structure represented by the following chemical formula 1, wherein the active hydrogen equivalent (A.H.E.W.) of the amine compound is 44 to 120.

[Chemical Formula 1]

Among the foods,

R ₁ , R ₂ and R ₃ are each independently a C ₂ -C ₁₀ alkyl group or a C ₂ -C ₁₀ alkylene group,

A and B are each independently a substituted or unsubstituted C ₆ -C ₁₄ aryl group, or a substituted or unsubstituted C ₃ -C ₁₄ heteroaryl group, wherein at least one of A and B is a substituted or unsubstituted C ₃ -C ₁₄ heteroaryl group,

X ₁ , X ₂ , X ₃ and X ₄ are each independently A, B or a hydrogen atom,

n is 0, 1, 2, 3, 4, 5, 6, or 7.

The above heteroaryl may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur and selenium, and preferably may contain 1 to 4 heteroatoms.

When the above A or B has a substituent, the substituent is at least one selected from the group consisting of CH ₂ OH, CH ₂ Y, CHOR ₄ , R ₄ , CHO and COOH, wherein Y is a halogen atom and R ₄ may be a C ₁ -C ₁₀ alkyl group.

The active hydrogen equivalent weight (A.H.E.W.) of the above amine compound can be calculated as the ratio of the molecular weight of the amine compound to the number of active hydrogens of the amine contained in the amine compound.

In the conventional non-solvent type curing agent composition, the content of free amine that exists without reacting is increased, and the active hydrogen equivalent is adjusted to less than 44 to secure the curing property and low viscosity of the composition, but skin irritation is high in that range.

When the active hydrogen equivalent of the amine compound of the present invention was adjusted to 44 to 120, it was confirmed that curability suitable for forming a coating and an article was secured while at the same time showing skin irritation that was 50% or less lower than that of the conventional one. Specifically, the active hydrogen equivalent of the amine compound may be 44 or more, 45 or more, 50 or more, 55 or more, 60 or more, 65 or more, 70 or more, 75 or more, 80 or more, 85 or more, 90 or more, 95 or more, 100 or more, 105 or more, 115 or more, or 120 or less, 115 or less, 110 or less, 105 or less, 100 or less, 95 or less, 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, 55 or less, 50 or less, or 45 or less. Preferably, when the active hydrogen equivalent of the amine compound is 45 or more and 110 or less, it can exhibit low skin irritation with a P.I.I. of 3.5 or less.

The weight average molecular weight of the above amine compound may be 180 to 450. Preferably, the weight average molecular weight of the above amine compound may be 183.2 to 414.5.

The above amine compound may be a reaction product of a reactant comprising at least one polyalkylene amine and at least one substituted or unsubstituted heteroaryl aldehyde. The polyalkylene amine and the substituted or unsubstituted heteroaryl aldehyde may react in the presence of a metal catalyst to form an imine, and an amine compound modified with a substituted or unsubstituted heteroaryl may be formed through a hydrogenation reaction. The amine compound is for use in a curing agent composition, and the curing agent composition may be used for curing or crosslinking an epoxy resin. Specifically, the curing agent composition may be solvent-free.

In conventional solvent-free curing agent compositions, an amine compound modified with a substituted or unsubstituted aryl polyalkylene amine was used to improve the chemical resistance and water resistance of a coating or article formed with the curing agent composition. However, the amine compound modified with a substituted or unsubstituted aryl has a structure similar to a surfactant in which the aryl-containing terminal is lipophilic and the amine-containing core is hydrophilic, resulting in high permeability to human skin, which can cause skin irritation or destroy the skin barrier. In addition, the aryl structure is toxic to the human body, and can exhibit strong skin irritation and corrosiveness (P.I.I. standard 6.0 or higher) to the skin.

The present invention provides an amine compound having a structure in which skin permeability, irritation, and corrosion are reduced by modifying an amine compound with heteroaryl instead of the aryl, or by modifying the amine compound with aryl and heteroaryl, and a curing agent composition comprising the same. That is, the amine compound may be modified with at least a substituted or unsubstituted heteroaryl, and when used in a curing agent composition, it can provide chemical resistance, water resistance, and low viscosity properties while simultaneously providing safety to the human body. According to one embodiment of the present invention, an amine compound modified only with heteroaryl exhibits weak skin irritation with a P.I.I. of less than 4, and in another embodiment, less than 3.5, and according to another embodiment, an amine compound modified with heteroaryl and aryl exhibits a P.I.I. of less than 5, and in another embodiment, less than 4, on the skin irritation scale.

The above polyalkylene amine may be a multifunctional amine having three or more active amine hydrogens. For example, the polyalkylene amine may be at least one selected from the group consisting of diethylenetriamine (DETA), triethylenetetramine (TETA), N-3-aminopropyl ethylenediamine (N3), N,N'-bis(3-aminopropyl)ethylenediamine (N4), N,N-bis(3-aminopropyl) ethylenediamine, N,N,N'-tris(3-aminopropyl) ethylenediamine, N,N,N',N'-tetrakis(3-aminopropyl) ethylenediamine, N-3-aminopropyl-1,3-propanediamine, N,N'-bis(3-aminopropyl)-1,3-propanediamine, N,N-bis(3-aminopropyl)-1,3-propanediamine, N,N,N'-tris(3-aminopropyl)-1,3-propanediamine, and N,N,N',N'-tetrakis(3-aminopropyl)-1,3-propanediamine.

Preferably, the polyalkyleneamine may be a mixture of two or more polyfunctional amines. For example, the polyalkyleneamine may be a mixture of diethylenetriamine, triethylenetetramine, and N,N'-bis(3-aminopropyl)ethylenediamine. The molar ratio of diethylenetriamine to triethylenetetramine in the reactant may be 2.0 times or more and 5.0 times or less. Specifically, the molar ratio of diethyltriamine to triethylenetetramine may be 2.5 times or more, 3.0 times or more, 3.5 times or more, 4.0 times or more, or 4.5 times or less, 4.0 times or less, 3.5 times or less, 3.0 times or less, and preferably 2.5 times or more and 5.0 times or less. The molar ratio of N,N'-bis(3-aminopropyl)ethylenediamine to triethylenetetramine in the reactant may be 3.0 times or more and 7.0 times or less. Specifically, the molar ratio of N,N'-bis(3-aminopropyl)ethylenediamine to triethylenetetramine may be 3.5 times or more, 4.0 times or more, 4.5 times or more, 5.0 times or more, 5.5 times or more, 6.0 times or more, or 6.5 times or less, 6.0 times or less, 5.5 times or less, 5.0 times or less, 4.5 times or less, 4.0 times or less, 3.5 times or less, and preferably 3.5 times or more and 6.5 times or less.

In the above substituted or unsubstituted heteroaryl aldehyde, the heteroaryl may be C ₃ -C ₁₄ heteroaryl, and the heteroaryl may include at least one selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, and selenium. In the case of the nitrogen atom, it may include a quaternized one.

When the above heteroaryl aldehyde has a substituent, the substituent is at least one selected from the group consisting of CH ₂ OH, CH ₂ Y, CHOR ₄ , R ₄ , CHO and COOH, wherein Y is a halogen atom and R ₄ may be a C ₁ -C ₁₀ alkyl group.

Non-limiting examples of the above heteroaryl include monocyclic heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, isoxazolyl, oxazolyl, triazinyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc.; polycyclic heteroaryl such as benzofuranyl, benzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, benzodioxolyl, etc.; and their corresponding N-oxides (e.g., pyridyl) N-oxide, quinolyl N-oxide), and their quaternary salts, etc. Preferably, the heteroaryl may be _C4 - _C12 heteroaryl. More preferably, the heteroaryl may be furyl, and the heteroaryl aldehyde may be furfural. Furfural is a dehydration reaction product of (pentose) sugars generated from various biomass such as oats, corn, wheat, and sawdust, and an amine compound manufactured from biomass such as furfural and a curing agent composition containing the same may be environmentally friendly through reduction of carbon emissions.

The reaction molar ratio of the polyalkylene amine and the substituted or unsubstituted heteroaryl aldehyde may be 1:1 to 1:2.5. Specifically, the reaction molar ratio may be 1:1.2 to 1:2.4, 1:1.5 to 1:2.4, or 1:8 to 1:2.2. Preferably, the reaction molar ratio may be 1:1.2 to 1:2.4. When the reaction molar ratio is less than 1:1, the active hydrogen equivalent of the amine compound appears to be less than 40, and the curing agent composition containing the same may exhibit skin irritation. When the reaction molar ratio exceeds 1:2.5, the viscosity of the curing agent composition containing the amine compound may increase, thereby reducing workability in a solvent-free form.

The reactant may further comprise one or more substituted or unsubstituted aryl aldehydes. It will be appreciated that the reactant may comprise one or more polyalkyleneamines, one or more substituted or unsubstituted heteroaryl aldehydes, and one or more substituted or unsubstituted aryl aldehydes, wherein at least a portion of the polyalkyleneamines is modified with substituted or unsubstituted heteroaryls.

In the above substituted or unsubstituted aryl aldehyde, the aryl may be C ₆ -C ₁₄ aryl, and may include a single or fused ring system. In addition, a structure in which one or more aryls are bonded through a chemical bond may also be included. Non-limiting examples of the aryl may include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, etc. Preferably, the aryl may be C ₆ -C ₁₀ aryl.

When the above reactant includes both the substituted or unsubstituted heteroaryl aldehyde and the substituted or unsubstituted aryl aldehyde, the molar ratio of the substituted or unsubstituted heteroaryl aldehyde may be greater than the molar ratio of the substituted or unsubstituted aryl aldehyde. Preferably, the molar ratio of the substituted or unsubstituted heteroaryl aldehyde and the substituted or unsubstituted aryl aldehyde may be 100:0 to 51:49. Specifically, the molar ratio may be 90:10, 80:20, 70:30, or 60:40. Preferably, the molar ratio may be 100:0 to 80:20. An amine compound satisfying the above ratio may exhibit skin irritation with a P.I.I. of less than 5, and an amine compound modified only with heteroaryl may exhibit low skin irritation with a P.I.I. of less than 4.

Another embodiment of the present invention relates to a curing agent composition comprising the above-described amine compound. Specifically, the curing agent composition may be a solvent-free type comprising an amine compound having a structure represented by the above-described chemical formula 1 and a curing accelerator.

The above curing accelerator may be a tertiary amine. Non-limiting examples of tertiary amine curing accelerators include triethanolamine, diethylaminopropylamine, benzyldimethylamine, N,N'-dimethylpiperazine, N-methylpyrrolidine, N-methylhydroxypiperidine, N,N,N'N'-tetramethyldiaminoethane, N,N,N',N',N'-pentamethyldiethylenetriamine, tributylamine, trimethylamine, diethyldecylamine, triethylenediamine, N-methylmorpholine, N,N,N',N'-tetramethylpropane diamine, N-methyl piperidine, N,N'-dimethyl-1,3-(4-piperidino)propane, pyridine, 1,8-diazobicyclo[5.4.0]undec-7-ene, 1,8-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, These include 4-(N-pyrrolidino)pyridine, triethylamine, and 2,4,6-tris(dimethylaminomethyl)phenol.

The curing agent composition of the present invention can exhibit low viscosity characteristics of 500 cps or less at 25°C even without a diluent such as benzyl alcohol. Preferably, the reactants may include two or more polyalkylene amines and heteroaryl aldehydes, and the curing agent composition including the reaction product, an amine compound, can exhibit low viscosity characteristics of 300 cps or less at 25°C. The curing agent composition satisfying the above low viscosity characteristics can be used in an environmentally friendly coating composition with a low solvent content.

The above curing agent composition may include 100 to 90 parts by weight of an amine compound having a structure of the above chemical formula 1 and 0 to 10 parts by weight of a curing accelerator. A curing agent composition satisfying the above-described content range may exhibit compatibility with an epoxy resin and low viscosity characteristics, and may have excellent workability and curing properties.

Another embodiment of the present invention relates to a coating composition comprising the above-described amine compound and epoxy resin, and to an article manufactured using the coating composition. For example, the article may comprise the above-described curing agent composition and the above-described coating composition.

The epoxy resin may comprise one or more polyfunctional epoxy resins. The polyfunctional epoxy resins may comprise two or more epoxy groups per molecule and may comprise a glycidyl ether of a polyhydric phenol, including a glycidyl ether of a dihydric phenol. Non-limiting examples of multifunctional epoxy resins include glycidyl ethers such as resorcinol, hydroquinone, bis-(4-hydroxy-3,5-difluorophenyl)-methane, 1,1-bis-(4-hydroxyphenyl)-ethane, 2,2-bis-(4-hydroxy-3-methylphenyl)-propane, 2,2-bis-(4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis-(4-hydroxyphenyl)-propane (commercially known as bisphenol A), bis-(4-hydroxyphenyl)-methane (commercially known as bisphenol F and which may include variable amounts of the 2-hydroxyphenyl isomer).

The coating composition may further comprise various additives depending on the manufacturing or end use of the article. The additives may include, for example, a solvent (including water), an accelerator, a plasticizer, a filler, fibers such as glass or carbon fibers, a pigment, a pigment dispersant, a rheology modifier, a thixotrope, a flow or smoothing aid, a surfactant, an antifoaming agent, a biocide, or any combination thereof.

The above coating composition can be applied to painting or coating large metal objects or cement substrates, including ships, bridges, industrial plants and equipment, and flooring. The coating composition can be applied by a number of techniques, including spraying, brushing, rollers, and paint mitts.

Non-limiting examples of the above articles may include coatings, adhesives, architectural products, flooring products, or composite products. The coatings may include various types and concentrations of pigments used in the paint and primer industries. The coating composition may form a layer having a thickness ranging from 10 to 500 μm for use as a protective coating applied to a substrate. Non-limiting examples of the substrates may include concrete and various types of metals and alloys. For use in flooring products or architectural products, the coating composition may form a layer having a thickness ranging from 50 to 10,000 μm depending on the type of product and the desired final properties. Coating products that deliver limited mechanical and chemical resistance may include a layer having a thickness ranging from 50 to 500 μm, whereas coating products that deliver high mechanical and chemical resistance, such as smooth flooring, may include a layer having a thickness ranging from 1,000 to 10,000 μm.

When applying the coating composition to architectural or flooring products, the coating composition of the present invention can be used with concrete or other materials commonly used in the construction industry. Non-limiting examples of applications of the coating composition include its use as a primer, a deep penetrating primer, a coating, a curing agent, and/or a sealant for new or old concrete. As a primer or sealant, the coating composition of the present invention can be applied to a surface to improve adhesive bonding prior to coating application. In the concrete and cement field, a coating is a formulation used for application on a surface to create a protective or decorative layer or coating. Crack injection and crack filling products can also be prepared from the compositions disclosed herein. The coating composition of the present invention can be mixed with cementitious materials, such as concrete mixtures, to form polymer or modified cements, tile grouts, and the like. Non-limiting examples of articles or composite products comprising the coating compositions disclosed herein include tennis rackets, skis, bicycle frames, airplane wings, glass fiber reinforced composites, and other molded articles.

Hereinafter, the present invention will be described in more detail through specific examples and experimental examples. The following examples and experimental examples are intended to illustrate the present invention, and the present invention is not limited by the following examples and experimental examples.

Example 1

At room temperature (25°C), 3 g of Pd catalyst, 31 g (0.30 mol) of DETA, 16 g (0.10 mol) of TETA, and 87 g (0.50 mol) of N4 were placed in an autoclave batch reactor equipped with a stirrer and mixed for 30 minutes. Then, 173 g (1.80 mol) of furfural was added over approximately 30 minutes, stirred at 100°C for 30 minutes, and then heated to 120°C. After reaching 120°C, hydrogen gas was supplied to maintain a pressure in the range of 50 to 60 bar, and the hydrogen gas consumption was checked. The reaction was terminated when the hydrogen gas consumption per hour was less than 1 bar. After the reaction was completed, the reactor was cooled to 60°C, hydrogen gas was removed, and the Pd catalyst was removed using a filter. The residue was completely dehydrated at 120°C and 20 torr to obtain a synthetic product.

Example 2

A synthetic product was obtained in the same manner as in Example 1, except that 105 g (1.10 mol) of furfural was added to 31 g (0.30 mol) of DETA, 16 g (0.10 mol) of TETA, and 87 g (0.50 mol) of N4.

Example 3

A synthetic product was obtained in the same manner as in Example 1, except that 210 g (2.19 mol) of furfural was added to 31 g (0.30 mol) of DETA, 16 g (0.10 mol) of TETA, and 87 g (0.50 mol) of N4.

Example 4

A synthetic product was obtained in the same manner as in Example 1, except that 174 g (1.81 mol) of furfural was added to 34.4 g (0.33 mol) of DETA, 11.2 g (0.08 mol) of TETA, and 87 g (0.50 mol) of N4.

Example 5

A synthetic product was obtained in the same manner as in Example 1, except that 174 g (1.81 mol) of furfural was added to 46.4 g (0.45 mol) of DETA, 14 g (0.10 mol) of TETA, and 61 g (0.35 mol) of N4.

Example 6

A synthetic product was obtained in the same manner as in Example 1, except that 227 g (1.80 mol) of hydroxymethylfurfural (HMF) was added to 31 g (0.30 mol) of DETA, 16 g (0.10 mol) of TETA, and 87 g (0.50 mol) of N4.

Example 7

A synthetic product was obtained in the same manner as in Example 1, except that 113.5 g (0.90 mol) of hydroxymethyl furfural and 86.5 g (0.90 mol) of furfural were added to 31 g (0.30 mol) of DETA, 16 g (0.10 mol) of TETA, and 87 g (0.50 mol) of N4.

Example 8

A synthetic product was obtained in the same manner as in Example 1, except that 20 g (0.19 mol) of benzaldehyde and 156 g (1.62 mol) of furfural were added to 31 g (0.30 mol) of DETA, 16 g (0.10 mol) of TETA and 87 g (0.50 mol) of N4.

Comparative Example 1

A synthetic product was obtained in the same manner as in Example 1, except that 191 g (1.80 mol) of benzaldehyde was added to 31 g (0.30 mol) of DETA, 16 g (0.10 mol) of TETA, and 87 g (0.50 mol) of N4.

Comparative Example 2

A synthetic product was obtained in the same manner as in Example 1, except that 86.5 g (0.90 mol) of furfural was added to 31 g (0.30 mol) of DETA, 16 g (0.10 mol) of TETA, and 87 g (0.50 mol) of N4.

Comparative Example 3

A synthetic product was obtained in the same manner as in Example 1, except that 227 g (2.36 mol) of furfural was added to 31 g (0.30 mol) of DETA, 16 g (0.10 mol) of TETA, and 87 g (0.50 mol) of N4.

Reference Example 1

A synthetic product was obtained in the same manner as in Example 1, except that 95.5 g (0.90 mol) of benzaldehyde and 86.5 g (0.90 mol) of furfural were added to 31 g (0.30 mol) of DETA, 16 g (0.10 mol) of TETA and 87 g (0.50 mol) of N4.

Reference Example 2

A synthetic product was obtained in the same manner as in Example 1, except that 110 g (0.90 mol) of salicylaldehyde and 86.5 g (0.90 mol) of furfural were added to 31 g (0.30 mol) of DETA, 16 g (0.10 mol) of TETA, and 87 g (0.50 mol) of N4.

Experimental Example 1. Confirmation of the physical properties of synthetic products in examples and comparative examples

The composition of the reactants used in the examples and comparative examples and the properties of the obtained synthetic products, such as active hydrogen equivalent (A.H.E.W.) and viscosity, were confirmed and are shown in Tables 1 and 2 below.

Active hydrogen equivalent

The active hydrogen equivalent was calculated according to the following equation 1.

[Formula 1]

Active hydrogen equivalent (A.H.E.W) = molecular weight / number of active hydrogens

viscosity

Viscosity was measured using a Brookfield viscometer at a temperature of 25℃, with the pointed end of the spindle immersed in the thermosel containing the sample, and a torque of 30% or more.

Example
1 Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 Example
8 Furfural 1.80 mol 1.10 mol 2.19 mol 1.81 mol 1.81 mol - 0.90 mol 1.62 mol HydroxyMethyl
Furfural - - - - - 1.80 mol 0.90 mol - Benzaldehyde - - - - - - - 0.19 Salicylaldehyde - - - - - - - - DETA 0.30 mol 0.30 mol 0.30 mol 0.33 mol 0.45 mol 0.30 mol 0.30 mol 0.30 mol TETA 0.10 mol 0.10 mol 0.10 mol 0.08 mol 0.10 mol 0.10 mol 0.10 mol 0.10 mol N4 0.50 mol 0.50 mol 0.50 mol 0.50 mol 0.35 mol 0.50 mol 0.50 mol 0.50 mol A.H.E.W. 82.3 45.4 106.7 82.7 82.8 97.8 89.7 82.9 viscosity
(@25℃) 170 cps 80 cps 260 cps 110 cps 90 cps 240 cps 200 cps 158 cps

Comparative example
1 Comparative example
2 Comparative example
3 Reference Example 1 Reference Example 2 Furfural - 0.90 mol 2.36 mol 0.90 mol 0.90 mol HydroxyMethyl
Furfural - - - - - Benzaldehyde 1.80 mol - - 0.90 mol - Salicylaldehyde - - - - 0.90 mol DETA 0.30 mol 0.30 mol 0.30 mol 0.30 mol 0.30 mol TETA 0.10 mol 0.10 mol 0.10 mol 0.10 mol 0.10 mol N4 0.50 mol 0.50 mol 0.50 mol 0.50 mol 0.50 mol A.H.E.W. 87 36.3 120.3 84.4 88.7 viscosity
(@25℃) 90 cps 73 cps 290 cps 135 cps 190 cps

Experimental Example 2. Confirmation of ASTM D 5946 contact angle of synthetic products of Example 1 and Comparative Example 1

The contact angles of the synthetic products obtained in Example 1 and Comparative Example 1 were determined according to ASTM D 5946. Specifically, a droplet of each synthetic product was dropped onto a solid surface, and the angle formed between the stationary droplet and the surface was measured. A smaller contact angle indicates greater hydrophilicity and superior adhesiveness.

3 μL of the synthetic products of Example 1 and Comparative Example 1 were dropped onto the surface of a glass substrate using a quantitative dispenser, and the change in contact angle was measured after 1 second. The contact angle was measured by measuring the angle from the length and height of a triangle formed by the height at which the height of the droplet is the highest with respect to the substrate and the length of the substrate when a perpendicular is lowered from the highest point, and the change in contact angle over time was measured up to 35 seconds, and this is shown in Fig. 1.

Referring to Fig. 1, it was confirmed that the sample of Example 1 had higher hydrophilicity than the sample of Comparative Example 1 over time, except immediately after the droplet was ejected. This result is consistent with the expectation that the hydrophilicity of the compound terminal would be improved as the sample of Example 1 included an amine compound modified with a heteroaryl group, compared to the sample of Comparative Example 1, which included an amine compound modified with only an aryl group.

Experimental Example 3. TG 404 Test of Synthetic Products of Examples and Comparative Examples

A skin irritation evaluation test according to OECD guideline TG 404 was performed on the synthetic products obtained in Examples 1, 6, 8 and Comparative Examples 1 to 4.

Specifically, the fur of rabbits (New Zealand White Rabbit, average weight 2.22 kg) was shaved, and one area measuring approximately 2.5 cm × 2.5 cm was designated as the administration area, with the midline of the dorsum of the shaved rabbit as the symmetrical axis. One area was designated as the untreated control area, and the other area was designated as the test substance administration area.

The synthetic products of the examples and comparative examples were used as test substance stock solutions, and 0.5 mL each was evenly applied to each 2.5 x 2.5 cm patch and applied to the test substance administration site, and only the patch was applied to the untreated control site. The irritation and corrosion test was divided into Initial and Confirmatory tests. In the Initial Test, three patches were applied sequentially, the first patch was removed 3 minutes after administration, the second patch was removed 1 hour after administration, and the third patch was removed 4 hours after administration. Since no severe irritation or corrosion was observed after each patch removal, the Confirmatory test was performed using a separate animal by applying one patch for 4 hours each. The skin reaction was evaluated at 1, 24, 48, and 72 hours after patch removal, and the Primary Skin Irritation Index (P.I.I.) was calculated to classify the degree of skin irritation of the test substance. After application to each part, the evaluation was performed according to Table 3 below, and the average score was summarized in Table 4. Using the scores, the P.I.I. index was calculated according to Equation 2 below, and summarized in Table 4.

Erythema and erythema formation (hereinafter referred to as "erythema") No erythema at all 0 Very mild erythema (barely visible to the naked eye) 1 Distinct erythema 2 Slightly severe erythema 3 Severe erythema (severe redness) and crusting 4 Edema formation (hereinafter referred to as "edema") No swelling at all 0 Very mild swelling (barely visible to the naked eye) 1 Mild edema (swelling so pronounced that the margins are clearly distinguishable) 2 Severe edema (swelling of about 1 mm) 3 Severe edema (swelling greater than 1 mm and extending beyond the exposed area) 4

[Formula 2]

P.I.I = (erythema score of all animals + edema score) / (number of animals × 4)

Sample 1 hour passed 24 hours have passed 48 hours have passed 72 hours have passed P.I.I erythema edema erythema edema erythema edema erythema edema Comparative Example 1 2 2 3 4 3 4 3 4 6.25 Comparative Example 2 2 2 2 2 2 2 3 2 4.25 Comparative Example 3 2 2 2 2 2 2 2 2 4.0 Reference Example 1 2 0 3 2 3 3 3 3 4.75 Reference Example 2 2 0 3 2 3 3 3 2 4.5 Example 1 2 0 2 2 2 2 2 0 3.00 Example 6 2 0 3 2 2 2 2 0 3.25 Example 8 2 2 2 2 2 2 2 1 3.75

Claims (13)

An amine compound having a structure represented by the following chemical formula 1 and having an active hydrogen equivalent weight (AHEW) of 44 to 120.
[Chemical Formula 1]

Among the foods,
R ₁ , R ₂ and R ₃ are each independently a C ₂ -C ₁₀ alkyl group or a C ₂ -C ₁₀ alkylene group,
A and B are each independently a substituted or unsubstituted C ₆ -C ₁₄ aryl group, or a substituted or unsubstituted C ₃ -C ₁₄ heteroaryl group, wherein at least one of A and B is a substituted or unsubstituted C ₃ -C ₁₄ heteroaryl group,
X ₁ , X ₂ , X ₃ and X ₄ are each independently A, B or a hydrogen atom,
n is 0, 1, 2, 3, 4, 5, 6, or 7. In the first paragraph,
An amine compound, wherein the above amine compound is a reaction product of a reactant comprising at least one polyalkylene amine and at least one substituted or unsubstituted heteroaryl aldehyde. In the second paragraph,
The above polyalkylene amine is an amine compound which is a multifunctional amine having three or more active amine hydrogens. In the third paragraph,
The above polyalkylene amine is at least one selected from the group consisting of diethylenetriamine, triethylenetetramine, N-3-aminopropyl ethylenediamine, N,N'-bis(3-aminopropyl)ethylenediamine, N,N-bis(3-aminopropyl) ethylenediamine, N,N,N'-tris(3-aminopropyl) ethylenediamine, N,N,N',N'-tetrakis(3-aminopropyl) ethylenediamine, N-3-aminopropyl-1,3-propanediamine, N,N'-bis(3-aminopropyl)-1,3-propanediamine, N,N-bis(3-aminopropyl)-1,3-propanediamine, N,N,N'-tris(3-aminopropyl)-1,3-propanediamine, and N,N,N',N'-tetrakis(3-aminopropyl)-1,3-propanediamine. In the second paragraph,
An amine compound in which the molar ratio of the polyalkylene amine and the substituted or unsubstituted heteroaryl aldehyde is 1:1 to 1:2.5. In the second paragraph,
An amine compound, wherein the reactant further comprises one or more substituted or unsubstituted aryl aldehydes. In Article 6,
An amine compound, wherein the molar ratio of the substituted or unsubstituted heteroaryl aldehyde is greater than the molar ratio of the substituted or unsubstituted aryl aldehyde. In paragraph 7,
An amine compound wherein the molar ratio of the substituted or unsubstituted heteroaryl aldehyde and the substituted or unsubstituted aryl aldehyde is 100:0 to 51:49. In the first paragraph,
An amine compound, wherein the heteroaryl comprises at least one selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, and selenium. In the first paragraph,
If the above A or B has a substituent,
The above substituent is at least one selected from the group consisting of CH ₂ OH, CH ₂ Y, CHOR ₄ , R ₄ , CHO and COOH,
The above Y is a halogen atom,
An amine compound wherein the above R ₄ is a C ₁ -C ₁₀ alkyl group. A curing agent composition comprising an amine compound according to claim 1. In Article 11,
The above reactant contains two or more kinds of polyalkylene amines,
A curing agent composition having a viscosity of 500 cps or less at 25°C. A coating composition comprising an amine compound according to claim 1 and an epoxy resin.