KR20160043195A - Organic Phosphorus Flame-Resistant Curing Agents And Methods thereof - Google Patents

Abstract

The present invention relates to an organic phosphorus-based flame-resistant curing agent and a method for preparing the same. The present invention relates to an organic phosphorus-based flame-resistant curing agent provided with flame resistance through phosphorus (P) by making a compound containing phosphorus react with an amine compound used as a conventional curing agent for epoxy or urethane, and a method for preparing the same. More particularly, the present invention relates to an organic phosphorus-based flame-resistant curing agent obtained by making i) a reaction product of an amine compound with formalin or formaldehyde react with ii) a phosphorus-based compound, or making i) an amine compound react with ii) a hydroxy group-containing phosphorus-based compound, or making i) a mixture of an amine compound with a phosphorus-based compound react with ii) a ketone compound, or making i) a reaction product of an amine compound with a ketone compound react with ii) a phosphorus-based compound; and a method for preparing the organic phosphorus-based flame resistant curing agent. According to the present invention, a flame resistant is not added to epoxy but a curing agent is directly imparted with flame resistance, thereby making it possible to obtain a flame resistant curing agent capable of providing flame resistance without degradation of epoxy properties. In addition, it is possible to obtain an eco-friendly curing agent capable of curing even at room temperature upon the reaction with epoxy and having excellent flame resistance without emission of harmful gases in fire accidents.

Description

[0001] Organophosphorus flame retardant curing agents and methods for their preparation [

The present invention relates to an organophosphorus flame retardant curing agent and a process for producing the same. More specifically, the present invention relates to an organophosphorus flame retardant curing agent and a method for producing the phosphorus (P) Based flame-retardant curing agent and a method for producing the same.

The epoxy resin is a generic term of a thermosetting resin having an epoxy group in a molecule and is excellent in heat resistance, electrical insulation, adhesiveness and the like. They are rarely used alone, and they are often used in combination with a filler such as silica and titanium oxide, a reinforcing agent or the like because of its good fusion strength with an inorganic material. Epoxy resins are widely used because their properties vary greatly depending on the difference between these curing agents, fillers and reinforcing agents. Currently, the most popular form is a condensate obtained by reacting bisphenol A (2,2-bis (4'-oxyphenol) propane) and epichlorohydrin (ECH) in the presence of sodium hydroxide. It is called the first resin (prepolymer) with a molecular weight of 300 ~ 4000, which accounts for about 90% of total demand.

Depending on the blending conditions of the raw materials, the first resin can be obtained in an oil-like form and a solid form having a softening point close to 160 ° C, so the reaction conditions are selected depending on the application. When an acid such as an amine such as m-phenylenediamine or an anhydride such as phthalic anhydride is added to the first resin, the ring opening of the epoxy group and the reaction with the hydroxy group occur to form a bridge bond, Depending on the reaction conditions, resins of different properties are produced. The epoxy resin is excellent in mechanical properties such as bending strength and hardness. There is no generation of volatile substances and shrinkage of volume at the time of curing, and a large adhesive force is given to the material surface when curing. Flammability and chemical resistance are high, but are slightly eroded by strong acid and strong base. The pigment can be colored at will by adding pigments, and the tomorrow's light is also great. The maximum operating temperature of the product is as low as 80 ℃. It shows excellent workability such as mold, burying and filling. Therefore, epoxy resins are used in a wide range of applications such as paints, insulating materials for electric and electronic devices, adhesives, mold materials, and stabilizers for vinyl chloride resins.

For example, in general, underground floors of public buildings, underground floors of apartments, floors of large discount marts, floors of public buildings, floor of factories are made of epoxy. However, since the epoxy flooring is made of an organic compound, it can cause toxic gas generation when a fire occurs. Especially, when a fire occurs on the floor of a factory, it can be very large. Secondary damage can occur if a fire occurs in an apartment or a public building. Nevertheless, in the case of architectural flooring, it is a reality that the flame retardant treatment is not generally performed, or only the inorganic flame retardant or the brominated flame retardant is mixed.

In case of the inorganic flame retardant, an excess amount should be used in order to exhibit flame retardancy. However, in this case, there is a problem in reduction of the epoxy property and moldability. In addition, in the case of a brominated flame retardant, a substitution of a halogen-free flame retardant agent is required because it causes damage to the human body due to environmental pollution and toxic gas generation due to the generation of dioxin in the event of a fire. In particular, development of a phosphorus flame retardant that does not release harmful gases to the human body is required.

In this connection, Korean Patent Application Laid-Open Publication No. 2013-0106909 A discloses an amino group-containing phosphoric acid ester flame retardant and a method for producing the flame retardant, and the flame retardant of the above document is an addition type structure. The flame retardant is a curing agent capable of reacting directly with an epoxy resin, It has the disadvantage of reducing the physical properties of the epoxy when mixed with the epoxy.

Thus, the present inventors have found that a curing agent which imparts direct flame retardancy to a curing agent, which is not a flame retardant addition type, is manufactured and compared with an epoxy curing method which is used in the conventional inorganic addition or halogen flame retardant addition method, The present inventors have completed the present invention based on the results of repeated experiments to exhibit a flame retardant effect in an environmentally friendly manner, and the curing agent according to the present invention can also be used in an epoxy or epoxy composite material.

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art as described above, and it is an object of the present invention to provide an organophosphorous modified amine instead of an inorganic additive type flame retardant to thereby exhibit an effect of curing at room temperature upon reaction with an epoxy or epoxy composite material, And an object of the present invention is to provide a method for producing the flame retardant.

In order to achieve the above object, the present invention provides an organophosphorus flame retardant curing agent produced by the reaction of i) a reaction product obtained by reacting an amine compound with formalin or formaldehyde, and ii) a phosphorus compound.

The present invention also provides an organophosphorus flame retardant curing agent produced by reacting i) an amine compound and ii) a phosphorus compound containing a hydroxy group.

The present invention also relates to a process for the preparation of a compound of formula (I), which comprises: i) mixing an amine compound with a phosphorus compound, and ii) reacting with a ketone compound; Or an organic phosphorus-based flame-retardant curing agent prepared by reacting a reaction product obtained by i) reacting an amine-based compound with a ketone-based compound and ii) a phosphorus compound.

In one embodiment of the present invention, the organophosphorus flame retardant curing agent according to the present invention can be represented by the following general formula (1).

An organophosphorus flame retardant curing agent represented by the following formula (1)

[Chemical Formula 1]

(Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms;

R ₃ is an alkylamine group having 1 to 10 carbon atoms or an arylamine group having 6 to 10 carbon atoms, R ₃ contains 2 to 10 amines and at least one of the 2 to 10 amines To three amines are located at the ends;

R ₄ and R ₅ are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms;

n ranges from more than 0 to less than 3).

In one embodiment of the present invention, the amine compound is selected from the group consisting of ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine TEPA), diprophenediamine (DPDA), diethylaminopropylamine (DEPA), hexamethylenediamine (HMDA), m-xylenediamine (MXDA), N-aminoethylpiperazine N-aminoethylpiperazine (AEPA), Lamiron C-260, Araldite HY-964, methanediamine, isophoronediamine (IPDA), sho be selected from -amine, m- phenylenediamine (m-phenylenediamine), diaminodiphenyl methane (diaminodiphenylmethane), diaminodiphenyl sulfone group consisting of (diaminodiphenylsulfone), and JEFFAMINE ^® D-230 polyether amine (polyetheramine) There.

In one embodiment of the present invention, the phosphorus compound may be selected from the group consisting of dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite, and diphenyl phosphite.

In one embodiment of the present invention, the phosphorus-containing compound having a hydroxy group is selected from the group consisting of hydroxymethyldiethylphosphonate, hydroxymethyldimethylphosphonate, hydroxymethyldiisopropylphosphate, Hydroxymethyldibutylphosphonate, hydroxymethyldiphenylphosphonate, hydroxymethyldibutylphosphonate, and hydroxymethyldiphenylphosphonate. The hydroxymethyldibutylphosphonate may be selected from the group consisting of hydroxymethyldisopropylphosphonate, hydroxymethyldibutylphosphonate, and hydroxymethyldiphenylphosphonate.

In one embodiment of the present invention, the ketone-based compound may be acetone.

The present invention also relates to a process for the production of a compound of formula (I), comprising the steps of: i) reacting an amine compound with formalin or formaldehyde; And ii) removing water produced after the reaction and mixing the phosphorus compound and reacting the phosphorus compound to produce an organophosphorus flame retardant curing agent.

In one embodiment of the present invention, the formalin or formaldehyde of step (i) may be mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound.

In one embodiment of the present invention, the phosphorus compound in step ii) may be mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound.

The present invention also provides a method for producing an organophosphorus flame retardant curing agent comprising the step of mixing and reacting an amine compound with a phosphorus compound containing a hydroxy group.

The present invention also relates to a process for preparing a phosphorus-containing compound, comprising the steps of: i) mixing an amine compound and a phosphorus compound; And ii) reacting the mixture with a ketone-based compound to produce an organic phosphorus-based flame-retardant curing agent.

The present invention also relates to a process for the production of i) a process comprising the steps of: i) reacting an amine compound with a ketone compound; And ii) reacting the reaction product with a phosphorus compound to produce an organophosphorus flame retardant curing agent.

In one embodiment of the present invention, the phosphorus compound may be mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound.

In one embodiment of the present invention, the ketone compound may be mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound.

In addition, the present invention provides a coating composition comprising an organophosphorus flame retardant curing agent according to the present invention.

The present invention provides an organophosphorus flame retardant curing agent and a method for producing the same, wherein the organophosphorus flame retardant curing agent according to the present invention comprises a) a reaction product obtained by i) reacting an amine compound with formalin or formaldehyde, and ii) ≪ / RTI > Or b) by reacting i) an amine compound and ii) a phosphorus compound comprising a hydroxy group; Or c) a reaction product obtained by mixing i) an amine compound and a phosphorus compound, ii) reacting the compound with a ketone compound, or ii) reacting the reaction product obtained by reacting an amine compound with a ketone compound, and ii) .

Therefore, the organophosphorus flame retardant curing agent obtained by this method has a form in which phosphorus is added to the existing amine curing agent, so that it can be used not only as a curing agent at room temperature but also with excellent flame retardancy The flame retardant effect can be obtained in an environmentally friendly manner without decreasing the physical properties or properties of the epoxy as compared with the conventional epoxy curing method using the inorganic additive or the halogen flame retardant addition method.

That is, by using the organophosphorus flame retardant curing agent of the present invention, the flame retardant is not added to the epoxy or epoxy composite material, but the flame retardancy is imparted directly to the curing agent. When the epoxy or epoxy composite material is mixed with epoxy or epoxy composite It is possible to obtain excellent flame retardancy without reducing the physical properties of the material.

Further, by using the organophosphorus flame retardant curing agent of the present invention, curing can be carried out even at room temperature when reacted with epoxy, and excellent flame retardancy can be obtained, so that eco-friendly properties in which harmful gas is not discharged in the event of fire or the like can be obtained .

1 to 7 illustrate a process for producing the organic phosphorus-based flame retardant of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention relates to an organophosphorus flame retardant curing agent prepared by i) reacting a reaction product obtained by reacting an amine compound with formalin or formaldehyde and ii) reacting a phosphorus compound.

The present invention also relates to an organophosphorus flame retardant curing agent prepared by reacting i) an amine compound and ii) a phosphorus compound containing a hydroxy group.

The present invention also relates to an organophosphorus flame retardant curing agent prepared by i) mixing an amine compound and a phosphorus compound, and then ii) reacting with a ketone compound.

The present invention also relates to an organophosphorus flame retardant curing agent produced by reacting i) a reaction product obtained by reacting an amine compound with a ketone compound, and ii) a phosphorus compound.

In one embodiment of the present invention, the organophosphorus flame retardant curing agent according to the present invention can be represented by the following general formula (1).

An organophosphorus flame retardant curing agent represented by the following formula (1)

[Chemical Formula 1]

(Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms;

R ₃ is an alkylamine group having 1 to 10 carbon atoms or an arylamine group having 6 to 10 carbon atoms, R ₃ contains 2 to 10 amines and at least one of the 2 to 10 amines To three amines are located at the ends;

R ₄ and R ₅ are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms;

n ranges from more than 0 to less than 3).

Further, as a method for producing the organic phosphorus-based flame retardant curing agent according to the present invention, the following three production methods are possible without limitation, and the production method will be described in detail as follows.

a) a first process comprising the steps of: i) reacting an amine compound with formalin or formaldehyde; And ii) removing water produced after the reaction and mixing the phosphorus compound and reacting the phosphorus compound to produce an organic phosphorus-based flame-retardant curing agent.

b) As a second production method, there is a method for producing an organophosphorus flame retardant curing agent comprising a step of mixing and reacting an amine compound with a phosphorus compound containing a hydroxy group.

c) a third process comprising: i) mixing an amine compound and a phosphorus compound; And ii) reacting the mixture with a ketone-based compound. The third method comprises: i) reacting an amine-based compound with a ketone-based compound; And ii) reacting the reaction product with a phosphorus compound to produce an organophosphorus flame retardant curing agent.

As an embodiment of the method a), it is possible to produce an organophosphorus flame retardant curing agent by reacting formaldehyde first with ethylenediamine, removing the produced water, and then adding diethylphosphite.

As an embodiment of the method b), a method of producing an organophosphorus flame retardant curing agent by reacting hydroxymethyldiethylphosphonate with ethylenediamine is possible.

As an embodiment of the c) method, it is possible to produce an organophosphorus flame retardant curing agent by mixing N-aminoethylpiperazine and diethylphosphite and then reacting with acetone.

All the above methods a) to c) are methods for preparing the same target compound. The present invention is characterized in that an amine-based compound such as ethylenediamine is reacted with a phosphorus-based compound to produce an organophosphorus-modified amine compound.

In one embodiment of the present invention, in the method a), the formalin or formaldehyde may be mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound, and the phosphorus compound may be mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound .

In one embodiment of the present invention, in the method c), the ketone compound may be mixed at 0.5 to 3 equivalents per equivalent of the amine compound, and the phosphorus compound may be mixed at 0.5 to 3 equivalents per equivalent of the amine compound .

In the above a) or c) method, phosphorus compounds include alkyl phosphites such as dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite, or aromatic phosphites such as diphenyl phosphite and the like But is not limited thereto.

In the a) or c) method, examples of the amine compound include ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine TEPA), diprophenediamine (DPDA), N-aminoethylpiperazine (AEP), isophorone diamine (IPDA), hexamethylenediamine (HMDA), m-xylenediamine -xylenediamine, MXDA), Lamiron C-260, Araldite HY-964, methanediamine, sho-amine, m-phenylenediamine ), diaminodiphenyl methane (diaminodiphenylmethane, DDM), diaminodiphenyl sulfone (diaminodiphenylsulfone, DDS) and JEFFAMINE D-230 ^® polyether amines (but the number of the amine to be used, such as polyetheramine), but is not limited thereto.

As the ketone compound, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopropyl methyl ketone, and the like may be used in the above c) It is not.

In the method b), the phosphorus compound may be mixed with 0.5 to 3 equivalents per equivalent of the amine compound.

In the above method b), as the phosphorus compound, hydroxymethyldiethylphosphonate, hydroxymethyldimethylphosphonate, hydroxymethyldiisopropylphosphonate, hydroxymethyldiisopropylphosphonate, But are not limited to, hydroxymethyldibutylphosphonate or hydroxymethyldiphenylphosphonate. The term " hydroxymethyldibutylphosphonate "

In the method b), as the amine compound, ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine (TEPA) Such as diprophenediamine (DPDA), N-aminoethylpiperazine (AEP), isophorone diamine (IPDA), hexamethylenediamine (HMDA), m-xylenediamine ), Lamiron C-260, araldite HY-964, methanediamine, sho-amine, m-phenylenediamine, diamino diphenylmethane (diaminodiphenylmethane, DDM), diaminodiphenyl sulfone (diaminodiphenylsulfone, DDS) and JEFFAMINE ^® D-230 polyether amine, but can be used include polymeric amine, such as (polyetheramine), but is not limited thereto.

In the methods a) to c), although the equivalence ratio is not limited to the disclosed values, it is difficult to use because the viscosity increases when the equivalent ratio exceeds 3.

The methods a) to c) can be carried out at -10 to 80 ° C, but preferably at -10 ° C to 30 ° C. However, if there is no problem in color and viscosity depending on the application, it can be produced at a reaction temperature of 0 to 80 ° C.

The following reaction formula illustrates the production process of the organophosphorus flame retardant curing agent of the present invention, and the following production method does not limit the method for producing the organophosphorus flame retardant curing agent according to the present invention.

Scheme a)

Scheme b)

Scheme c)

Further, a coating composition containing the organophosphorus-based flame retardant according to the present invention can be produced. Additives used in paints include, but are not limited to, wetting and dispersing agents, preservatives, defoamers, film formers, pH adjusting agents, thickeners, plasticizers, drying promoters and the like. In addition, additives used in the art can be used in the present invention. The type and amount of use thereof are different from each other, so that the kind and amount thereof are not limited.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.

Example

[Example 1] Production of curing agent 1

Add 5.5 kg of DETA (diethylenetriamine) to a 20 L reactor and add 4.6 kg of 35% formalin while keeping it below 20 ° C. After completion of the reaction, the produced water is removed under vacuum while maintaining the internal temperature of the reactor at 40 to 60 ° C. Thereafter, 7.36 kg of diethylphosphite is added to the reaction solution while maintaining the internal temperature of the reactor at 30 占 폚 or lower. Temperature is controlled by using an ice bath because heat is generated at this time. After the addition, the mixture is aged for about 1 hour and then concentrated under reduced pressure to remove a trace amount of water. The final product, 12.9 kg, was obtained with a yield of 95%.

[Example 2] Production of curing agent 2

In a 500-mL reactor, add 140 g of EDA (ethylenediamine) and add 200 g of 35% formalin while keeping the temperature below 20 ° C. After completion of the reaction, the produced water is removed under vacuum while maintaining the internal temperature of the reactor at 40 to 60 ° C. Thereafter, 322 g of diethylphosphite is added to the reaction solution while maintaining the internal temperature of the reactor at 30 占 폚 or lower. At this time, the temperature is controlled by using an ice bath because heat is generated. After the addition, the mixture is aged for about 1 hour and then concentrated under reduced pressure to remove a trace amount of water. The final product was 475 g, 97% yield.

[Example 3] Production of curing agent 3

Add 100 g of MXDA (m-xylenediamine) to a 500 mL reactor and add 63 g of 35% formalin while keeping the temperature below 20 ° C. After completion of the reaction, the produced water is removed under vacuum while maintaining the internal temperature of the reactor at 40 to 60 ° C. Thereafter, 102 g of diethylphosphite is added to the reaction solution while maintaining the internal temperature of the reactor at 30 占 폚 or lower. At this time, the temperature is controlled by using an ice bath because heat is generated. After the addition, the mixture is aged for about 1 hour and then concentrated under reduced pressure to remove a trace amount of water. The final product, 205 g, was obtained in a yield of 95%.

[Example 4] Production of curing agent 4

In a 500 mL reactor, add 100 g of EDA and keep below 0 ° C. 364 g of hydroxymethyldiethylphosphonate (DEP-OH) is added while maintaining the temperature of the reactor using an ice bath so as not to exceed 10 캜. After completion of the addition, the reaction is completed while stirring and aging for about 1 hour.

The reaction was completed by confirming the disappearance of DEP-OH by TLC (thin layer chromatography). When the reaction is completed, the water produced by the reaction is concentrated under reduced pressure to remove it. The resulting compound was obtained in 420 g, 97% yield.

[Example 5] Production of curing agent 5

In a 500 mL reactor, add 100 g of EDA and keep below 0 ° C. 476 g of hydroxymethyl diethylphosphonate (DEP-OH) are added while maintaining the reactor temperature using an ice bath so that the temperature does not exceed 10 캜. After completion of the addition, the reaction is completed while stirring and aging for about 1 hour.

The reaction was completed by confirming the disappearance of DEP-OH via TLC. When the reaction is completed, the water produced by the reaction is concentrated under reduced pressure to remove it. The resulting compound was obtained in 520 g, 97% yield.

[Example 6] Production of curing agent 6

In a 500 mL reactor, add 100 g of DETA and keep it below 0 ° C. 212 g of hydroxymethyldiethylphosphonate (DEP-OH) are added to the reaction mixture while maintaining the reactor temperature using an ice bath so as not to exceed 10 ° C. After completion of the addition, the reaction is completed while stirring and aging for about 1 hour.

The reaction was completed by confirming the disappearance of DEP-OH via TLC. When the reaction is completed, the water produced by the reaction is concentrated under reduced pressure to remove it. The resulting compound was 284 g, 97% yield.

[Example 7] Production of curing agent 7

Add 100 g of N-aminoethylpiperazine (NAEP) to a 500 mL reactor and keep it below 0 ° C. 130 g of hydroxymethyl diethylphosphonate (DEP-OH) was added at an excess of 40 C using an ice bath while maintaining the reactor temperature. After completion of the addition, the reaction is completed while stirring and aging for about 1 hour.

The reaction was completed by confirming the disappearance of DEP-OH via TLC. When the reaction is complete, 50 g of toluene is added to remove the water generated by the reaction, and the reaction mixture is removed with an azeotropic compound under vacuum. The resulting compound was obtained in a yield of 95% at 207 g.

[Example 8] Production of curing agent 8

100 g of NAEP (N-aminoethylpiperazine) and 107 g of diethylphosphite are placed in a 500 mL reactor, and the temperature is raised to 30 to 40 ° C. Then, 50 g of acetone is added dropwise. The desired visible reaction temperature is maintained at 50 to 60 ° C or lower. When the dropwise addition is completed, the mixture is further stirred for 3 to 4 hours while maintaining the temperature at 50 to 60 ° C. After stirring, the reaction is terminated when the diethylphosphite completely disappears on the TLC. When the reaction is completed, 70 g of toluene is added to the water produced in the reaction and the mixture is azeotropically removed. The resulting compound was obtained in 231 g, 97% yield.

The present invention has been described with reference to the preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (23)

(Ii) an organophosphorus flame retardant curing agent prepared by reacting a reaction product obtained by reacting an amine compound with formalin or formaldehyde and (ii) a phosphorus compound. An organic phosphorus flame retardant curing agent produced by reacting i) an amine compound and ii) a phosphorus compound containing a hydroxy group. (Ii) an organic phosphorus-based flame-retardant curing agent prepared by mixing an amine compound and a phosphorus compound, and (ii) reacting the phosphorus compound with a ketone-based compound. An organophosphorus flame retardant curing agent produced by reacting i) a reaction product obtained by reacting an amine compound with a ketone compound, and ii) a phosphorus compound. An organophosphorus flame retardant curing agent represented by the following formula (1)
[Chemical Formula 1]

(Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms;
R ₃ is an alkylamine group having 1 to 10 carbon atoms or an arylamine group having 6 to 10 carbon atoms, R ₃ contains 2 to 10 amines and at least one of the 2 to 10 amines To three amines are located at the ends;
R ₄ and R ₅ are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms;
n ranges from more than 0 to less than 3). 5. The method according to any one of claims 1 to 4,
The amine compound may be selected from the group consisting of ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine (TEPA), diprophenediamine , DPDA), N-aminoethylpiperazine (AEP), isophorone diamine (IPDA), hexamethylenediamine (HMDA), m-xylenediamine (MXDA), lamellone C (HY-964), methanediamine, sho-amine, m-phenylenediamine, diaminodiphenylmethane , DDM), diaminodiphenyl sulfone (diaminodiphenylsulfone, DDS) and JEFFAMINE ^® D-230 polyether amine (an organic phosphorus flame retardant curing agent, characterized in that the polyetheramine) selected from the group consisting of. The method of claim 1, 3, or 4,
Wherein said phosphorus compound is selected from the group consisting of dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite, and diphenyl phosphite. 3. The method of claim 2,
The phosphorus compound may be at least one selected from the group consisting of hydroxymethyldiethylphosphonate, hydroxymethyldimethylphosphonate, hydroxymethyldiisopropylphosphonate, hydroxymethyldibutylphosphonate hydroxymethyldibutylphosphonate, hydroxymethyldibutylphosphonate, and hydroxymethyldiphenylphosphonate. < RTI ID = 0.0 > 11. < / RTI > The method according to claim 3 or 4,
Wherein the ketone-based compound is acetone. I) mixing the amine compound with formalin or formaldehyde to react; And
Ii) removing water generated after the reaction and mixing phosphorus compounds to react them. A method for producing an organophosphorus flame retardant curing agent, which comprises mixing an amine compound and a phosphorus compound containing a hydroxy group and reacting them. I) mixing an amine compound and a phosphorus compound; And
Ii) reacting the mixture with a ketone-based compound to produce an organic phosphorus-based flame-retardant curing agent. I) reacting an amine compound with a ketone compound; And
Ii) reacting the reaction product with a phosphorus compound to produce an organophosphorus flame retardant curing agent. 14. The method according to any one of claims 10 to 13,
The amine compound may be selected from the group consisting of ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine (TEPA), diprophenediamine , DPDA), N-aminoethylpiperazine (AEP), isophorone diamine (IPDA), hexamethylenediamine (HMDA), m-xylenediamine (MXDA), lamellone C (HY-964), methanediamine, sho-amine, m-phenylenediamine, diaminodiphenylmethane , DDM), diaminodiphenyl sulfone (diaminodiphenylsulfone, DDS) and JEFFAMINE ^® D-230 polyether amine (characterized in that the polyetheramine) selected from the group consisting of. 14. The method according to claim 10, 12 or 13,
Wherein said phosphorus compound is selected from the group consisting of dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite and diphenyl phosphite. 12. The method of claim 11,
The phosphorus compound may be at least one selected from the group consisting of hydroxymethyl diethyl phosphonate, hydroxymethyl dimethyl phosphonate, hydroxymethyl diisopropyl phosphonate, hydroxymethyl dibutyl phosphonate, and hydroxymethyl diphenyl phosphonate ≪ / RTI > 11. The method of claim 10,
Characterized in that the formalin or formaldehyde of step (i) is mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound. 11. The method of claim 10,
Wherein the phosphorus compound in step ii) is mixed in an amount of 0.5 to 3 equivalents per equivalent of the amine compound. 12. The method of claim 11,
Wherein the phosphorus compound is mixed at 0.5 to 3 equivalents per equivalent of the amine compound. The method according to claim 12 or 13,
Wherein the ketone-based compound is acetone. The method according to claim 12 or 13,
Wherein the ketone compound is mixed at 0.5 to 3 equivalents per equivalent of the amine compound. The method according to claim 12 or 13,
Wherein the phosphorus compound is mixed at 0.5 to 3 equivalents per equivalent of the amine compound. A coating composition comprising the organophosphorus flame retardant curing agent according to any one of claims 1 to 5.

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