Polymerizable composition

Abstract

The present application relates to a polymerizable composition, a prepolymer, a phthalonitrile resin, a composite, a method for producing the same, and a use thereof. The present application can provide a polymerizable composition, a prepolymer and a phthalonitrile resin capable of forming a composite showing proper curing property, melting temperature and process window and having excellent physical properties such as heat resistance and rigidity.

Claims

1. A polymerizable composition comprising a phthalonitrile compound and a compound of Formula 1 below: ##STR00022## wherein, X.sub.1 to X.sub.3 are each the same or different aromatic divalent radical, Y.sub.1 and Y.sub.2 are each the same or different aryl group substituted with at least one amine group, R.sub.1 to R.sub.4 are each independently a hydrogen atom, an alkyl group, an alkoxy group or an aryl group and n is a number in a range of 0 to 20.

2. The polymerizable composition according to claim 1, wherein X.sub.1 to X.sub.3 are each a divalent radical derived from an aromatic compound having 6 to 30 carbon atoms, and Y.sub.1 and Y.sub.2 are each a monovalent radical derived from an aromatic compound having 6 to 30 carbon atoms.

3. The polymerizable composition according to claim 1, wherein X.sub.1 to X.sub.3 are each a radical derived from a compound represented by Formula 2 or 3 below or Y.sub.1 and Y.sub.2 are each a radical derived from a compound represented by Formula 2 or 3 below: ##STR00023## wherein, R.sub.1 to R.sub.6 are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group, a carboxyl group or an amine group, and when Y.sub.1 or Y.sub.2 in Formula 1 is derived from Formula 2, at least one of R.sub.1 to R.sub.6 is an amine group; ##STR00024## wherein, R.sub.1 to R.sub.10 are each independently hydrogen, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, an amine group or an aryl group, and X is a single bond, an alkylene group, an alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, NR.sub.11, S(O), S(O).sub.2, -L.sub.9-Ar.sub.3-L.sub.10- or -L.sub.9-Ar.sub.3-L.sub.10-Ar.sub.4-L.sub.11-, where R.sub.11 is hydrogen, an alkyl group, an alkoxy group or an aryl group, Ar.sub.3 and Ar.sub.4 are arylene groups and L.sub.9 to L.sub.11 are each independently a single bond, an oxygen atom, an alkylene group or an alkylidene group, and when Y.sub.1 or Y.sub.2 in Formula 1 is derived from Formula 3, at least one of R.sub.1 to R.sub.10 is an amine group.

4. The polymerizable composition according to claim 1, further comprising a filler.

5. The polymerizable composition according to claim 1, wherein the compound of Formula 1 is contained in an amount of about 0.02 mol to about 1.5 mol per mole of the phthalonitrile compound.

6. A prepolymer formed by the reaction of the polymerizable composition of claim 1.

7. A phthalonitrile resin formed by polymerizing the polymerizable composition of claim 1.

8. A composite comprising the phthalonitrile resin of claim 7 and a filler.

9. The composite according to claim 8, wherein the filler is a metal material, a ceramic material, glass, metal oxide, metal nitride or a carbonaceous material.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIGS. 1 to 14 are results of NMR measurement for compounds prepared in Preparation Examples.

MODE FOR INVENTION

(2) Hereinafter, the polymerizable composition or the like of the present application will be specifically described by way of Examples and Comparative Examples, but the scope of the polymerizable composition and the like is not limited to the following Examples.

(3) 1. NMR (Nuclear Magnetic Resonance) Analysis

(4) NMR analysis was carried out by using a 500 MHz NMR equipment from Agilent as the manufacturer's manual. A sample for NMR measurement was prepared by dissolving the compound in DMSO (dimethyl sulfoxide)-d6.

(5) 2. DSC (Differential Scanning Calorimetry) Analysis

(6) DSC analysis was carried out in a N.sub.2 flow atmosphere using a Q20 system from TA instrument while raising the temperature from 35 C. to 400 C. at a heating rate of 10 C./min.

(7) 3. TGA (Thermogravimetric Analysis) Analysis

(8) TGA analysis was performed using a TGA e850 instrument from Mettler-Toledo. In the case of the compounds prepared in Preparation Examples, they were analyzed in a N.sub.2 flow atmosphere while raising the temperature from 25 C. to 800 C. at a heating rate of 10 C./min.

Preparation Example 1. Synthesis of Compound (Pn1)

(9) A compound of Formula A below was synthesized in the following manner. 32.7 g of a compound of Formula B below and 120 g of DMF (dimethylformamide) were introduced into a 3 neck RBF (round bottom flask) and dissolved by stirring at room temperature. Subsequently, 51.9 g of a compound of Formula C was added and 50 g of DMF was added, and then dissolved by stirring. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added together and the temperature was raised to 85 C. with stirring. After reacting for about 5 hours in the above state, it was cooled to room temperature. The cooled reaction solution was neutralized and precipitated by pouring it into a 0.2N hydrochloric acid aqueous solution, and washed with water after filtering. The filtered reactant was then dried in a vacuum oven at 100 C. for 1 day, and after removing water and the residual solvent, a compound (PN1) of Formula A below was obtained in a yield of about 80 wt %. The NMR results for the compound of Formula A above were described in FIG. 1.

(10) ##STR00007##

Preparation Example 2. Synthesis of Compound (PN2)

(11) A compound of Formula D below was synthesized in the following manner. 28.0 g of 4,4-bis(hydroxyphenyl)methane and 150 mL of DMF (dimethylformamide) were introduced into a 500 mL 3 neck RBF (round bottom flask) and dissolved at room temperature. Subsequently, 48.5 g of 4-nitrophthalonitrile was added to the mixture and 50 g of DMF was added, and then dissolved by stirring. Subsequently, 58.1 g of potassium carbonate and 50 g of DMF were added together and the temperature was raised to 85 C. with stirring. After reacting for about 5 hours, it was cooled to room temperature. The cooled reaction solution was neutralized and precipitated by pouring it into a 0.2N hydrochloric acid aqueous solution, and washed with water after filtering. The filtered reactant was then dried in a vacuum oven at 100 C. for 1 day, and after removing water and the residual solvent, the target compound (PN2) was obtained in a yield of about 83 wt %. The NMR results for the compound (PN2) of Formula D above were described in FIG. 2.

(12) ##STR00008##

Preparation Example 3. Synthesis of Compound (CA1)

(13) A compound (CA1) of Formula E below was synthesized in the following manner. 53.2 g of a compound of Formula F below and 80.1 g of a compound of Formula G below were introduced into a 3 neck RBF (round bottom flask) and the temperature was raised to 260 C. The mixture was reacted for about 1 hour while removing H.sub.2O generated in the above state. Subsequently, the reactant was cooled to room temperature to obtain a blue solid. The obtained solid was triturated and then dried in a vacuum oven after removing the residual monomer using MeOH (methanol) and filtering to yield a compound (CA1) of Formula E below in a yield of about 88 wt %. The NMR results for the compound of Formula E were described in FIG. 3. Considering the amount of the monomer used, n in Formula E below was theoretically 3, but it was confirmed to be 3.5 in NMR. This difference is presumed to be because during the reaction the substance of Formula G has sublimated at high temperature.

(14) ##STR00009##

(15) In Formula E, n is about 3.5.

(16) ##STR00010##

Preparation Example 4. Synthesis of Compound (CA2)

(17) A compound (CA2) in which n in Formula E of Preparation Example 3 was about 0 to 1.5 was synthesized in the following manner. 33.2 g of the compound of Formula F in Preparation Example 3 and 80.1 g of the compound of Formula G were introduced into a 3 neck RBF (round bottom flask) and the temperature was raised to 260 C. The mixture was reacted for about 1 hour while removing H.sub.2O generated in the above state. Subsequently, the reactant was cooled to room temperature to obtain a blue solid. The obtained solid was triturated and then dried in a vacuum oven after removing the residual monomer using MeOH (methanol) and filtering to yield a compound (CA2) of Formula E, in which n in Formula E of Preparation Example 3 was 0 to 1.5, in a yield of about 86 wt %. The NMR results for the compound (CA2) were described in FIG. 4. Considering the amount of the monomer used, n in the compound (CA2) was theoretically 0, but it was confirmed to be about 1.5 in NMR. This difference is presumed to be because during the reaction the substance of Formula G has sublimated at high temperature.

Preparation Example 5. Synthesis of Compound (CA3)

(18) A compound (CA3) in which n in Formula E of Preparation Example 3 was about 0 to 0.5 was synthesized in the following manner. 28.2 g of the compound of Formula F in Preparation Example 3 and 136.2 g of the compound of Formula G were introduced into a 3 neck RBF (round bottom flask) and the temperature was raised to 260 C. The mixture was reacted for about 1 hour while removing H.sub.2O generated in the above state. Subsequently, the reactant was cooled to room temperature to obtain a blue solid. The obtained solid was triturated and then dried in a vacuum oven after removing the residual monomer using MeOH (methanol) and filtering to yield a compound (CA2) of Formula E, in which n in Formula E of Preparation Example 3 was 0 to 0.5, in a yield of about 93 wt %. The NMR results for the compound (CA2) were described in FIG. 5. In order to obtain a compound, in which n in Formula E was 0, an excessive amount of the compound of Formula G was added, but it was confirmed to be about 0.5 in NMR. This difference is presumed to be because the compound of Formula E, to which two or more compounds of Formula F have been introduced, has been generated due to the high-temperature reaction.

Preparation Example 6. Synthesis of Compound (CA4)

(19) A compound (CA4) of Formula H below was synthesized in the following manner. 66.4 g of the compound of Formula F in Preparation Example 3 and 54.1 g of a compound of Formula I below were introduced into a 3 neck RBF (round bottom flask) and the temperature was raised to 260 C. The mixture was reacted for about 1 hour while removing H.sub.2O generated in the above state. Subsequently, the reactant was cooled to room temperature to obtain an orange solid. The obtained solid was triturated and then dried in a vacuum oven after removing the residual monomer using MeOH (methanol) and filtering to yield a compound (CA4) of Formula H below in a yield of about 85 wt %. The NMR results for the compound of Formula H were described in FIG. 6. Considering the amount of the monomer used, n in Formula H below was theoretically 3, but it was confirmed to be 4 in NMR. This difference is presumed to be because during the reaction the substance of Formula I has sublimated at high temperature.

(20) ##STR00011##

(21) In Formula E, n is about 4.

(22) ##STR00012##

Preparation Example 7. Synthesis of Compound (CA5)

(23) A compound (CA5) in which n in Formula H of Preparation Example 6 was about 0 to 1.5 was synthesized in the following manner. 41.5 g of the compound of Formula F in Preparation Example 3 and 54.1 g of the compound of Formula I in Preparation Example 5 were introduced into a 3 neck RBF (round bottom flask) and the temperature was raised to 260 C. The mixture was reacted for about 1 hour while removing H.sub.2O generated in the above state. Subsequently, the reactant was cooled to room temperature to obtain a red solid. The obtained solid was triturated and then dried in a vacuum oven after removing the residual monomer using MeOH (methanol) and filtering to yield a compound (CA5) in a yield of about 80 wt %. The NMR results for the compound (CA5) were described in FIG. 7. Considering the amount of the monomer used, n in the compound (CA5) was theoretically 0, but it was confirmed to be about 1.5 in NMR. This difference is presumed to be because during the reaction the substance of Formula I has sublimated at high temperature.

Preparation Example 8. Synthesis of Compound (CA6)

(24) A compound (CA6) in which n in Formula H of Preparation Example 6 was about 0 to 0.7 was synthesized in the following manner. 58.1 g of the compound of Formula F in Preparation Example 3 and 113.5 g of the compound of Formula I in Preparation Example 5 were introduced into a 3 neck RBF (round bottom flask) and the temperature was raised to 260 C. The mixture was reacted for about 1 hour while removing H.sub.2O generated in the above state. Subsequently, the reactant was cooled to room temperature to obtain a red solid. The obtained solid was triturated and then dried in a vacuum oven after removing the residual monomer using MeOH (methanol) and filtering to yield a compound (CA6) in a yield of about 92 wt %. The NMR results for the compound (CA6) were described in FIG. 8. In order to obtain a compound, in which n in Formula H was 0, an excessive amount of the compound of Formula I was added, but it was confirmed to be about 0.7 in NMR. This difference is presumed to be because the compound of Formula E, to which two or more compounds of Formula F have been introduced, has been generated due to the high-temperature reaction.

Preparation Example 9 Synthesis of Compound (CA7)

(25) A compound (CA7) of Formula J below was synthesized in the following manner. 25 g of the compound of Formula F in Preparation Example 3 and 154 g of a compound of Formula K below were introduced into a 3 neck RBF (round bottom flask) and the temperature was raised to 260 C. The mixture was reacted for about 1 hour while removing H.sub.2O generated in the above state. Subsequently, the reactant was cooled to room temperature to obtain a white solid. The obtained solid was triturated and then dried in a vacuum oven after removing the residual monomer using diethyl ether and filtering to yield a compound (CA7) of Formula J below in a yield of about 89 wt %. The NMR results for the compound of Formula J were described in FIG. 9. In order to obtain a compound, in which n in Formula J was 0, an excessive amount of the compound of Formula K was added, but it was confirmed to be about 0.7 in NMR. This difference is presumed to be because the compound of Formula E, to which two or more compounds of Formula F have been introduced, has been generated due to the high-temperature reaction.

(26) ##STR00013##

(27) In Formula J, n is about 0.7.

(28) ##STR00014##

Preparation Example 10 Synthesis of Compound (CA8)

(29) A compound (CA8) of Formula L below was synthesized in the following manner. 33.2 g of a compound of Formula M below and 80.1 g of the compound of Formula G in Preparation Example 3 were introduced into a 3 neck RFB (round bottom flask) and the temperature was raised to 260 C. The mixture was reacted for about 1 hour while removing H.sub.2O generated in the above state. Subsequently, the reactant was cooled to room temperature to obtain a blue solid. The obtained solid was triturated and then dried in a vacuum oven after removing the residual monomer using methanol and filtering to yield a compound (CA8) of Formula L below in a yield of about 85 wt %. The NMR results for the compound of Formula L were described in FIG. 10. In order to obtain a compound, in which n in Formula L was 0, an excessive amount of the compound of Formula G was added, but it was confirmed to be about 0.5 in NMR. This difference is presumed to be because the compound, to which two or more compounds of Formula M have been introduced, has been generated due to the high-temperature reaction.

(30) ##STR00015##

(31) In Formula L, n is about 0.5.

(32) ##STR00016##

Preparation Example 11. Synthesis of Compound (CA9)

(33) A compound (CA9) of Formula N below was synthesized in the following manner. 58.1 g of the compound of Formula M in Preparation Example 10 and 94.6 g of the compound of Formula I in Preparation Example 6 were introduced into a 3 neck RBF (round bottom flask) and the temperature was raised to 260 C. The mixture was reacted for about 1 hour while removing H.sub.2O generated in the above state. Subsequently, the reactant was cooled to room temperature to obtain a red solid. The obtained solid was triturated and then dried in a vacuum oven after removing the residual monomer using methanol and filtering to yield a compound (CA9) of Formula N below in a yield of about 87 wt %. The NMR results for the compound of Formula N were described in FIG. 11. In order to obtain a compound, in which n in Formula N was 0, an excessive amount of the compound of Formula G was added, but it was confirmed to be about 1.2 in NMR. This difference is presumed to be because the reaction has proceeded rapidly due to the high-temperature reaction and the compound of Formula I has easily sublimed, thereby generating the compound to which two or more compounds of Formula M have been introduced.

(34) ##STR00017##

(35) In Formula N, n is about 1.2.

Preparation Example 12. Synthesis of Compound (CA10)

(36) A compound (CA10) of Formula 0 was synthesized in the following manner. 25 g of the compound of Formula M in Preparation Example 10 and 154 g of the compound of Formula K in Preparation Example 9 were introduced into a 3 neck RBF (round bottom flask) and the temperature was raised to 260 C. The mixture was reacted for about 1 hour while removing H.sub.2O generated in the above state. Subsequently, the reactant was cooled to room temperature to obtain a pale green solid. The obtained solid was triturated and then dried in a vacuum oven after removing the residual monomer using methanol and filtering to yield a compound (CA10) of Formula O below in a yield of about 85 wt %. The NMR results for the compound of Formula O were described in FIG. 12. In order to obtain a compound, in which n in Formula N was O, an excessive amount of the compound of Formula K was added, but it was confirmed to be about 0.7 in NMR.

(37) ##STR00018##

(38) In Formula O, n is about 0.7.

Preparation Example 13. Synthesis of Compound (CA11)

(39) A compound (CA11) of Formula P below was synthesized in the following manner. 28 g of the compound of Formula F in Preparation Example 3 and 156 g of a compound of Formula Q below were introduced into a 3 neck RBF (round bottom flask) and the temperature was raised to 260 C. The mixture was reacted for about 1 hour while removing H.sub.2O generated in the above state. Subsequently, the reactant was cooled to room temperature to obtain a white solid. The obtained solid was triturated and then dried in a vacuum oven after removing the residual monomer using diethyl ether and filtering to yield a compound (CA11) of Formula P below in a yield of about 81 wt %. The NMR results for the compound of Formula P were described in FIG. 13. In order to obtain a compound, in which n in Formula P was 0, an excessive amount of the compound of Formula Q was added, but it was confirmed to be about 1.8 in NMR. This difference is presumed to be because the reaction has proceeded rapidly due to the high-temperature reaction and the compound, to which two or more compounds of the Formula F have been introduced, has been generated.

(40) ##STR00019##

(41) In Formula P, n is about 1.8.

(42) ##STR00020##

Preparation Example 14. Synthesis of Compound (CA12)

(43) A compound (CA14), in which n in Formula E of Preparation Example 3 was about 0.9, was synthesized through Yamazaki reaction. 14 g of LiCl, 100 g of NMP and 41 g of pyridine were introduced into a 3 neck RBF (round bottom flask) in turn, and the temperature was raised to 100 C. Subsequently, 17 g of the compound of Formula F in Preparation Example 3 and 44 g of the compound of Formula G in Preparation Example 3 were added to the 3 neck RBF (round bottom flask) and 62 g of triphenylphosphine was further added thereto. The reactant was stirred at 100 C. for about 3 hours. After the reaction, the reactant was cooled to room temperature and precipitated in methanol to obtain a yellow solid. The obtained solid was filtered and then dried in a vacuum oven to obtain a compound (CA12), in which n in Formula E of Preparation Example 3 was about 0.9, in a yield of about 78 wt %. The NMR results for this compound (CA12) were described in FIG. 14. Considering the amount of the monomer used, n in Formula E below was theoretically 0, but it was confirmed to be 0.9 in NMR.

Preparation Example 15. Compound (CA13)

(44) A compound of Formula R below was commercially available from TCI (Tokyo Chemical Industry Co., Ltd.) and used without further purification.

(45) ##STR00021##

(46) The TGA analysis results performed on the compounds of Preparation Examples 3 to 15 were summarized in Table 1 below. From Table 1, it can be confirmed that the compounds (CA1 to CA12) of Preparation Examples 3 to 14 have excellent thermal stability over the compound (CA13) of Preparation Example 15. For example, the compound (CA13) was completely decomposed at around 330 C., while the compounds (CA1 to CA12) had a Td10% in a range of 350 C. to 450 C. and hardly caused decomposition by heat even when burned at high temperature.

(47) TABLE-US-00001 TABLE 1 Residue Td10% (at 800 C.) Td100% ( C.) (%) ( C.) Preparation Example 3 CA 1 449.5 43.8 Preparation Example 4 CA 2 408.7 42.8 Preparation Example 5 CA 3 395 39.3 Preparation Example 6 CA 4 425.8 51.5 Preparation Example 7 CA 5 404.1 44.3 Preparation Example 8 CA 6 389.2 47.7 Preparation Example 9 CA 7 435.8 29.7 Preparation Example 10 CA 8 378 35.5 Preparation Example 11 CA 9 358.6 40.3 Preparation Example 12 CA 10 442.3 30.4 Preparation Example 13 CA 11 449.3 42.0 Preparation Example 14 CA 12 349.2 53.3 Preparation Example 15 CA 13 264 0 331

(48) Also, from the above results, it can be confirmed that the higher the molecular weight, the thermal stability is more improved and it can be seen that the thermal stability can be controlled depending on the structure and the type of the monomer. From Table 1, it can be confirmed that the compounds of the specific structure of the present application can sufficiently obtain desired heat resistance and thermal stability even at a low molecular weight and can prevent thermal decomposition at a burning temperature, which is a problem upon using conventional curing agents of monomolecular materials, to obtain better curing efficiency and excellent physical properties.

Example 1

(49) To the compound (PN1) of Preparation Example 1, about 12 mol % of the compound (CA2) of Preparation Example 4 was added relative to the used amount of the compound (PN1) and mixed well to prepare a polymerizable composition. The composition was subjected to a DSC analysis to measure the processing temperature and the curing initiation temperature and to confirm the process window of the temperature difference. The relevant results are described in Table 2, and if the polymerizable composition is melted at about 240 C. and stirred for 5 minutes, it is possible to prepare a prepolymer.

Example 2

(50) To the compound (PN1) of Preparation Example 1, about 12 mol % of the compound (CA5) of Preparation Example 7 was added relative to the used amount of the compound (PN1) and mixed well to prepare a polymerizable composition. The composition was subjected to a DSC analysis to measure the processing temperature and the curing initiation temperature and to confirm the process window of the temperature difference. The relevant results are described in Table 2, and if the polymerizable composition is melted at about 240 C. and stirred for 5 minutes, it is possible to prepare a prepolymer.

Example 3

(51) To the compound (PN1) of Preparation Example 1, about 12 mol % of the compound (CA2) of Preparation Example 4 was added relative to the used amount of the compound (PN1) and mixed well to prepare a polymerizable composition. The composition was subjected to a DSC analysis to measure the processing temperature and the curing initiation temperature and to confirm the process window of the temperature difference. The relevant results are described in Table 2, and if the polymerizable composition is melted at about 240 C. and stirred for 5 minutes, it is possible to prepare a prepolymer.

Example 4

(52) To the compound (PN2) of Preparation Example 2, about 12 mol % of the compound (CA5) of Preparation Example 7 was added relative to the used amount of the compound (PN2) and mixed well to prepare a polymerizable composition. The composition was subjected to a DSC analysis to measure the processing temperature and the curing initiation temperature and to confirm the process window of the temperature difference. The relevant results are described in Table 2, and if the polymerizable composition is melted at about 240 C. and stirred for 5 minutes, it is possible to prepare a prepolymer.

Comparative Example 1

(53) To the compound (PN1) of Preparation Example 1, about 12 mol % of the compound (CA13) of Preparation Example 15 was added relative to the used amount of the compound (PN1) and mixed well to prepare a polymerizable composition. The composition was subjected to a DSC analysis to measure the processing temperature and the curing initiation temperature and to confirm the process window of the temperature difference. The relevant results are described in Table 2, and if the polymerizable composition is melted at about 240 C. and stirred for 5 minutes, it is possible to prepare a prepolymer.

Comparative Example 2

(54) To the compound (PN2) of Preparation Example 2, about 12 mol % of the compound (CA13) of Preparation Example 15 was added relative to the used amount of the compound (PN2) and mixed well to prepare a polymerizable composition. The composition was subjected to a DSC analysis to measure the processing temperature and the curing initiation temperature and to confirm the process window of the temperature difference. The relevant results are described in Table 2, and if the polymerizable composition is melted at about 240 C. and stirred for 5 minutes, it is possible to prepare a prepolymer.

(55) TABLE-US-00002 TABLE 2 Processing Curing Initiation Process Temperature Temperature window ( C.) ( C.) ( C.) Example 1 175.3 258.5 83.2 Example 2 175.7 255.9 80.2 Example 3 128.7 250.4 121.7 Example 4 128.6 260.4 131.8 Comparative Example 1 177.6 309.2 131.6 Comparative Example 2 190.1 288.3 98.2

(56) From the above results, it can be confirmed that Comparative Example 1 in the results of Examples 1 and 2 and Comparative Example 1, to which the same monomer PN1 is applied, exhibits a wider process window than Examples 1 and 2. This is because Comparative Example 1 and Examples 1 and 2 have similar processing temperatures, but Examples 1 and 2 have the curing initiation temperature lower than that of Comparative Example 1. However, it can be confirmed that the curing initiation temperature of Comparative Example 1 is extremely high, such as 310 C., whereas Examples 1 and 2 exhibit at a low value of around 255 C. Nevertheless, considering that the curing agent (CA13) applied in Comparative Example 1 is completely pyrolyzed at a temperature of about 330 C. in Table 1, it can be confirmed that it is not easy to substantially apply Comparative Example 1. In the case of Examples 1 and 2, it can be confirmed that through the application of the compounds of the specific structure, the curing initiation temperature is lowered, whereby the low-temperature curing is possible. If the curing temperature is high, special equipment to be applied at high temperature is required, and the production cost is also raised in order to achieve a high temperature. Furthermore, when the low-temperature curing is possible, it is possible to perform a rapid curing with a low viscosity at the same temperature, thereby improving workability and productivity.

(57) In addition, it can be confirmed that Examples 3 and 4 have a low curing temperature while showing a wider process window than Comparative Example 2.