Hardening agent composition and curable composition containing the same

Abstract

A curing agent composition containing a first compound represented by the following chemical formula 1 with n = 1 and a second compound represented by the following chemical formula 1 with n = 2, having a high decomposition temperature (Td) and excellent solubility, and capable of preventing curing deviation caused by partial decomposition of the curing agent during vacuum high-temperature crosslinking. [Chemical formula 1] JPEG2025522596000032.jpg14170

Description

Technical Field

[0001] The present invention relates to a curing agent composition and a curable composition containing the same.

Background Art

[0002] In the currently accelerating fifth-generation communication system "5G", it is expected that in data communication of various devices including smartphones, new large-capacity and high-speed communication will be promoted. The need for low dielectric tangent materials is gradually increasing, and at least a dielectric tangent of 0.005 or less is required at 1 GHz, and a material that can achieve this heat resistance and dielectric characteristics (dielectric tangent) is required.

[0003] In particular, in order to realize excellent low dielectric characteristics, in 5G CCLs (copper-clad laminations), triallyl isocyanurate (TAIC) is mainly used as a curing agent. Triallyl isocyanurate (TAIC) provides 5G CCLs with low dielectric characteristics by curing the polymer while the double bonds present at the ends are crosslinked with the polymer by an initiator.

[0004] However, when triallyl isocyanurate (TAIC) is crosslinked under vacuum high-temperature conditions, due to the low decomposition temperature (Td) of triallyl isocyanurate (TAIC), a part of triallyl isocyanurate (TAIC) volatilizes, and curing deviation occurs by site, resulting in a problem that heat resistance and durability are reduced. Therefore, in order to prevent the occurrence of curing deviation, the need for a curing agent with a high decomposition temperature (Td) is increasing.

Summary of the Invention

Problems to be Solved by the Invention

[0005] The technical problem to be solved by the present invention is to provide a crosslinking agent having a high decomposition temperature and a curable composition containing the same.

Means for Solving the Problem

[0006] One aspect of the present invention relates to a curing agent composition containing a first compound represented by the following chemical formula 1 with n = 1 and a second compound with n = 2.

[0007] [Chemical formula 1] JPEG2025522596000002.jpg13170

[0008] [Chemical formula 2] JPEG2025522596000003.jpg43170

[0009] In the above chemical formulas 1 and 2, X is represented by the above chemical formula 2, X1 is N or CR1, X2 is N or CR2, X3 is N or CR3, *, *’ and *” are, independently of each other, bonding sites with Y or Z in the above chemical formula 1, Y is a C2-C 15 alkenyl group, Z is a C8-C 21 alkenylphenyl group, R1 to R3 are, independently of each other, hydrogen, a C1-C 15 alkyl group, a C2-C 15 alkenyl group or a C8-C 21 alkenylphenyl group, n is an integer from 0 to 3.

[0010] Another aspect of the present invention relates to a curable composition containing the above curing agent composition.

Effects of the Invention

[0011] The curing agent composition according to the present invention has a high decomposition temperature, and even when crosslinked under vacuum high-temperature conditions, it is possible to prevent curing deviation caused by partial decomposition of the curing agent composition.

[0012] Further, the curing agent composition according to the present invention can have excellent solubility even when the decomposition temperature increases.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Figure 3

Figure 4

Modes for Carrying Out the Invention

[0014] Hereinafter, various aspects and various specific examples of the present invention will be described more specifically.

[0015] The terms and words used in this specification and the claims are not to be construed as being limited to general or dictionary meanings. The inventor must interpret them according to the meaning and concept that conform to the technical idea of the present invention, based on the principle that the inventor can appropriately define the concept of the terms in order to explain his invention in the best way.

[0016] The terms used in the present invention are merely used for describing specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present invention, terms such as "including" or "having" are used to specify the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and it should not be understood as precluding the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0017] Specifically, the curing agent composition according to one aspect of the present invention includes a first compound represented by the following Chemical Formula 1 with n = 1 and a second compound with n = 2.

[0018] [Chemical Formula 1] JPEG2025522596000004.jpg14170

[0019] [Chemical Formula 2] JPEG2025522596000005.jpg43170

[0020] In Chemical Formulas 1 and 2, In Chemical Formula 1, X is represented by Chemical Formula 2, In Chemical Formula 2, X1 is N or CR1, X2 is N or CR2, X3 is N or CR3, and *, *', and *" are, independently of each other, bonding sites with Y or Z in Chemical Formula 1. Y is a C2-C 15 alkenyl group, and Z is a C8-C 21 alkenylphenyl group. R1 to R3 are, independently of each other, hydrogen, a C1-C 15 alkyl group, a C2-C 15 alkenyl group, or a C8-C 21 alkenylphenyl group, and n is an integer from 0 to 3.

[0021] According to a specific example, the first compound may be represented by the following Chemical Formula 1-1.

[0022] [Chemical Formula 1-1] JPEG2025522596000006.jpg20170

[0023] In Chemical Formula 1-1, X is represented by Chemical Formula 2, Y is a C2-C 15 alkenyl group, and Z is a C8-C 21 alkenylphenyl group.

[0024] For example, the first compound may also include the following Compound 1.

[0025] [Compound 1] JPEG2025522596000007.jpg79170

[0026] According to a specific example, the second compound may be represented by the following Chemical Formula 1-2.

[0027] [Chemical Formula 1-2] JPEG2025522596000008.jpg21170

[0028] In Chemical Formula 1-2, X is represented by Chemical Formula 2, Y is a C2-C 15 alkenyl group, and Z is a C8-C 21 alkenylphenyl group.

[0029] For example, the second compound may also include the following Compound 2.

[0030] [Compound 2] JPEG2025522596000009.jpg80170

[0031] According to a specific example, the ratio of the content of the first compound to the content of the second compound is also 10:90 to 90:10.

[0032] According to one specific example, the ratio of the content of the first compound to the content of the second compound is also 40:60 to 90:10, 45:55 to 90:10, 50:50 to 90:10, 40:60 to 80:20, or 40:60 to 70:30.

[0033] According to one specific example, the content of the first compound is more than or equal to the content of the second compound. When the content of the first compound is more than the content of the second compound, the curing agent composition has a high decomposition temperature (Td) and excellent solubility.

[0034] According to one specific example, the curing agent composition further contains a third compound represented by Chemical Formula 1 with n being 3, or a fourth compound represented by Chemical Formula 1 with n being 0. For example, the curing agent composition further contains a third compound represented by Chemical Formula 1 with n being 3. For example, the curing agent composition further contains a fourth compound represented by Chemical Formula 1 with n being 0. For example, the curing agent composition further contains a third compound represented by Chemical Formula 1 with n being 3 and a fourth compound represented by Chemical Formula 1 with n being 0.

[0035] According to one specific example, the third compound can be represented by the following Chemical Formula 1-3.

[0036] [Chemical Formula 1-3] JPEG2025522596000010.jpg21170

[0037] In Chemical Formula 1-3, X is represented by Chemical Formula 2, and Z is a C8-C 21 alkenylphenyl group.

[0038] For example, the third compound also includes the following Compound 3.

[0039] <Compound 3> JPEG2025522596000011.jpg80170

[0040] According to one specific example, the fourth compound may be represented by the following Chemical Formula 1-4.

[0041] [Chemical Formula 1-4] JPEG2025522596000012.jpg21170

[0042] In Chemical Formula 1-4, X is represented by Chemical Formula 2, and Y is a C2-C 15 alkenyl group.

[0043] For example, the fourth compound may also include the following Compound 4.

[0044] [Compound 4] JPEG2025522596000013.jpg56170

[0045] According to one specific example, based on the total weight of the curing agent composition, the total weight of the third compound and the fourth compound is also 25% by weight or less.

[0046] According to one specific example, based on the total weight of the curing agent composition, the total weight of the third compound and the fourth compound is also 24% by weight or less, 22% by weight or less, 21% by weight or less, or 20% by weight or less.

[0047] According to one specific example, in Chemical Formula 2, X1, X2, and X3 are also identical to each other.

[0048] According to one specific example, X1, X2, and X3 are each also N.

[0049] According to one specific example, in Chemical Formula 1, the Y may be represented by the following Chemical Formula 3.

[0050] [Chemical Formula 3] JPEG2025522596000014.jpg18170

[0051] In Chemical Formula 3, m is an integer from 0 to 5, * is a bonding site with the chemical formula 2.

[0052] For example, in the chemical formula 3, when m is 0, the Y is also a vinyl group.

[0053] According to one specific example, in the chemical formula 3, m is also an integer from 1 to 3.

[0054] According to one specific example, Y is also an allyl group.

[0055] According to one specific example, in the chemical formula 1, the Z can be represented by any one of the following chemical formulas 4-1 to 4-3.

[0056] [Chemical formula 4-1] JPEG2025522596000015.jpg31170

[0057] [Chemical formula 4-2] JPEG2025522596000016.jpg41170

[0058] [Chemical formula 4-3] JPEG2025522596000017.jpg31170

[0059] In the chemical formulas 4-1 to 4-3, l is an integer from 0 to 5, * is a bonding site with the chemical formula 2.

[0060] For example, in the chemical formulas 4-1 to 4-3, when l is 0, the Z is also a vinylphenyl group.

[0061] According to one specific example, in the chemical formulas 4-1 to 4-3, l is also an integer from 1 to 3.

[0062] According to one specific example, in the chemical formula 1, the Z can be represented by the chemical formula 4-1.

[0063] According to one specific example, in Chemical Formula 1, Z is represented by Chemical Formula 4-1, and n is also 1.

[0064] According to one specific example, the decomposition temperature (Td) of the curing agent composition is also 150°C or higher. For example, the decomposition temperature (Td) may mean the temperature at the point where the mass of the sample is reduced by 5% based on the measurement result of a thermogravimetric analyzer (TGA). For example, the decomposition temperature (Td) of the curing agent composition is also 160°C or higher, 170°C or higher, 180°C or higher, or 190°C or higher. For example, when the curing agent composition satisfies the decomposition temperature (Td) range, even if it is cross-linked under vacuum high-temperature conditions, the curing agent composition will not decompose, and it is possible to effectively prevent the occurrence of curing deviation by part.

[0065] The curable composition according to one aspect of the present invention also includes the curing agent composition, a base polymer, and an initiator.

[0066] The base polymer can be bonded to the double bond contained in the curing agent composition and cross-linked with adjacent base polymers, for example.

[0067] According to one specific example, the base polymer also includes modified polyphenylene oxide (mPPO: modified polyphenylene oxide). For example, the modified polyphenylene oxide (mPPO) also includes polyphenylene oxide modified with acrylate or polyphenylene oxide modified with methacrylate.

[0068] According to one specific example, the modified polyphenylene oxide (mPPO) can be represented by the following Chemical Formula 5.

[0069] [Chemical Formula 5] JPEG2025522596000018.jpg27170

[0070] In Chemical Formula 5, n and m are each independently an integer of 1 or more.

[0071] The initiator can initiate the crosslinking reaction between the curing agent composition and the base polymer.

[0072] According to one specific example, the initiator also contains a peroxide-based initiator.

[0073] According to one specific example, the peroxide-based initiator contains dicumyl peroxide, diacyl peroxide, 2,4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauryl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, or any combination thereof.

[0074] According to one specific example, the initiator also contains dicumyl peroxide.

[0075] According to one specific example, the ratio of the number of moles of the initiator to the number of moles of the curing agent composition is also 0.01 to 0.5. For example, the ratio of the number of moles of the initiator to the number of moles of the curing agent composition is also 0.05 to 0.5, 0.1 to 0.5, 0.1 to 0.4, or 0.2 to 0.4.

[0076] According to one specific example, the curable composition also contains a solvent.

[0077] According to one specific example, the solvent contains toluene, acetone, methyl ethyl ketone, ethyl acetate, or any combination thereof.

[0078] According to one specific example, the solvent also contains toluene.

[0079] According to one specific example, the content of the base polymer contained in the curable composition is 50 to 90% by weight based on the total weight of the solid content, the content of the curing agent composition is 1 to 35% by weight based on the total weight of the solid content, and the content of the initiator is also 1 to 15% by weight based on the total weight of the solid content. The total weight of the solid content may mean the total weight of the remaining components excluding the solvent in the curable composition.

[0080] According to one specific example, the ratio of the weight of the base polymer to the weight of the curing agent composition is also 0.1 to 10. For example, the ratio of the weight of the base polymer to the weight of the curing agent composition is 1 to 10, 2 to 10, 1 to 8, 1 to 6, 1 to 4, or 1 to 3.

[0081] [Definition of Terms] In this specification, C1-C 15 The alkyl group means a linear or branched aliphatic hydrocarbon monovalent group having 1 to 15 carbon atoms. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, tert-pentyl group, neopentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, sec-isopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, and the like.

[0082] In this specification, C2-C 15 The alkenyl group is C2-C 15 It means a monovalent hydrocarbon group containing one or more carbon-carbon double bonds in the middle or at the end of the alkyl group. Specific examples thereof include ethenyl group, propenyl group, butenyl group, and the like.

[0083] In this specification, C8-C 21 The alkenylphenyl group means a monovalent benzene group substituted with one or more C2-C 15 alkenyl groups. Specific examples thereof include 2-ethenylphenyl group, 3-ethenylphenyl group, 4-ethenylphenyl group, 2-propenylphenyl group, 3-propenylphenyl group, 4-propenylphenyl group, 2-butenylphenyl group, 3-butenylphenyl group, 4-butenylphenyl group, etc.

[0084] In this specification, C6-C 60 The aryl group means a monovalent group having a C6-C 60 carbocyclic aromatic system, and includes phenyl group, pentalenyl group, naphthyl group, azulenyl group, indacenyl group, acenaphthyl group, phenalenyl group, phenanthrenyl group, anthracenyl group, fluoranthenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, perylenyl group, pentaphenyl group, heptalenyl group, naphthacenyl group, picenyl group, hexacenyl group, pentacenyl group, rubicenyl group, coronenyl group, ovalenyl group, etc. When the C6-C 60 aryl group contains two or more rings, the two or more rings may be linked to each other.

[0085] Hereinafter, the present invention will be described in more detail through examples. It will be self-evident to those having ordinary knowledge in the technical field to which the present invention pertains that those examples are merely for explaining the present invention more specifically, and the scope of the present invention is not limited by those examples.

[0086] Production Example 1. Production of Hardener Composition 15.0 parts by mass of cyanuric chloride, 105.0 parts by mass of toluene, 2.62 parts by mass of tetrabutylammonium bromide (TBAB), and 11.46 parts by mass of 2-allylphenol were placed in a five-necked flask equipped with a thermometer, a condenser, and a stirrer, and stirred.

[0087] 6.83 parts by mass of 50% NaOH was charged, and the exotherm was not controlled. The temperature was directly raised to 70 °C and reacted for 1 hour.

[0088] It was cooled to 25 °C, 9.92 parts by mass of allyl alcohol and 13.68 parts by mass of 50% NaOH were charged, the temperature was raised to 70 °C, and reacted for 5 hours.

[0089] It was cooled to 25 °C, 30 parts by mass of water was added, and washed. The washing was repeated 5 times in total, and the toluene layer was removed by filtration through diatomaceous earth. Then, the product was concentrated under reduced pressure to obtain 24 parts by mass of the curing agent composition (yield 85% (pale yellow oil)).

[0090] The curing agent composition contains 44 wt% of Compound 1 corresponding to the first compound where n = 1 in Chemical Formula 1, 37 wt% of Compound 2 corresponding to the second compound where n = 2 in Chemical Formula 1, 12 wt% of Compound 3 corresponding to the third compound where n = 3 in Chemical Formula 1, and 8 wt% of Compound 4 corresponding to the fourth compound where n = 0 in Chemical Formula 1.

[0091] <Compound 1> JPEG2025522596000019.jpg79170

[0092] <Compound 2> JPEG2025522596000020.jpg80170

[0093] <Compound 3> JPEG2025522596000021.jpg79170

[0094] <Compound 4> JPEG2025522596000022.jpg56170

[0095] Production Example 2. Production of Hardener Composition Into a five-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 15.0 parts by mass of cyanuric chloride, 105.0 parts by mass of toluene, 2.62 parts by mass of tetrabutylammonium bromide (TBAB), and 16.37 parts by mass of 2-allylphenol were added and stirred.

[0096] 9.76 parts by mass of 50% NaOH was added, and the exotherm was not controlled. The temperature was directly raised to 70 °C and reacted for 1 hour.

[0097] It was cooled to 25 °C, 7.09 parts by mass of allyl alcohol and 9.76 parts by mass of 50% NaOH were added, the temperature was raised to 70 °C, and reacted for 5 hours.

[0098] It was cooled to 25 °C, 30 parts by mass of water was added, and washed with water. The water washing was repeated 5 times in total, and the toluene layer was removed by filtration through diatomaceous earth. Then, the product was concentrated under reduced pressure to obtain 24 parts by mass of a curing agent composition (yield 81%, light yellow oil).

[0099] The said curing agent composition contains 38 wt% of compound 1 corresponding to the first compound where n = 1 in the said chemical formula 1, 42 wt% of compound 2 corresponding to the second compound where n = 2 in the said chemical formula 1, 15 wt% of compound 3 corresponding to the third compound where n = 3 in the said chemical formula 1, and 5 wt% of compound 4 corresponding to the fourth compound where n = 0 in the said chemical formula 1.

[0100] Production Example 3. Production of Hardener Composition Into a five-necked flask equipped with a thermometer, a cooling tube, and a stirrer, 15.0 parts by mass of cyanuric chloride, 105.0 parts by mass of toluene, 2.62 parts by mass of tetrabutylammonium bromide (TBAB), and 21.83 parts by mass of 2-allylphenol were added and stirred.

[0101] 13.01 parts by mass of 50% NaOH was added, and the exotherm was not controlled. The temperature was directly raised to 70 °C and reacted for 1 hour.

[0102] Cooled to 25 °C, 4.96 parts by mass of allyl alcohol and 6.83 parts by mass of 50% NaOH were added, the temperature was raised to 70 °C, and the reaction was carried out for 5 hours.

[0103] Cooled to 25 °C, 30 parts by mass of water was added and washed. The washing was repeated 5 times in total, and the toluene layer was removed by filtration through diatomaceous earth. Then, the product was concentrated under reduced pressure to obtain 24 parts by mass of a curing agent composition (yield 79%, pale yellow oil).

[0104] The said curing agent composition contains 33 wt% of Compound 1 corresponding to the first compound where n = 1 in the said Chemical Formula 1, 46 wt% of Compound 2 corresponding to the second compound where n = 2 in the said Chemical Formula 1, 18 wt% of Compound 3 corresponding to the third compound where n = 3 in the said Chemical Formula 1, and 3 wt% of Compound 4 corresponding to the fourth compound where n = 0 in the said Chemical Formula 1.

[0105] Production Example 4. Production of Hardener Composition The curing agent composition of Production Example 1 was subjected to silica column (Hexane (Hex): Ethyl acetate (EA) = 1:1) conditions to remove Compound 3 corresponding to the third compound where n = 3 in the said Chemical Formula 1 and Compound 4 corresponding to the fourth compound where n = 0 in the said Chemical Formula 1.

[0106] The purified curing agent composition contains 55 wt% of Compound 1 corresponding to the first compound where n = 1 in the said Chemical Formula 1 and 45 wt% of Compound 2 corresponding to the second compound where n = 2 in the said Chemical Formula 1.

[0107] Production Example 5. Production of Hardener Composition The curing agent composition of Production Example 2 was subjected to silica column (Hexane (Hex): Ethyl acetate (EA) = 1:1) conditions to remove Compound 3 corresponding to the third compound where n = 3 in the said Chemical Formula 1 and Compound 4 corresponding to the fourth compound where n = 0 in the said Chemical Formula 1.

[0108] The refined hardener composition contains 45% by weight of Compound 1 corresponding to the first compound where n = 1 in Chemical Formula 1 and 55% by weight of Compound 2 corresponding to the second compound where n = 2 in Chemical Formula 1.

[0109] Production Example 6. Production of Hardener Composition The hardener composition of Production Example 2 was separated into Compound 1 corresponding to the first compound where n = 1 in Chemical Formula 1 and Compound 2 corresponding to the second compound where n = 2 in Chemical Formula 1 under the conditions of a silica column (Hexane (Hex): Ethyl Acetate (EA) = 1:1).

[0110] Thereafter, 80% by weight of Compound 1 corresponding to the first compound where n = 1 in Chemical Formula 1 was mixed, and 20% by weight of Compound 2 corresponding to the second compound where n = 2 in Chemical Formula 1 was mixed to prepare a hardener composition.

[0111] Production Example 7. Production of Hardener Composition The hardener composition of Production Example 2 was separated into Compound 1 corresponding to the first compound where n = 1 in Chemical Formula 1 and Compound 2 corresponding to the second compound where n = 2 in Chemical Formula 1 under the conditions of a silica column (Hexane (Hex): Ethyl Acetate (EA) = 1:1).

[0112] Thereafter, 20% by weight of Compound 1 corresponding to the first compound where n = 1 in Chemical Formula 1 was mixed, and 80% by weight of Compound 2 corresponding to the second compound where n = 2 in Chemical Formula 1 was mixed to prepare a hardener composition.

[0113] Comparative Production Example 1. Production of 2,4,6-Tris(2-allylphenoxy)-1,3,5-triazine (TAPT) To a flask equipped with a thermometer, a condenser, and a stirrer, 15.0 parts by mass of cyanuric chloride, 40.8 parts by mass of toluene, 4.1 parts by mass of dimethylformamide, 32.9 parts by mass of 2-allylphenol, and 67.6 parts by mass of potassium carbonate were added, and the temperature was raised to 100°C.

[0114] After reacting at 100 °C for 6 hours and cooling, 200 parts by mass of toluene was added, followed by washing with water and concentration under reduced pressure, to obtain 37.9 parts by mass (yield 98%) of an etherification reaction product (AP-CC) of cyanuric chloride and 2-allylphenol represented as the following Compound 3 (2,4,6-tris(2-allylphenoxy)-1,3,5-triazine (TAPT)). The melting point of the obtained reaction product was 110 °C.

[0115] <Compound 3> JPEG2025522596000023.jpg80170

[0116] Evaluation Example 1: Solubility Evaluation A curing agent composition according to Production Example 1 was prepared. A photograph of the curing agent composition according to Production Example 1 is shown in FIG. 1.

[0117] 2,4,6-Tris(2-allylphenoxy)-1,3,5-triazine (TAPT) produced in Comparative Production Example 1 was dissolved in toluene to prepare solutions having concentrations of 10%, 20% and 50% respectively. Whether the curing agent composition or TAPT was dissolved in the prepared solutions was visually evaluated to evaluate the solubility in toluene. The evaluation results are shown in FIG. 2 and Table 1 below.

[0118] Referring to FIG. 1, FIG. 2 and Table 1, the curing agent composition produced in Production Example 1 existed in a liquid state at room temperature and did not require further dissolution, while TAPT produced in Comparative Production Example 1 existed in a solid state at room temperature and required further dissolution.

[0119] Also, TAPT produced in Comparative Production Example 1 had no solubility in a solution with a concentration of 50%, and tended to partially precipitate in a solution with a concentration of 20%, and a highly concentrated solution in toluene could not be produced. Therefore, there was a problem that TAPT was precipitated due to evaporation of toluene during curing when the TAPT solution was under high temperature conditions in a vacuum state.

[0120] Evaluation Example 2: Measurement of Decomposition Temperature (Td) Using a thermogravimetric analyzer (TGA), under purging gas N2 conditions, the temperature was increased by 20 °C per minute until the maximum temperature reached 900 °C. The decomposition temperatures (Td) of the curing agent compositions produced in Production Examples 1 to 7 and Comparative Production Example 1, triallyl isocyanurate (TAIC: CAS 1025-15-6, product number 114235) purchased from Sigma-Aldrich, and triallyl cyanurate (TAC: CAS 101-37-1, product number 291609) were measured. The decomposition temperature (Td) was measured using a thermogravimetric analyzer at the temperature when the weight of the sample was reduced by 5%. The measurement results are shown in Table 1.

[0121] Also, the result of measuring the decomposition temperature (Td) of the curing agent composition produced according to Production Example 1 is shown in Figure 3, and the result of measuring the decomposition temperature (Td) of triallyl isocyanurate (TAIC) is shown in Figure 4.

[0122] Referring to Figure 3, Figure 4, and Table 1, when comparing the 5% loss intervals, the decomposition temperature (Td) of triallyl isocyanurate (TAIC) corresponding to the compound 4 is 142.73 °C, while the decomposition temperature (Td) of the curing agent composition produced in Production Example 1 is 190.29 °C, and the decomposition temperature (Td) has increased by 50 °C.

[0123] Thereby, even when a crosslinking reaction is carried out under vacuum high-temperature conditions, the curing agent composition can effectively prevent the occurrence of curing deviation due to the decomposition of the curing agent composition.

[0124]

Table 1

[0125] Example 1 To 20.0 parts by mass of polyphenylene oxide modified with methacrylate (mPPO) (SA-9000, manufactured by Sabic), 5.0 parts by mass of a curing agent (the curing agent composition of Production Example 1) was added, and 20.93 parts by mass of toluene was added as a solvent. The mixture was dissolved with a sonicator for 2 hours (maximum temperature 40 °C). Then, 0.582 parts by mass of dicumyl peroxide (DCP), which is an initiator, was added to produce a varnish.

[0126] After impregnating the varnish with glass fiber, it was dried in an oven at 130 °C for 3 minutes. Then, it was pressed at 180 °C for 2 hours to produce a copper-clad laminate (CCL).

[0127] Examples 2 to 7, and Comparative Examples 1 to 3 A copper-clad laminate (CCL) was produced in the same manner as in Example 1, except that the content of the solvent, the type and content of the curing agent, and the content of the initiator were changed as shown in Table 2 below.

[0128] Evaluation Example 3: Measurement of Glass Transition Temperature (Tg) As a differential scanning calorimeter, DSC (Q20, manufactured by TA Instrument) was used. 10 mg of the copper-clad laminates (CCLs) according to Examples 1 to 7 and Comparative Examples 1 to 3 were respectively set on an aluminum support stage, nitrogen gas was introduced at a flow rate of 50 ml / min, and the temperature was raised from 30 °C to 300 °C at a heating rate of 20 °C / min. The glass transition temperature was measured according to JIS K 7121-1987. Also, the glass transition temperature of the copper-clad laminate (CCL) was repeatedly measured 4 times under the same conditions, and the measurement results are shown in Table 2 below.

[0129]

Table 2

[0130] Referring to Table 2 above, it was confirmed that the copper clad laminate (CCL) containing the curing agent composition according to the examples of the present application has a glass transition temperature (Tg) at a similar level when compared with the copper clad laminate (CCL) containing the curing agent composition according to the comparative examples. However, when the curing agent composition according to the examples was included, it was confirmed that even when the glass transition temperature (Tg) value was repeatedly measured, the deviation between the repeatedly measured glass transition temperatures (Tg) was reduced compared to the case where the curing agent composition according to the comparative examples was included.

[0131] That is, the curing agent composition according to the examples has a reduced dispersion value of the glass transition temperature (Tg) compared to the curing agent composition according to the comparative examples. Thereby, during vacuum high-temperature curing, the curing deviation due to partial volatilization of the curing agent composition can be effectively prevented.

[0132] In addition, Comparative Example 1 containing TAPT according to Comparative Production Example 1 was different from the curing agent composition according to the examples. Since TAPT was not dissolved and was mostly precipitated, it was impossible to measure the glass transition temperature (Tg) of the copper clad laminate (CCL).

[0133] The above-described examples and comparative examples are illustrative for explaining the present invention, and the present invention is not limited thereto. For those having ordinary knowledge in the technical field to which the present invention pertains, various modifications can be made therefrom and the present invention can be implemented. Therefore, the technical protection scope of the present invention is defined by the scope of the claims.

Claims

1. A curing agent composition comprising a first compound represented by the following chemical formula 1 with n being 1 and a second compound represented by the following chemical formula 1 with n being 2: [Chemical formula 1] [Chemical formula 2] In the above chemical formulas 1 and 2, X is represented by the above chemical formula 2, X １ is N or CR １ and X ２ is N or CR ２ and X ３ is N or CR ３ and *, *' and *" are, independently of each other, bonding sites with Y or Z in the above chemical formula 1, Y is C ２ -C １５ an alkenyl group, Z is C ８ -C ２１ an alkenylphenyl group, R １ or R ３ is, independently of each other, hydrogen, C １ -C １５ alkyl group, C ２ -C １５ alkenyl group or C ８ -C ２１ alkenylphenyl group, and n is an integer from 0 to 3.

2. The curing agent composition according to claim 1, wherein the ratio of the content of the first compound to the content of the second compound is from 10:90 to 90:

10.

3. The curing agent composition according to claim 1, wherein the content of the first compound is more than or equal to the content of the second compound.

4. The curing agent composition according to claim 1, further comprising a third compound represented by the above chemical formula 1 with n being 3 or a fourth compound represented by the above chemical formula 1 with n being 0.

5. The curing agent composition according to claim 4, wherein the total weight of the third compound and the fourth compound is 25% by weight or less based on the total weight of the curing agent composition.

6. In the chemical formula (2), X １ or X ３ is N, respectively. The curing agent composition according to claim 1.

7. In the above chemical formula 1, The curing agent composition according to claim 1, wherein Y is represented by the following chemical formula 3: [Chemical formula 3] In the above chemical formula 3, m is an integer from 0 to 5, * is a bonding site with the above chemical formula 2.

8. The curing agent composition according to claim 1, wherein Z is represented by any one of the following chemical formulas 4-1 to 4-3: [Chemical formula 4-1] [Chemical formula 4-2] [Chemical formula 4-3] In the above chemical formulas 4-1 to 4-3, l is an integer from 0 to 5, * is a bonding site with the above chemical formula 2.

9. The curing agent composition according to claim 1, wherein the decomposition temperature (Td) of the curing agent composition is 150 °C or higher.

10. A curable composition comprising the curing agent composition according to claim 1, a base polymer, and an initiator.

11. The curable composition according to claim 10, wherein the base polymer comprises acrylate-modified polyphenylene oxide (mPPO) or methacrylate-modified polyphenylene oxide (mPPO).

12. The curable composition according to claim 10, wherein the initiator comprises a peroxide-based initiator.

13. The curable composition according to claim 10, wherein the ratio of the number of moles of the initiator to the number of moles of the curing agent composition is from 0.01 to 0.

5.

14. The curable composition according to claim 10, wherein the ratio of the weight of the base polymer to the weight of the curing agent composition is from 0.1 to 10.

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