Curing agent composition and curable composition comprising same

Abstract

A curing agent composition includes: a first compound represented by Formula 1, wherein n = 1; and a second compound represented by Formula 1, where n = 2, the curing agent composition exhibits a high decomposition temperature and excellent solubility, so that uneven curing caused by partial decomposition of the curing agent when cross-linking in vacuum at a high temperature can be prevented. Formula 1, # imgabs0 #

Description

Technical Field

[0001] The present invention provides a curing agent composition and a curable composition comprising the same. Background Art

[0002] In the fifth generation communication system "5G" which is currently being developed at an accelerated pace, progress is expected in new large capacity and high-speed communication in data communication of various devices including smartphones. The demand for materials with low dielectric loss tangent is increasing, and a dielectric loss tangent of at least 0.005 or less at 1 GHz is required, and a material that can achieve these heat resistance and dielectric properties (dielectric loss tangent) is required.

[0003] In particular, triallyl isocyanurate (TAIC) is often used as a curing agent in 5G copper-clad laminates (CCLs) to achieve excellent low dielectric properties. Since the double bonds at the ends of TAIC are cross-linked with the polymer through an initiator, TAIC cures the polymer to provide a CCL for 5G with low dielectric properties.

[0004] However, since TAIC has a low decomposition temperature (Td), if cross-linked under vacuum and high temperature conditions, TAIC partially evaporates, causing localized uneven curing, which may cause deterioration of heat resistance and durability. In this context, in order to prevent uneven curing, the demand for curing agents with high decomposition temperatures (Td) is increasing. Summary of the invention

[0005] Technical issues

[0006] One aspect of the present disclosure provides a cross-linking agent having a high decomposition temperature and a curable composition including the same.

[0007] Technical Solution

[0008] One aspect of the present disclosure relates to a curing agent composition, comprising: a first compound represented by Formula 1, wherein n=1; and a second compound represented by Formula 1, wherein n=2.

[0009] <Formula 1>

[0010]

[0011] <Formula 2>

[0012]

[0013] In equation 1 and equation 2,

[0014] X can be expressed by formula 2,

[0015] X1 can be N or CR1,

[0016] X2 can be N or CR2,

[0017] X3 can be N or CR3,

[0018] *, *' and *" may each independently be a binding site for Y or Z in Formula 1,

[0019] Y can be C2 to C 15 Alkenyl,

[0020] Z can be C8 to C 21 Alkenylphenyl,

[0021] R1 to R3 can each independently be hydrogen, C1 to C 15 Alkyl, C2 to C 15 Alkenyl or C8 to C 21 Alkenylphenyl,

[0022] n can be an integer from 0 to 3.

[0023] Another aspect of the present disclosure relates to a curable composition including the curing agent composition.

[0024] Beneficial Effects

[0025] The curing agent composition according to the present disclosure, since it has a high decomposition temperature, can prevent uneven curing due to partial decomposition of the curing agent composition even when cross-linked at a high temperature in a vacuum.

[0026] Furthermore, the curing agent composition according to the present disclosure may have excellent solubility even if the decomposition temperature increases. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is a photograph of the liquid curing agent composition prepared according to Preparation Example 1.

[0028] Figure 2 This is a photograph for evaluating the solubility of the composition prepared according to Comparative Preparation Example 1.

[0029] Figure 3 is a graph showing the measurement results of the decomposition temperature of the curing agent composition prepared according to Preparation Example 1 measured using a thermogravimetric analyzer (TGA).

[0030] Figure 4 is a graph showing the measurement results of the decomposition temperature of TAIC measured using a thermogravimetric analyzer (TGA). DETAILED DESCRIPTION

[0031] Hereinafter, various aspects and embodiments of the present disclosure will be described in more detail.

[0032] The terms or words used in this specification and claims should not be understood as conventional or dictionary meanings, but should be understood as meanings and concepts consistent with the technical concepts of the present disclosure based on the principle that the inventor can appropriately define the concepts of the terms in order to best describe his invention.

[0033] The terms used in this specification are only used to describe the purpose of specific embodiments, and are not intended to limit the present disclosure. As used in this specification, the singular form is also intended to include the plural form, unless the context clearly indicates otherwise. As used in this specification, the terms "include" and / or "comprise" specify the presence of the described features, integers, steps, operations, elements, components or combinations thereof, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components or combinations thereof.

[0034] In particular, the curing agent composition according to one aspect of the present disclosure may include: a first compound represented by Formula 1, wherein n=1; and a second compound represented by Formula 1, wherein n=2.

[0035] <Formula 1>

[0036]

[0037] <Formula 2>

[0038]

[0039] In equation 1 and equation 2,

[0040] In formula 1,

[0041] X can be expressed by formula 2,

[0042] In Formula 2, X1 may be N or CR1, X2 may be N or CR2, X3 may be N or CR3, and *, *' and *" may each independently be a binding site with Y or Z in Formula 1,

[0043] Y can be C2 to C 15 Alkenyl, Z can be C8 to C 21 Alkenylphenyl,

[0044] R1 to R3 can each independently be hydrogen, C1 to C 15 Alkyl, C2 to C 15 Alkenyl or C8 to C 21 The term "alkenylphenyl" may be an alkenylphenyl group, and n may be an integer from 0 to 3.

[0045] According to the embodiment, the first compound may be represented by the following Formula 1-1.

[0046] <Formula 1-1>

[0047]

[0048] In Formula 1-1, X can be represented by Formula 2, and Y can be C2 to C 15 Alkenyl, Z can be C8 to C 21 Alkenylphenyl.

[0049] For example, the first compound can include Compound 1.

[0050] <Compound 1>

[0051]

[0052] According to the embodiment, the second compound may be represented by Formula 1-2.

[0053] <Formula 1-2>

[0054]

[0055] In Formula 1-2, X can be represented by Formula 2, and Y can be C2 to C 15 Alkenyl, Z can be C8 to C 21 Alkenylphenyl.

[0056] For example, the second compound can include Compound 2.

[0057] <Compound 2>

[0058]

[0059] According to an embodiment, a ratio of the content of the first compound to the content of the second compound may be about 10:90 to about 90:10.

[0060] According to embodiments, the ratio of the content of the first compound to the content of the second compound may be about 40:60 to about 90:10, about 45:55 to about 90:10, about 50:50 to about 90:10, about 40:60 to about 80:20, or about 40:60 to about 70:30.

[0061] According to an embodiment, the content of the first compound may be greater than or equal to the content of the second compound. If the content of the first compound is greater than the content of the second compound, the curing agent composition may exhibit a high decomposition temperature and excellent solubility.

[0062] According to an embodiment, the curing agent composition may further include: a third compound represented by Formula 1, wherein n is 3; or a fourth compound represented by Formula 1, wherein n is 0. For example, the curing agent composition may further include a third compound represented by Formula 1, wherein n is 3. For example, the curing agent composition may further include a fourth compound represented by Formula 1, wherein n is 0. For example, the curing agent composition may further include: a third compound represented by the above Formula 1, wherein n is 3; and a fourth compound represented by the above Formula 1, wherein n is 0.

[0063] According to the embodiment, the third compound may be represented by Formula 1-3.

[0064] <Formula 1-3>

[0065]

[0066] In Formula 1-3, X may be represented by Formula 2, and Z may be C8 to C 21 Alkenylphenyl.

[0067] For example, the third compound may include Compound 3 below.

[0068] <Compound 3>

[0069]

[0070] According to the embodiment, the fourth compound may be represented by Formula 1-4.

[0071] <Formula 1-4>

[0072]

[0073] In Formula 1-4, X can be represented by Formula 2 above, and Y can be C2 to C 15 Alkenyl.

[0074] For example, the fourth compound may include Compound 4.

[0075] <Compound 4>

[0076]

[0077] According to an embodiment, the sum of the weight of the third compound and the weight of the fourth compound may be 25 wt % or less relative to the total weight of the curing agent composition.

[0078] According to an embodiment, the sum of the weight of the third compound and the weight of the fourth compound may be 24 wt % or less, 22 wt % or less, 21 wt % or less, or 20 wt % or less relative to the total weight of the curing agent composition.

[0079] According to an embodiment, in Formula 2, X1, X2, and X3 may be the same.

[0080] According to an embodiment, X1, X2 and X3 may each be N.

[0081] According to the embodiment, Y in Formula 1 may be represented by Formula 3.

[0082] <Formula 3>

[0083]

[0084] In formula 3,

[0085] m can be an integer from 0 to 5,

[0086] * can be a binding site with Formula 2.

[0087] For example, in Formula 3, if m is 0, Y may be a vinyl group.

[0088] According to the embodiment, in Formula 3, m may be an integer of 1 to 3.

[0089] According to an embodiment, Y may be an allyl group.

[0090] According to the embodiment, Z in Formula 1 may be represented by any one of Formula 4-1 to Formula 4-3.

[0091] <Formula 4-1>

[0092]

[0093] <Formula 4-2>

[0094]

[0095] <Formula 4-3>

[0096]

[0097] In Formula 4-1 to Formula 4-3,

[0098] l can be an integer from 0 to 5,

[0099] * can be a binding site with Formula 2.

[0100] For example, in Formula 4-1 to Formula 4-3, if l is 0, Z may be a vinylphenyl group.

[0101] According to the embodiment, in Formula 4-1 to Formula 4-3, l may be an integer of 1 to 3.

[0102] According to the embodiment, Z in the above Formula 1 may be represented by the following Formula 4-1.

[0103] According to the embodiment, Z in the above Formula 1 may be represented by the following Formula 4-1, and n may be 1.

[0104] According to the embodiment, the decomposition temperature (Td) of the curing agent composition may be 150°C or more. For example, the decomposition temperature (Td) may refer to the temperature at which the mass of the sample measured by a thermogravimetric analyzer (TGA) is reduced by 5%. For example, the decomposition temperature (Td) of the curing agent composition may be 160°C or more, 170°C or more, 180°C or more, or 190°C or more. For example, if the decomposition temperature of the curing agent composition satisfies the above range, the curing agent composition will not undergo decomposition even when cross-linked under vacuum and high temperature conditions, thereby effectively preventing local uneven curing.

[0105] The curable composition according to one aspect of the present disclosure may include: the curing agent composition; a base polymer; and an initiator.

[0106] For example, a base polymer can crosslink with an adjacent base polymer by bonding to double bonds in the curing agent composition.

[0107] According to an embodiment, the base polymer may include modified polyphenylene ether (mPPO). For example, mPPO may include acrylate-modified polyphenylene ether or methacrylate-modified polyphenylene ether.

[0108] According to the embodiment, the modified polyphenylene ether may be represented by Formula 5 below.

[0109] <Formula 5>

[0110]

[0111] In Formula 5, n and m may each independently be an integer greater than or equal to 1.

[0112] The initiator may initiate a crosslinking reaction between the curing agent composition and the base polymer.

[0113] According to an embodiment, the initiator may include a peroxide-based initiator.

[0114] According to an embodiment, the peroxide-based initiator may include dicumyl peroxide, diacyl peroxide, 2,4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, or any combination thereof.

[0115] According to an embodiment, the initiator may include dicumyl peroxide.

[0116] According to an embodiment, the ratio of the number of moles of initiator to the number of moles of curing agent composition can be from about 0.01 to about 0.5. For example, the ratio of the number of moles of initiator to the number of moles of curing agent composition can be from about 0.05 to about 0.5, from about 0.1 to about 0.5, from about 0.1 to about 0.4, or from about 0.2 to about 0.4.

[0117] According to an embodiment, the curable composition may further include a solvent.

[0118] According to an embodiment, the solvent may include toluene, acetone, methyl ethyl ketone, ethyl acetate, or any combination thereof.

[0119] According to an embodiment, the solvent may include toluene.

[0120] According to an embodiment, the content of the base polymer included in the curable composition may be about 50 wt % to about 90 wt % relative to the total weight of the solid, the content of the curing agent composition may be about 1 wt % to about 35 wt % relative to the total weight of the solid, and the content of the initiator may be about 1 wt % to about 15 wt % relative to the total weight of the solid. The total weight of the solid may refer to the total weight of all components in the curable composition except the solvent.

[0121] According to an embodiment, the ratio of the weight of the base polymer to the weight of the curing agent composition may be from about 0.1 to about 10. For example, the ratio of the weight of the base polymer to the weight of the curing agent composition may be from about 1 to about 10, from about 2 to about 10, from about 1 to about 8, from about 1 to about 6, from about 1 to about 4, or from about 1 to about 3.

[0122] [Definition of terms]

[0123] The terms "C1 to C 15 The term “alkyl” refers to a straight or branched aliphatic monovalent hydrocarbon group having 1 to 15 carbon atoms, and as specific examples may include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, tert-decyl and the like.

[0124] The terms "C2 to C 15 "Alkenyl" refers to a C2 to C 15 The alkyl group is a monovalent hydrocarbon group containing one or more C═C double bonds in the middle or at the terminal, and as specific examples, may include ethenyl, propenyl, butenyl, and the like.

[0125] The terms "C8 to C 21 "Alkenylphenyl" refers to a phenyl group substituted with one or more C2 to C 15 The monovalent phenyl group of the alkenyl group, and as specific examples, may include 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl, 2-propenylphenyl, 3-propenylphenyl, 4-propenylphenyl, 2-butenylphenyl, 3-butenylphenyl, 4-butenylphenyl and the like.

[0126] The terms "C6 to C 60 The term "aryl group" refers to a monovalent group having a carbocyclic aromatic system containing 6 to 60 carbon atoms, and may include, for example, phenyl, pentalenyl, naphthyl, azulenyl, indacenyl, acenaphthyl, phenalenyl, phenanthrenyl, anthracenyl, fluoranthenyl, triphenylene, pyrenyl, yl group, peryl group, pentaphenyl group, heptalenyl group, naphthacenyl group, picenyl group, hexacenyl group, pentaphenyl group, rubicenyl group, coronenyl group, ovalenyl group, etc. 60 When the aryl group includes two or more rings, the two or more rings may be linked to each other.

[0127] Hereinafter, the inventive concept will be described in more detail by way of examples. The following examples are provided only for a better understanding of the inventive concept, and it is obvious to those skilled in the art that the scope of the inventive concept is not limited by these examples.

[0128] Preparation Example 1. Preparation of curing agent composition

[0129] In a five-necked flask equipped with a thermometer, a condenser and a stirrer, the following components were added and stirred: 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.

[0130] Then, 6.83 parts by mass of 50% NaOH was added thereto, and while the temperature was raised to 70° C. without controlling the heat, the mixture was reacted for 1 hour.

[0131] Then, the mixture was cooled to 25°C, 9.92 parts by mass of allyl alcohol and 13.68 parts by mass of 50% NaOH were added thereto, and the mixture was heated to 70°C and reacted for 5 hours.

[0132] The mixture was then cooled to 25°C and washed with water by adding 30 parts by mass of water. The washing was repeated 5 times in total, and the toluene layer was removed by filtration through diatomaceous earth. The obtained product was then concentrated under reduced pressure to produce 24 parts by mass of a curing agent composition (85% yield, light yellow oil).

[0133] The curing agent composition comprises: 44 wt % of compound 1, corresponding to the first compound of formula 1, wherein n=1; 37 wt % of compound 2, corresponding to the second compound of formula 1, wherein n=2; 12 wt % of compound 3, corresponding to the third compound of formula 1, wherein n=3; and 8 wt % of compound 4, corresponding to the fourth compound of formula 1, wherein n=0.

[0134] <Compound 1>

[0135]

[0136] <Compound 2>

[0137]

[0138] <Compound 3>

[0139]

[0140] <Compound 4>

[0141]

[0142] Preparation Example 2. Preparation of curing agent composition

[0143] In a five-necked flask equipped with a thermometer, a condenser and a stirrer, the following components were added and stirred: 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.

[0144] Then, 9.76 parts by mass of 50% NaOH was added thereto, and while the temperature was raised to 70° C. without controlling the heat, the mixture was reacted for 1 hour.

[0145] The mixture was then cooled to 25°C, and after 7.09 parts by mass of allyl alcohol and 9.76 parts by mass of 50% NaOH were added thereto, the mixture was heated to 70°C and the mixture was reacted for 5 hours.

[0146] The mixture was then cooled to 25°C and washed with water by adding 30 parts by mass of water. The washing was repeated 5 times in total, and the toluene layer was removed by filtration through diatomaceous earth. The obtained product was then concentrated under reduced pressure to produce 24 parts by mass of a curing agent composition (81% yield, light yellow oil).

[0147] The curing agent composition comprises: 38 wt % of compound 1, corresponding to the first compound of formula 1, wherein n=1; 42 wt % of compound 2, corresponding to the second compound of formula 1, wherein n=2; 15 wt % of compound 3, corresponding to the third compound of formula 1, wherein n=3; and 5 wt % of compound 4, corresponding to the fourth compound of formula 1, wherein n=0.

[0148] Preparation Example 3. Preparation of curing agent composition

[0149] In a five-necked flask equipped with a thermometer, a condenser and a stirrer, the following components were added and stirred: 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.

[0150] Then, 13.01 parts by mass of 50% NaOH was added thereto, and while the temperature was raised to 70° C. without controlling the heat, the mixture was reacted for 1 hour.

[0151] The mixture was then cooled to 25°C, 4.96 parts by mass of allyl alcohol and 6.83 parts by mass of 50% NaOH were added thereto, and the mixture was heated to 70°C and reacted for 5 hours.

[0152] The mixture was then cooled to 25°C and washed with water by adding 30 parts by mass of water. The washing was repeated 5 times in total, and the toluene layer was removed by diatomaceous earth filtration. The obtained product was then concentrated under reduced pressure to produce 24 parts by mass of a curing agent composition (79% yield, light yellow oil).

[0153] The curing agent composition comprises: 33 wt % of compound 1, corresponding to the first compound of formula 1, wherein n=1; 46 wt % of compound 2, corresponding to the second compound of formula 1, wherein n=2; 18 wt % of compound 3, corresponding to the third compound of formula 1, wherein n=3; and 3 wt % of compound 4, corresponding to the fourth compound of formula 1, wherein n=0.

[0154] Preparation Example 4. Preparation of curing agent composition

[0155] The curing agent composition of Preparation Example 1 was purified on a silica chromatography column (Hex:EA=1:1) by removing Compound 3 corresponding to the third compound of Formula 1 (wherein n=3) and Compound 4 corresponding to the fourth compound of Formula 1 (wherein n=0).

[0156] The purified curing agent composition contained: 55 wt % of Compound 1, which corresponds to the first compound of Formula 1, wherein n=1; and 45 wt % of Compound 2, which corresponds to the second compound of Formula 1, wherein n=2.

[0157] Preparation Example 5. Preparation of curing agent composition

[0158] The curing agent composition of Preparation Example 2 was purified on a silica chromatography column (Hex:EA=1:1) by removing Compound 3 corresponding to the third compound of Formula 1 (wherein n=3) and Compound 4 corresponding to the fourth compound of Formula 1 (wherein n=0).

[0159] The purified curing agent composition contained: 45 wt % of Compound 1, which corresponds to the first compound of Formula 1, wherein n=1; and 55 wt % of Compound 2, which corresponds to the second compound of Formula 1, wherein n=2.

[0160] Preparation Example 6. Preparation of curing agent composition

[0161] The curing agent composition of Preparation Example 2 was purified on a silica chromatography column (Hex:EA=1:1) by removing Compound 1 corresponding to the first compound of Formula 1 (wherein n=1) and Compound 2 corresponding to the second compound of Formula 1 (wherein n=2).

[0162] Thereafter, a curing agent composition was prepared by mixing 80 wt % of Compound 1 corresponding to the first compound of Formula 1 (wherein n=1) and 20 wt % of Compound 2 corresponding to the second compound of Formula 1 (wherein n=2).

[0163] Preparation Example 7. Preparation of curing agent composition

[0164] The curing agent composition of Preparation Example 2 was purified on a silica chromatography column (Hex:EA=1:1) by removing Compound 1 corresponding to the first compound of Formula 1 (wherein n=1) and Compound 2 corresponding to the second compound of Formula 1 (wherein n=2).

[0165] Thereafter, a curing agent composition was prepared by mixing 20 wt % of Compound 1 corresponding to the first compound of Formula 1 (wherein n=1) and 80 wt % of Compound 2 corresponding to the second compound of Formula 1 (wherein n=2).

[0166] Comparative Preparation Example 1. Preparation of 2,4,6-tris(2-allylphenoxy)-1,3,5-triazine (TAPT)

[0167] In a flask equipped with a thermometer, a condenser and a stirrer were added 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, and the temperature was raised to 100°C.

[0168] The obtained mixture was reacted at 100° C. for 6 hours, then cooled, and after 200 parts by mass of toluene was added thereto, the obtained mixture was washed with water and concentrated under reduced pressure to obtain 37.9 parts by mass of an esterification reaction product of cyanuric chloride and 2-allylphenol (AP-CC), which was represented as the following compound 3 (TAPT (2,4,6-tris (2-allylphenoxy) -1,3,5-triazine)). The melting point of the obtained reaction product was 110° C.

[0169] <Compound 3>

[0170]

[0171] Evaluation Example 1: Solubility Evaluation

[0172] The curing agent composition of Preparation Example 1 was prepared. Figure 1 A photograph of the curing agent composition of Preparation Example 1 is shown.

[0173] The TAPT prepared in Comparative Preparation Example 1 was dissolved in toluene to prepare solutions having concentrations of 10%, 20%, and 50%, respectively. The solubility in toluene was evaluated by visually evaluating whether the curing agent composition or TAPT was completely dissolved in the prepared solution. The evaluation results are shown in Figure 2 and Table 1.

[0174] Reference Figure 1 , Figure 2 As shown in Table 1, the curing agent composition prepared in Preparation Example 1 remained in a liquid state at room temperature and thus did not require further dissolution, whereas the TAPT prepared in Comparative Preparation Example 1 remained in a solid state and thus required further dissolution.

[0175] Furthermore, since the TAPT prepared in Comparative Preparation Example 1 showed no solubility in a 50% concentration solution and partially precipitated in a 20% concentration solution, a high concentration solution in toluene could not be prepared. Therefore, when the TAPT solution was cured at a high temperature under vacuum, there was a problem that TAPT precipitated as toluene evaporated.

[0176] Evaluation Example 2: Measurement of Decomposition Temperature (Td)

[0177] Using a thermogravimetric analyzer (TGA), the decomposition temperature of each of the curing agent compositions prepared in Preparation Examples 1 to 7 and Comparative Preparation Example 1, triallyl isocyanurate (TAIC, CAS1025-15-6, product number 114235) and triallyl cyanurate (TAC, CAS101-37-1, product number 291609) purchased from Sigma-Aldrich was measured at a rate of 20°C per minute under N2 gas purge. The temperature at which the weight of the sample measured by the thermogravimetric analyzer was reduced by 5% was taken as the decomposition temperature. The measurement results are shown in Table 1.

[0178] In addition, the measurement results of the decomposition temperature of the curing agent composition prepared in Preparation Example 1 are shown in Figure 3 The measurement results of the decomposition temperature of TAIC are shown in Figure 4 middle.

[0179] Reference Figure 3 , Figure 4 As shown in Table 1, within the 5% loss portion, the decomposition temperature of TAIC corresponding to Compound 4 is 142.73°C, while the curing agent composition of Preparation Example 1 exhibits a decomposition temperature of 190.29°C, which is increased by 50°C.

[0180] This indicates that the curing agent composition can effectively prevent uneven curing due to decomposition of the curing agent composition even when the cross-linking reaction is performed under vacuum and high temperature conditions.

[0181] Table 1

[0182]

[0183] Example 1

[0184] 5.0 parts by mass of a curing agent (the curing agent composition of Preparation Example 1) and 20.93 parts by mass of toluene as a solvent were added to 20.0 parts by mass of a methacrylate-modified polyphenylene ether (mPPO, Sabic, SA-9000), and the resulting mixture was dissolved in an ultrasonic oscillator (temperature up to 40° C.) for 2 hours. Then, 0.582 parts by mass of dicumyl peroxide (DCP) as an initiator was added thereto to prepare a varnish.

[0185] After the varnish was impregnated with the glass fiber, the obtained product was dried in an oven at 130° C. for 3 minutes. Then, the obtained product was pressed at 180° C. for 2 hours to manufacture a copper clad laminate (CCL).

[0186] Examples 2 to 7 and Comparative Examples 1 to 3

[0187] A copper clad laminate (CCL) was prepared according to the same procedure as in Example 1, except that the amount of the solvent, the type and amount of the curing agent, and the amount of the initiator were changed as shown in Table 2.

[0188] Evaluation Example 3: Measurement of glass transition temperature (Tg)

[0189] Using DSC (Q20) (TA Instrument) as a differential scanning calorimeter, 10 mg of each copper clad laminate (CCL) of Examples 1 to 7 and Comparative Examples 1 and 2 was placed on an aluminum-based support, and the temperature was increased from 30° C. to 300° C. at a rate of 20° C. / min while nitrogen was flowing at a flow rate of 50 mL / min, and the glass transition temperature was measured according to JIS K7121-1987. In addition, the glass transition temperature of each CCL was measured four times under the same conditions, and the measurement results are shown in Table 2.

[0190] Table 2

[0191]

[0192]

[0193] Referring to Table 2, it can be found that the CCL including the curing agent composition according to the embodiment of the present disclosure has a similar level of Tg as compared to the CCL including the curing agent composition according to the comparative example. Specifically, it can be found that in the case of including the curing agent composition according to the embodiment, even when Tg is repeatedly measured, the deviation of the Tg value in repeated measurements is smaller than that of the case of including the curing agent composition according to the comparative example.

[0194] In other words, the curing agent composition according to the embodiment exhibits a smaller Tg variation than the curing agent composition according to the comparative example. Therefore, uneven curing due to partial evaporation of the curing agent composition during curing at high temperature under vacuum can be effectively prevented.

[0195] Furthermore, unlike the curing agent composition according to the example, in the case of Comparative Example 1 including the TAPT according to Comparative Preparation Example 1, since most of the TAPT was precipitated instead of dissolved, the Tg of the CCL could not be measured.

[0196] The above-mentioned embodiments and comparative examples are only used to illustrate the present disclosure, and are not intended to limit the present disclosure. It is obvious to those skilled in the art that many changes and modifications can be made without departing from the scope and concept of the present disclosure. Therefore, the appended claims are intended to cover all such changes and modifications falling within the scope of the present disclosure.

Claims

1. A curing agent composition comprising: a first compound represented by Formula 1, wherein n is 1; and A second compound represented by Formula 1, wherein n is 2, <Formula 1> <Formula 2> in, In equation 1 and equation 2, X is represented by formula 2, X1 is N or CR1, X2 is N or CR2, X3 is N or CR3, *, *' and *" are each independently a binding site to Y or Z in Formula 1, Y is C2 to C 15 Alkenyl, Z is C8 to C 21 Alkenylphenyl, R1 to R3 are each independently hydrogen, C1 to C 15 Alkyl, C2 to C 15 Alkenyl or C8 to C 21 Alkenylphenyl, n is an integer of 0-3.

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 10:90 to 90:

10.

3. The curing agent composition according to claim 1, wherein The content of the first compound is greater 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 Formula 1, wherein n is 3; or A fourth compound represented by Formula 1, wherein n is 0.

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

6. The curing agent composition according to claim 1, wherein X1 to X3 in Formula 2 are each N.

7. The curing agent composition according to claim 1, wherein In Formula 1, Y is represented by Formula 3: <Formula 3> Among them, in formula 3, m is an integer from 0 to 5, * is the binding site with formula 2.

8. The curing agent composition according to claim 1, wherein Z is represented by any one of Formula 4-1 to Formula 4-3: <Formula 4-1> <Formula 4-2> <Formula 4-3> Among them, in Formula 4-1 to Formula 4-3, 1 is an integer from 0 to 5, * is the binding site with 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; base polymer; and Initiator.

11. The curable composition according to claim 10, wherein The base polymer includes acrylate-modified polyphenylene ether or methacrylate-modified polyphenylene ether.

12. The curable composition according to claim 10, wherein The initiator includes a peroxide initiator.

13. The curable composition according to claim 10, wherein The ratio of the mole number of the initiator to the mole number of the curing agent composition is 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 0.1 to 10.

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