Curing agent composition and curable composition containing the same

Abstract

A curing agent composition comprising a first compound represented by chemical formula 1 and a second compound represented by chemical formula 2, wherein when the curing agent composition is used, dielectric properties, chemical resistance, and high-temperature stability can be improved.

Description

[Technical Field]

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

[0002] In recent years, with the increase in the volume of information and communication, information communication in the high-frequency band has become increasingly active. This has led to a growing need for materials that can handle high-frequency ranges. In particular, materials with low dielectric loss tangents are required to reduce transmission loss in the high-frequency band, and there is a demand for materials that can achieve high heat resistance while having a dielectric loss tangent of 0.005 or less at least 10 GHz.

[0003] In particular, for high-frequency Copper-Clad Laminations (CCLs) that achieve excellent low dielectric loss tangent characteristics, triallyl isocyanurate (TAIC) is mainly used as a curing agent. TAIC provides high-frequency Copper-Clad Laminations with low dielectric properties by curing the polymer through crosslinking of terminal double bonds with the polymer by the initiator.

[0004] However, when crosslinking TAIC (triallyl isocyanurate) under vacuum and high-temperature conditions, the low decomposition temperature (Td, Td, decomposition temperature) of TAIC causes some of the TAIC to volatilize, resulting in hardening variations in different areas. This leads to a problem of reduced heat resistance and durability.

[0005] As a result, there is a growing need for curing agent compositions that have low dielectric loss tangent characteristics while also having a high decomposition temperature (Td) in order to prevent the occurrence of curing deviations. [Overview of the project] [Problems to be Solved by the Invention]

[0006] The technical problem to be solved by the present invention is to provide a curable composition having a high decomposition temperature while having low dielectric tangent characteristics. [Means for Solving the Problems]

[0007] One aspect of the present invention relates to a curing agent composition containing a first compound represented by the following chemical formula 1; and a second compound represented by the following chemical formula 2.

[0008] [Chemical formula 1] JPEG2026521616000001.jpg6770

[0009] [Chemical formula 2] JPEG2026521616000002.jpg6570

[0010] Among the above chemical formulas 1 and 2, R

[0013] ,

[0012] , , , , , or R 13 and R 21 or R 23 are, independently of each other, hydrogen, a C1 to C 15 alkyl group or a C2 to C 15 alkenyl group, a11 is an integer from 0 to 5.

[0011] Another aspect of the present invention relates to a curable composition containing the above curing agent composition. [Advantages of the Invention]

[0012] The curing agent composition according to the present invention has a benzyl group that is bulkier than an allyl group, and as the size of the network structure formed using the curing agent composition increases, the size of the voids increases, and the dielectric properties of an article manufactured using the curing agent composition can be improved.

[0013] Furthermore, by including both the first and second compounds in the curing agent composition, the chemical resistance, high-temperature stability, and mechanical properties can be improved. [Modes for carrying out the invention]

[0014] The following sections will provide a more detailed explanation of various aspects and specific examples of the present invention.

[0015] The terms or words used herein and in the claims shall not be construed to be limited to their ordinary or dictionary meanings, but rather to be construed as meanings and concepts consistent with the technical idea of ​​the invention, based on the principle that an inventor may appropriately define the concept of a term in order to best describe their invention.

[0016] The terms used in this invention are used solely to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this invention, terms such as “includes” or “having” are intended to specify the existence of features, numbers, stages, operations, components, parts, or combinations thereof as described in the specification, and should be understood not to preemptively exclude the existence or possibility of adding one or more other features, numbers, stages, operations, components, parts, or combinations thereof.

[0017] Specifically, a curing agent composition relating to one aspect of the present invention comprises a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2.

[0018] <Chemical formula 1> JPEG2026521616000003.jpg6170

[0019] <Chemical formula 2> JPEG2026521616000004.jpg6264

[0020] Among the above formulas 1 and 2, R 11 or R 13 and R 21 or R 23 are, independently of each other, hydrogen, a C1 to C 15 alkyl group or a C2 to C 15 alkenyl group, a11 is an integer from 0 to 5.

[0021] According to one specific example, the 5% weight loss decomposition temperature (Td) of the curing agent composition can be 150 °C or higher. For example, the decomposition temperature Td means the temperature at the point where the mass of the sample has decreased by 5% based on the measurement results of a thermogravimetric analyzer (TGA). For example, the decomposition temperature Td of the curing agent composition can be 150 to 240 °C, 160 °C to 240 °C, 170 °C to 240 °C, or 180 °C to 240 °C. For example, when the curing agent composition satisfies the above decomposition temperature range, the chemical resistance and high-temperature stability of the article manufactured using the curing agent composition can be improved.

[0022] According to one specific example, the content of the first compound is 70 to 99% by weight based on the total weight of the curing agent composition, and the content of the second compound can be 1 to 30% by weight based on the total weight of the curing agent composition.

[0023] According to one specific example, the content of the first compound can be 75 to 99% by weight, 80 to 99% by weight, 85 to 99% by weight, or 90 to 99% by weight based on the total weight of the curing agent composition.

[0024] According to one specific example, the content of the second compound can be 1 to 25% by weight, 1 to 20% by weight, 1 to 15% by weight, or 1 to 10% by weight based on the total weight of the curing agent composition.

[0025] According to one specific example, among the chemical formula 1, R 11 or R 13 are, independently of each other, hydrogen or a C1 to C15 It can be an alkyl group.

[0026] In one specific example, of the chemical formula 1, R 11 R 13 These can be hydrogen, a methyl group, or an ethyl group, independently of each other.

[0027] In one specific example, the first compound can be represented by the following chemical formula 1-1.

[0028] <Chemical formula 1-1> JPEG2026521616000005.jpg6070

[0029] In one specific example, of the chemical formula 2, R 21 R 23 These are, independently of each other, hydrogen or C1 or C 15 It can be an alkyl group.

[0030] In one specific example, of the chemical formula 2, R 21 R 23 These can be hydrogen, a methyl group, or an ethyl group, independently of each other.

[0031] In one specific example, the second compound can be represented by the following chemical formula 2-1.

[0032] <Chemical formula 2-1> JPEG2026521616000006.jpg6870

[0033] In one specific example, the curing agent composition may further contain a third compound represented by the following chemical formula 3.

[0034] <Chemical formula 3> JPEG2026521616000007.jpg5877

[0035] Of the above chemical formula 3, R 31 R 33 These are, independently of each other, hydrogen, C1 or C15 Alkyl group or C2 or C 15 It is an alkenyl group, a31 and a32 are independent integers between 0 and 5.

[0036] For example, in the chemical formula 3, R 31 R 33 These are, independently of each other, hydrogen or C1 or C 15 It can be an alkyl group.

[0037] For example, in the chemical formula 3, R 31 R 33 These can be hydrogen, a methyl group, or an ethyl group, independently of each other.

[0038] In one specific example, the first compound can be represented by the following chemical formula 3-1.

[0039] <Chemical formula 3-1> JPEG2026521616000008.jpg5977

[0040] In one specific example, the content of the third compound may be 20% by weight or less relative to the total weight of the curing agent composition. For example, the content of the third compound may be 1 to 20% by weight, 1 to 15% by weight, 1 to 10% by weight, or 1 to 5% by weight relative to the total weight of the curing agent composition.

[0041] In one specific example, the curing agent composition may further contain a fourth compound represented by the following chemical formula 4.

[0042] <Chemical formula 4> JPEG2026521616000009.jpg5683

[0043] Of the aforementioned chemical formula 4, R 41 R 43 These are, independently of each other, hydrogen, C1 or C 15 Alkyl group or C2 or C 15It is an alkenyl group, a41, a42, and a43 are independent integers between 0 and 5.

[0044] To give one specific example, of the chemical formula 4, R 41 R 43 These are, independently of each other, hydrogen or C1 or C 15 It can be an alkyl group.

[0045] To give one specific example, of the chemical formula 4, R 41 R 43 These can be hydrogen, a methyl group, or an ethyl group, independently of each other.

[0046] In one specific example, the fourth compound can be represented by the following chemical formula 4-1.

[0047] <Chemical formula 4-1> JPEG2026521616000010.jpg6083

[0048] In one specific example, the content of the fourth compound in the curing agent composition may be 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, or 1% by weight or less, based on the total weight of the curing agent composition.

[0049] A curable composition according to one aspect of the present invention may comprise the curing agent composition; a base polymer; and an initiator.

[0050] The base polymer can be crosslinked with adjacent base polymers by, for example, bonding with double bonds contained in the curing agent composition.

[0051] In one specific example, the base polymer may include modified polyphenylene oxide (mPPO). For example, the modified polyphenylene oxide may include polyphenylene oxide modified with acrylate, methacrylate, aryl group, or vinyl group.

[0052] For example, modified polyphenylene oxide can be represented by the following chemical formula 5.

[0053] <Chemical formula 5> JPEG2026521616000011.jpg32129

[0054] In the aforementioned chemical formula 5, n and m are independent integers of 1 or greater, and X is C1-C 15 Alkylene group or C2-C 15 It is an alkenylene group. For example, in the above chemical formula 5, X may be a methylene group, an ethylene group, an n-propylene group, an isopropylene group, or a butylene group.

[0055] The initiator can initiate a crosslinking reaction between the curing agent composition and the base polymer.

[0056] In one specific example, the initiator may include a peroxide-based initiator.

[0057] In one specific example, the peroxide initiator may include dicumyl peroxide, diacyl peroxide, 2,4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauryl peroxide, propionyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, or any combination thereof.

[0058] In one specific example, the initiator may include dicumyl peroxide.

[0059] In one specific example, the ratio of the number of moles of the initiator to the number of moles of the curing agent composition may be 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 may be 0.05 to 0.5, 0.1 to 0.5, 0.1 to 0.4, or 0.2 to 0.4.

[0060] In one specific example, the curable composition may further contain a solvent.

[0061] In one specific example, the solvent may include toluene, acetone, methyl ethyl ketone, ethyl acetate, or any combination thereof.

[0062] In one specific example, the solvent may include toluene.

[0063] In one specific example, the content of the base polymer in the curable composition may be 50 to 90% by weight relative to the total weight of solids, the content of the curing agent composition may be 1 to 35% by weight relative to the total weight of solids, and the content of the initiator may be 1 to 15% by weight relative to the total weight of solids. The total weight of solids refers to the sum of the weights of the remaining components of the curable composition excluding the solvent.

[0064] In one specific example, the ratio of the weight of the base polymer to the weight of the curing agent composition may be 0.1 to 10. For example, the ratio of the weight of the base polymer to the weight of the curing agent composition may be 1 to 10, 2 to 10, 1 to 8, 1 to 6, 1 to 4, or 1 to 3.

[0065] In one specific example, the glass transition temperature (Tg) of the curable composition may be 260°C or lower. For example, the glass transition temperature (Tg) of the curing agent composition may be 180 to 260°C, 180 to 250°C, 180 to 245°C, or 200 to 245°C.

[0066] In one specific example, the dielectric constant (Dk) of the curable composition may be 2.55 or less. For example, the dielectric constant (Dk) of the curing agent composition may be 2 to 2.55, 2 to 2.5, 2 to 2.4, or 2.2 to 2.3.

[0067] In one specific example, the dielectric loss tangent (Df) of the curable composition may be 0.0044 or less. For example, the dielectric loss tangent (Df) of the curing agent composition may be 0.002 to 0.0044, 0.002 to 0.004, 0.002 to 0.0038, or 0.0025 to 0.0035.

[0068] [Definition of Terms] In this specification, C1-C 15 Alkyl groups refer to linear or branched aliphatic hydrocarbon monovalent groups having 1 to 15 carbon atoms. Specific examples 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, and tert-decyl groups. C1-C in this specification 15 An alkylene group refers to a linear or branched aliphatic hydrocarbon divalent group having 1 to 15 carbon atoms.

[0069] C2-C in this specification 15 The alkenyl group is C2-C 15 This refers to a monovalent hydrocarbon group containing one or more carbon-carbon double bonds in the middle or terminal of the alkyl group, and specific examples include the ethenyl group, profene group, and butenyl group. C2-C 15 The alkenylene group is C2-C 15 This refers to a divalent hydrocarbon group containing one or more carbon-carbon double bonds in the middle or terminal of the alkylene group.

[0070] The present invention will be described in more detail below with reference to examples. These examples are merely for the purpose of illustrating the present invention more concretely, and it will be obvious to those with ordinary skill in the art to which the present invention pertains that the scope of the present invention is not limited by these examples.

[0071] Manufacturing Example 1. Manufacturing of a curing agent composition Manufacturing of DAIC (diallyl-isocyanurate) In a five-necked flask equipped with a thermometer, condenser, and stirrer, 15.0 parts by mass of cyanuric acid, 120.0 parts by mass of water, 0.12 parts by mass of CuCl, and 27.9 parts by mass of 50% NaOH were added and stirred.

[0072] 18.67 parts by mass of allyl chloride was added, and the mixture was heated to 45°C and reacted for 1 hour. After cooling to 30°C, 4.56 parts by mass of phosphoric acid was added to precipitate DAIC.

[0073] After filtering the precipitated DAIC, it was washed with 30 parts by mass of water, then with 30 parts by mass of methanol, and dried in a 100°C vacuum oven for 12 hours to obtain 13 parts by mass of DAIC (purity 96%, pale blue powder).

[0074] <daic> JPEG2026521616000012.jpg4170

[0075] Manufacturing of curing agent compositions 10.0 parts by mass of DAIC, 15.0 parts by mass of DMF, and 3.90 parts by mass of 50% NaOH were added to a five-necked flask equipped with a thermometer, condenser, and stirrer, and the mixture was stirred.

[0076] 6.17 parts by mass of benzyl chloride were added, and the mixture was heated to 100°C and reacted for 1 hour. After cooling to 30°C, the resulting NaCl was filtered through a paper filter, and the remaining solution was placed back into a five-necked flask and concentrated under reduced pressure at 100°C.

[0077] The flask in which concentration was completed was washed with 30 parts by mass of ethyl acetate (EA) and 15 parts by mass of water, and then washed again twice with 15 parts by mass of water.

[0078] Subsequently, the organic layer in the flask was filtered to 2.0 parts by mass of diatomaceous earth, and the diatomaceous earth was washed with 5 parts by mass of ethyl acetate (EA). Then, the mixture was concentrated under reduced pressure at a temperature of 70°C, 10 parts by mass of methanol was added, and the mixture was recrystallized by concentrating under reduced pressure at a temperature of 10°C. The resulting powder was filtered, washed with 10 parts by mass of methanol, and dried in a vacuum oven at 45°C for 12 hours to obtain 9 parts by mass of a curing agent composition (purity 96%, white powder).

[0079] The ratios of the content of the following first, second, and third compounds contained in the aforementioned curing agent composition are shown in Table 1 below.

[0080] <First compound> JPEG2026521616000013.jpg5870

[0081] <Second compound> JPEG2026521616000014.jpg6770

[0082] <Third compound> JPEG2026521616000015.jpg5470

[0083] Manufacturing Examples 2 to 10. Manufacturing of Curing Agent Composition A curing agent composition was prepared in the same manner as in Production Example 1, except that the amount of reactants added was adjusted to change the ratio of the contents of the first, second, and third compounds in the curing agent composition as shown in Table 1 below.

[0084] Manufacturing Examples 11 to 16. Manufacturing of Curing Agent Compositions After producing the DAIC in Production Example 1, compound 1 and compound 2 were separated by column separation (Hexane:EA=1:1), and then compound 1 and compound 2 were mixed in the same proportion as in Table 1. The curing agent composition was then produced in the same manner as in Production Example 1.

[0085] Comparative manufacturing example 1. Preparation of the second compound A curing agent composition containing the second compound was prepared using TAIC (triallyl isocyanurate, product number 114235) from Sigma-aldrich.

[0086] <Second compound> JPEG2026521616000016.jpg6270

[0087] Comparative manufacturing example 2. Manufacturing of the third compound In 205 g of dimethylformamide, 35.6 g (0.21 mol) of allyl isocyanurate and 59.68 g (0.47 mol) of benzyl chloride were reacted at 100°C for 2 hours in the presence of 65.16 g (0.47 mol) of potassium carbonate. After cooling, the reaction mixture was filtered to remove inorganic substances, the filtrate was distilled under reduced pressure to recover the solvent, and the residue was diluted with chloroform and then extracted with alkaline aqueous solution and acid aqueous solution. The obtained extract was washed with water, dried over anhydrous magnesium sulfate and filtered, the chloroform in the filtrate was recovered by distillation under reduced pressure, and isopropyl alcohol was added to the residue to precipitate crystals, which were then filtered. The resulting cake was dried to prepare a curing agent composition containing the third compound described below (purity 99% by weight).

[0088] <Third compound> JPEG2026521616000017.jpg5470

[0089] Evaluation Example 1: Measurement of Decomposition Temperature (Td) Using a thermogravimetric analyzer (TGA), the temperature was increased by 20°C per minute under purging gas N2 conditions up to a maximum of 900°C, and the 5% loss Td (°C) of the curing agent compositions produced in Production Examples 1 to 16 and Comparative Production Examples 1 and 2 was measured. The measurement results are shown in Table 1.

[0090] [Table 1]

[0091] Referring to Table 1, the curing agent composition containing the first compound, the first compound, and the third compound showed an increased decomposition temperature. As a result, the curing agent composition exhibited excellent high-temperature stability.

[0092] Example 1 20.0 parts by mass of methacrylate-modified polyphenylene oxide (KPU-6000) was mixed with 5.0 parts by mass of a curing agent (curing agent composition of Production Example 1) and 20.64 parts by mass of toluene as a solvent, and dissolved in a sonicator for 2 hours (maximum temperature 40°C). Then, 0.226 parts by mass of dicumyl peroxide (DCP), which is an initiator, was added to produce varnish.

[0093] After impregnating the varnish with glass fibers, it was dried at room temperature for 10 minutes, and then heat-dried in an oven at 130°C for 3 minutes. The dried cured material was powdered, and the powder was poured into a frame measuring 1.5 cm x 1.5 cm x 0.5 cm (width x length x height). Then, the frame containing the cured material powder was placed between the copper foils. The copper foils were pressed to 300 bar at 70°C using a pressure press, and then the temperature was raised to 230°C and held for 2 hours. After the pressure was removed, the copper foils and frame were removed to obtain the pressed cured material. The pressed cured material was cut into 1 cm x 1 cm pieces to prepare samples.

[0094] Examples 2 to 16 and Comparative Examples 1 and 2 Samples were prepared in the same manner as in Example 1, except that the solvent content, the type and content of the curing agent, and the initiator content were changed as shown in Table 2 below.

[0095] Evaluation Example 2: Measurement of Dielectric Constant (Dk) and Dielectric Loss Tangent (Df) The 10 GHz dielectric constant of the samples in Examples 1 to 16 and Comparative Examples 1 and 2 was measured using a measurement device (AET's ADMS01O Series).

[0096] For measuring the dielectric constant of the samples in Examples 1 to 16 and Comparative Examples 1 and 2, a frequency of 9.3 GHz was selected for the measurement equipment. For measurement calibration, the frequencies of two reference materials were input. PTFE (Dk=2.03) and SiO2 (Dk=4.41) were selected as the two reference materials for calibration.

[0097] First, the dielectric constant of air was measured as a blank (Dk=1). After the blank measurement was completed, the dielectric constant of PTFE, which was initially selected as the dielectric constant reference, was measured. After placing the sample on the probe and turning on the vacuum pump, the measurement button was pressed to measure the dielectric constant.

[0098] After measuring PTFE, the dielectric constant of SiO2, which was selected as the second dielectric constant reference, was measured. After calibration, the dielectric constants of PTFE and SiO2, which were selected as reference materials, were measured, and if the error range between the actual value and the measured value exceeded ±1% of the reference value, the calibration was repeated.

[0099] Subsequently, the samples from Examples 1 to 16 and Comparative Examples 1 and 2 were placed on the probe, the vacuum pump was turned on, and after preparing them to achieve maximum pressure, the dielectric constant was measured. The dielectric constant and dielectric loss tangent values ​​were calculated from the dielectric constant measurement results and are listed in Table 2 below.

[0100] [Table 2]

[0101] Referring to Table 2 above, the examples prepared from curing agent compositions containing both the first and second compounds showed improved dielectric properties, with reduced dielectric constants and dielectric loss tangents, compared to the comparative examples prepared from curing agent compositions containing only the second compound or only the third compound.

[0102] The above-described examples and comparative examples are illustrative for illustrating the present invention, and the present invention is not limited thereto. Since a person with ordinary skill in the art to which the present invention pertains can implement the present invention by modifying them in various ways, the scope of technical protection of the present invention must be defined by the appended claims.< / daic>

Claims

1. The first compound represented by the following chemical formula 1, A curing agent composition comprising a second compound represented by the following chemical formula 2: <Chemical formula 1> <Chemical formula 2> Of the above chemical formulas 1 and 2, R １１ R １３ and R ２１ R ２３ These are, independently of each other, hydrogen and C １ C １５ Alkyl alkyl group or C ２ C １５ It is an alkenyl group, a11 is an integer between 0 and 5.

2. The content of the first compound is 70 to 99% by weight relative to the total weight of the curing agent composition. The curing agent composition according to claim 1, wherein the content of the second compound is 1 to 30% by weight relative to the total weight of the curing agent composition.

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

4. Of the above chemical formula 1, R １１ or R １３ The curing agent composition according to claim 1, wherein R and R are each independently hydrogen, a methyl group or an ethyl group.

5. Of the chemical formula 2 mentioned above, R ２１ R ２３ The curing agent composition according to claim 1, wherein each is independently a hydrogen atom, a methyl group, or an ethyl group.

6. The curing agent composition according to claim 1, further comprising a third compound represented by the following chemical formula 3: <Chemical formula 3> Of the above chemical formula 3, R ３１ R ３３ These are, independently of each other, hydrogen and C １ C １５ Alkyl or C ２ C １５ It is an alkenyl group, a31 and a32 are independent integers between 0 and 5.

7. Of the above chemical formula 3, R ３１ R ３３ The curing agent composition according to claim 6, wherein each is independently a hydrogen atom, a methyl group, or an ethyl group.

8. The curing agent composition according to claim 6, wherein the content of the third compound is 20% by weight or less relative to the total weight of the curing agent composition.

9. The curing agent composition according to claim 1, Base polymer and A curable composition comprising an initiator.

10. The curable composition according to claim 9, wherein the base polymer comprises an acrylate, a methacrylate, a polyphenylene oxide modified with an aryl group or a vinyl group.

11. The curable composition according to claim 9, wherein the initiator comprises a peroxide-based initiator.

12. The curable composition according to claim 9, wherein the ratio of the number of moles of the initiator to the number of moles of the curing agent composition is 0.01 to 0.

5.

13. The curable composition according to claim 9, wherein the ratio of the weight of the base polymer to the weight of the curing agent composition is 0.1 to 10.

14. The dielectric constant (Dk) of the curable composition is 2.55 or less. The curable composition according to claim 9, wherein the dielectric loss tangent (Df) of the curable composition is 0.0044 or less.

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