Compounds having a mesogenic skeleton, curable compositions, encapsulants, printed circuit board materials, and electrical and electronic components

Abstract

This invention provides a compound for obtaining a cured product that exhibits both excellent heat dissipation and dielectric properties. [Solution] The compound is represented by the following general formula (1). In formula (1), R 1 and R 2 Each of the following independently represents a monovalent organic group with 2 to 15 carbon atoms that contains a radical polymerizable group, and each of the following independently represents an integer from 0 to 4. JPEG2026047174000016.jpg36169

Description

Technical Field

[0001] Embodiments of the present invention relate to a novel compound having a mesogenic skeleton, a curable composition containing the compound, a sealing material and a printed circuit board material, and an electric and electronic component resin-sealed using the sealing material.

Background Art

[0002] With the progress of high density and high integration of electric and electronic components, improvement in reliability of electric and electronic components is required. For such reliability improvement, various studies have been made on sealing materials for protecting electric and electronic components from external factors such as heat, moisture, dust and the like.

[0003] For example, Patent Document 1 discloses a sealing resin composition obtained by blending an inorganic filler and a heterocyclic compound together with a specific maleimide resin and another thermosetting resin. Patent Document 2 discloses using a liquid resin composition containing an alicyclic epoxy resin, an acid anhydride, a curing accelerator, an inorganic filler, and an anti-settling agent to seal a power module including a substrate for a power module and a power semiconductor element by a casting method.

[0004] In the case of a substrate material for forming a printed circuit board, those having excellent dielectric properties are also required. For example, Patent Document 3 discloses a resin composition containing a modified polyphenylene ether compound, a crosslinkable curing agent, and a flame retardant as a material for constituting a printed wiring board. Patent Document 4 discloses a resin composition containing a radically polymerizable compound such as a polyphenylene ether compound and a phosphate ester compound having an alicyclic hydrocarbon structure as a material for constituting a wiring board.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

[0006] In recent years, with the miniaturization and high performance of electric and electronic devices, it has become an urgent task to improve the heat dissipation of materials used in electric and electronic components. In addition, in the development of encapsulating materials and printed circuit boards for 5G communication and 6G communication, materials with a low dielectric loss tangent are required to reduce transmission loss. That is, due to the increase in heat generation caused by the increase in signal transmission loss and the delay of electrical signals, there are concerns about failures and performance degradation. Therefore, it is required to reduce transmission loss, and for this purpose, materials with a low dielectric loss tangent are necessary.

[0007] Conventionally, although there are materials with excellent heat dissipation and materials with excellent dielectric properties respectively, the fact is that almost no materials have achieved both heat dissipation and dielectric properties.

[0008] An embodiment of the present invention aims to provide a novel compound capable of obtaining a cured product that achieves both heat dissipation and dielectric properties, a curable composition using the same, an encapsulating material, a printed circuit board material, and an electric and electronic component. [Means for Solving the Problems]

[0009] The present invention includes the following embodiments. [1] A compound represented by the following general formula (1). [Chemical Formula] (In formula (1), R[[ID=4)3]] and R 2 each independently represent a monovalent organic group having 2 to 15 carbon atoms containing a radically polymerizable group, and p, q, and r each independently represent an integer of 0 to 4.) [2] The compound according to [1], wherein the radical polymerizable group is a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group. [3] The compound according to [1] or [2], wherein p, q, and r in formula (1) are each independently 0 or 1. [4] A curable composition comprising any one of the compounds described in [1] to [3]. [5] A sealing material containing a compound described in any one of the items [1] to [3]. [6] [5] An electrical or electronic component sealed in resin using the sealing material described above. [7] A printed circuit board material containing a compound described in any one of the items [1] to [3]. [Effects of the Invention]

[0010] With the compound according to the embodiment of the present invention, a cured product can be obtained that achieves both heat dissipation and dielectric properties. [Brief explanation of the drawing]

[0011] [Figure 1] DSC chart of the compound obtained in Example 1 [Figure 2] IR spectrum of the compound obtained in Example 1 [Figure 3] ¹H-NMR spectrum of the compound obtained in Example 1 [Figure 4] 1H-NMR spectrum of the intermediate (TAM phenol) in Example 1 [Figure 5] DSC chart of the compound obtained in Example 2 [Figure 6] Compound IR spectrum obtained in Example 2 [Figure 7] ¹H-NMR spectrum of the compound obtained in Example 2 [Figure 8] 1H-NMR spectrum of the intermediate (TA phenol) in Example 2 [Figure 9] DSC chart of the compound obtained in Example 9 [Figure 10] Compound IR spectrum obtained in Example 9 [Figure 11] ¹H-NMR spectrum of the compound obtained in Example 9 [Figure 12] 1H-NMR spectrum of the intermediate (PMAM phenol) in Example 9 [Modes for carrying out the invention]

[0012] The compound according to this embodiment is a compound represented by the following general formula (1) (hereinafter referred to as "compound (1)"). Compound (1) is expected to exhibit liquid crystalline properties due to having a highly planar mesogenic skeleton in which π-π interactions occur, and therefore it is thought that a cured product with excellent heat dissipation can be obtained by forming an ordered structure. Furthermore, since radical polymerizable groups introduced at both ends are used as curing reaction groups, it is thought that the formation of a highly polar structure in the cured product, as in epoxy resins, can be prevented, thereby lowering the dielectric loss tangent. Therefore, both heat dissipation and dielectric properties can be achieved. In addition, compound (1) is cured by radical polymerization and can be molded at relatively low temperatures, thus offering excellent moldability.

[0013] [ka]

[0014] In general formula (1), R 1 and R 2 Each of these independently represents a monovalent organic group with 2 to 15 carbon atoms that contains a radical polymerizable group. 1 and R 2 They may be the same or different, but preferably they are the same.

[0015] R 1 and R 2 The number of carbon atoms in each is more preferably 2 to 12, and even more preferably 3 to 10.

[0016] Examples of the radical polymerizable group include a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group. Among these, a vinyl group or an allyl group is more preferable from the viewpoint of dielectric properties.

[0017] When the monovalent organic group containing a radical polymerizable group contains an atom other than the radical polymerizable group, from the viewpoint of dielectric properties, it is preferable that the atom does not contain a heteroatom, that is, it consists only of carbon atoms and hydrogen atoms other than the radical polymerizable group. Specific examples of the monovalent organic group containing a radical polymerizable group include a vinylbenzyl group which may have a substituent, an allyl group (-CH2-CH=CH2), an acryloyl group (-C(=O)-CH=CH2), a methacryloyl group (-C(=O)-C(CH3)=CH2), and the like. As the vinylbenzyl group which may have a substituent, a group represented by the following general formula (2) is preferable.

[0018] [Chemical formula] In the general formula (2), n represents an integer of 0 to ⅘, and R 3 each independently represents an alkyl group having 1 to 3 carbon atoms, and * represents a bond to an oxygen atom. n is preferably 0 or 1, and more preferably 0. R 3 is preferably a methyl group. The bonding position of the vinyl group (-CH=CH2) to the benzene ring may be ortho, meta, or para to the methylene group, preferably meta or para, and either one of R 1 and R 2 may be meta and the other may be para.

[0019] In the general formula (I), p, q, and r each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.

[0020] In general formula (1), the bonding positions of the two imino groups C=N to the central benzene ring may be ortho, meta, or para, preferably meta or para, and more preferably para. That is, general formula (1) is preferably represented by the following general formula (1A) or general formula (1D). Hereinafter, the compound represented by general formula (1A) according to a preferred embodiment of compound (1) will be referred to as "compound (1A)", and the compound represented by general formula (1D) will be referred to as "compound (1D)". [ka] R in general formulas (1A) and (1D) 1 , R 2 , p, q, and r are the R values ​​in general formula (1), respectively. 1 , R 2 It is the same as p, q, and r.

[0021] In general formula (1), the -OR of the benzene rings on the left and right 1 and -OR 2 The bonding positions of each can be independently ortho, meta, or para relative to the imino group C=N, and these can be mixed within a single molecule. Preferably, in general formula (1), -OR 1 and -OR 2 Both are in the para position relative to the imino group. More preferably, general formula (1) is represented by the following general formula (1B) or general formula (1E), that is, in general formula (1A) or general formula (1D), -OR 1 and -OR 2 It is preferable that both are bonded to the imino group at the para position. Hereinafter, the compound represented by general formula (1B) in a preferred embodiment of compound (1) will be referred to as "compound (1B)", and the compound represented by general formula (1E) will be referred to as "compound (1E)".

[0022] [ka] R in general formulas (1B) and (1E) 1 , R 2 , p, q, and r are the R values ​​in general formula (1), respectively.1 , R 2 It is the same as p, q, and r.

[0023] In a preferred embodiment, compounds (1), (1A), (1B), (1D), and (1E) are, respectively, represented by the general formula (1), (1A), (1B), (1D), and (1E), where R 1 and R 2 Each independently represents a monovalent organic group having 2 to 12 carbon atoms, containing a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group, and each independently represents an integer from 0 to 2. More preferably, in general formulas (1), (1A), and (1B), R 1 and R 2 Each of these independently represents a monovalent organic group having 3 to 10 carbon atoms, containing a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group, and p, q, and r are each independently 0 or 1.

[0024] In one embodiment, compound (1) may be a compound represented by the following general formula (1C) (hereinafter referred to as "compound (1C)") or a compound represented by the following general formula (1F) (hereinafter referred to as "compound (1F)"). [ka]

[0025] In general formulas (1C) and (1F), R 1 and R 2 These are R in the general formula (1) above, respectively. 1 and R 2 This is the same as, that is, each independently represents a monovalent organic group with 2 to 15 carbon atoms containing a radical polymerizable group, and the preferred number of carbon atoms and specific examples are also the same as R in general formula (1). 1 and R 2 This is the same as the previous example. In equations (1C) and (1F), q and r each independently represent either 0 or 1.

[0026] Compound (1) can be produced by any method, and the method of production is not particularly limited. For example, 1 mole of substituted or unsubstituted benzenedicarboxylase is reacted with 2 moles of substituted or unsubstituted aminophenol to obtain an intermediate having phenolic hydroxyl groups at both ends, represented by the following general formula (3) (hereinafter referred to as "intermediate (3)"). Then, 1 mole of intermediate (3) is reacted with 2 moles of an organic halogen compound represented by general formula (4). This yields compound (1). [ka] [ka]

[0027] In general formula (3), p, q, and r each independently represent an integer from 0 to 4, preferably from 0 to 2, and more preferably 0 or 1. The bond positions of the two imino groups C=N to the central benzene ring may be ortho, meta, or para, and are preferably para or meta. The bond positions of the -OH groups at both ends to the benzene ring may each independently be ortho, meta, or para relative to the imino group C=N, and are preferably both para.

[0028] In general formula (4), X represents a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a chlorine atom or a bromine atom. 4 R in general formula (1) 1 and R 2 This is the same as, that is, it represents a monovalent organic group with 2 to 15 carbon atoms that contains a radical polymerizable group, and preferred carbon number and specific examples are also R 1 and R 2 It is the same as this.

[0029] The above intermediate (3) is produced, for example, by dehydration condensation of a substituted or unsubstituted benzenedicarboxylate with a substituted or unsubstituted aminophenol in the presence of an acid catalyst. The reaction between intermediate (3) and the organic halogen compound of formula (4) can be carried out under basic conditions, for example by Williamson ether synthesis, to produce compound (1).

[0030] The melting point of compound (1) is not particularly limited, but is preferably 80°C to 250°C, and more preferably 120°C to 220°C. Here, the melting point of compound (1) is the value measured by the method described in the Examples section.

[0031] Compound (1) has radical polymerizable groups at both ends and is therefore a thermosetting resin (curable compound) that can be cured (thermally cured) by radical polymerization. For this reason, compound (1) can be a component of a curable composition as a curable component that is cured by radical polymerization. That is, the curable composition according to the embodiment contains compound (1).

[0032] The curable composition may use compound (1) alone as the curable component, or it may use compound (1) together with other curable compounds. In that case, 100% by mass of the curable component preferably contains 20% by mass or more of compound (1), more preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more.

[0033] Other curable compounds used in combination with compound (1) are not particularly limited, but compounds having multiple radical polymerizable groups in one molecule are preferred. For example, a compound in which radical polymerizable groups are introduced at both ends of a polyphenylene ether (hereinafter referred to as "modified PPE") is one such example.

[0034] Examples of modified PPE include hydroxyl-terminated polyphenylene ethers whose ends are modified with vinyl benzyl ether using chloromethylstyrene, etc., and polyphenylene ether (meth)acrylate.

[0035] Modified PPE is a curable compound that yields a cured product with excellent dielectric properties. Therefore, by using modified PPE in combination, the dielectric properties can be further improved. In a curable composition according to one embodiment, 100% by mass of the curable component may contain 20 to 95% by mass of compound (1) and 5 to 80% by mass of modified PPE, or it may contain 30 to 90% by mass of compound (1) and 10 to 70% by mass of modified PPE.

[0036] The curable composition according to this embodiment may, as needed, contain various additives such as thermoplastic resins, polymerization initiators, curing accelerators, inorganic fillers, organic fillers, flame retardants, and colorants, along with the curable components.

[0037] The form of the curable composition is not particularly limited and can be, for example, in powder, granular, or tablet form. This allows it to be molded into a predetermined shape using known molding methods such as transfer molding, injection molding, or compression molding. Here, "granular form" refers to aggregates formed by solidifying powders of the curable composition, and "tablet form" refers to a curable composition molded into a predetermined shape by tablet molding.

[0038] When forming a cured product of a predetermined shape using a curable composition, for example, the curable composition containing compound (1) is melted by heating the curable composition, and the molten curable composition is heat-cured in a mold to obtain a cured product of the predetermined shape.

[0039] The curing conditions for curing the curable composition are not particularly limited; for example, it can be cured by heating at 120°C to 250°C for 5 to 60 minutes.

[0040] The compound (1) or curable composition according to this embodiment has excellent heat dissipation and dielectric properties, and can therefore be used as a encapsulant for electrical and electronic components, for example. That is, the encapsulant according to this embodiment includes compound (1) or the curable composition containing compound (1).

[0041] In one embodiment, the encapsulant for electrical and electronic components is a material for protecting the electrical and electronic components from external factors such as heat, moisture, and dust. The form of use of the encapsulant is not particularly limited; for example, all or part of an electronic element such as a semiconductor element or an electronic substrate may be embedded inside the encapsulant, or all or part of an electronic element on an electronic substrate may be covered with the encapsulant.

[0042] The electrical and electronic components to be sealed are not particularly limited and include, for example, general semiconductor elements such as power semiconductors, electronic control units, electronic circuit boards, capacitors, transformers, and sensors.

[0043] The compound (1) or curable composition according to the embodiment has excellent heat dissipation and dielectric properties, and can therefore be used as a printed circuit board material. That is, the printed circuit board material according to one embodiment includes compound (1) or the curable composition containing compound (1). A printed circuit board, such as a printed wiring board or printed circuit board according to one embodiment, can be manufactured using this printed circuit board material.

[0044] Examples of printed circuit board materials include rigid printed circuit board materials such as single-sided boards, double-sided boards, multilayer boards, and build-up boards, as well as flexible printed circuit board materials in the form of films or sheets. [Examples]

[0045] The present invention will be described in more detail below based on examples and comparative examples, but it is not limited thereto.

[0046] In the following examples, IR (infrared absorption spectroscopy) 1 The measurement methods for H-NMR and DSC (Differential Scanning Calorimetry) are as follows.

[0047] [IR] The products obtained in Examples 1, 2, and 9 were subjected to IR measurements using the KBr method with a Nicolet 6700 from Thermo Fisher Scientific.

[0048] [ 1 [H-NMR] The products obtained in Examples 1, 2, and 9 were dissolved in deuterated chloroform and subjected to nuclear magnetic resonance (JEOL, 399.78 MHz), 1 1H-NMR measurements were performed.

[0049] [DSC] The melting points of the products obtained in Examples 1, 2, and 9 were measured using a DSC8230 (manufactured by Rigaku Corporation) under a nitrogen atmosphere at a heating rate of 5°C / min.

[0050] [Example 1] 0.05 moles (6.7 g) of terephthalaldehyde, 0.1 moles (12.3 g) of 4-amino-3-methylphenol, 0.01 g of zinc chloride, and 130 g of solvent (Solmix AP-7, manufactured by Nippon Alcohol Sales Co., Ltd.) were placed in a 300 mL reactor and reacted at 80°C for 2 hours. A yellow solid precipitated. After thoroughly washing the obtained solid with the solvent, it was dried under reduced pressure at 80°C for 3 hours to recover 14.2 g of the compound represented by the following formula (5) (terephthalylidenebis(4-amino-3-methylphenol)). Hereinafter, this compound will be referred to as TAM phenol (TAM-phenol). [ka]

[0051] 0.035 moles (12.04 g) of TAM phenol, 18.5 g of dimethyl sulfoxide (DMSO), and 46.1 g of toluene were added to a 300 mL reactor, and the TAM phenol was dissolved at 75°C. Next, 0.093 moles (14.2 g) of chloromethylstyrene (AGC Seimi Chemical Co., Ltd. "CMS-P", a mixture of meta and para isomers), 0.4 g of tetrabutylammonium bromide, and 19.8 g of 48% sodium hydroxide aqueous solution were added to the reactor, and the reaction was carried out at 75°C for 3 hours. Subsequently, the reaction solution, after removing the solid by filtration, was cooled to room temperature, and a yellow solid precipitated. The precipitated yellow solid was removed by filtration and dried under reduced pressure at 80°C for 3 hours to recover 7.0 g of powdered yellow solid.

[0052] Regarding the obtained yellow solid, IR, 1 ¹H-NMR and DSC measurements confirmed that the compound is represented by the following formula (6). Hereinafter, this compound will be referred to as TAM-phenol VB modified compound (TAM-phenol VB modified compound). In formula (6), the bonding positions of the vinyl groups (-CH=CH2) to the benzene rings at both ends are a mixture of meta and para isomers of chloromethylstyrene used for terminal modification, resulting in a mixture of meta and para isomers relative to the methylene group. That is, it is thought that the compound includes those with both ends in the meta position, those with both ends in the para position, and / or those with one end in the meta position and the other in the para position. [ka]

[0053] The DSC chart of the TAM phenol VB modified product is shown in Figure 1, and its melting point was 130.8°C.

[0054] The IR spectrum of the TAM phenol VB modified product is shown in Figure 2, at 1635 cm⁻¹. -1 Absorption based on the vinyl group C=C is observed at 1620 cm². -1 Absorption based on the imino group C=N is observed at 1107 cm⁻¹. -1Absorption based on the ether bond CH2-O-Ar was observed. This indicates that a vinylbenzyl group has been introduced into the intermediate TAMphenol.

[0055] TAM phenol VB modified 1 The 1H-NMR spectrum is shown in Figure 3, and the chemical shift values, couplings, and hydrogen atom ratios of each peak are as follows. δ(ppm):8.43(d, 2H, J=1.6Hz), 7.98(s, 4H), 7.30-7.48(m, 8H), 6.97-7.00(m, 2H), 6.89(m, 2H), 6.80-6.90(m, 2H), 6.67-6.77(m, 2H), 5.72-5.81(m, 2H),5.22-5.37(m,2H), 5.06(d, 4H, J=2.4Hz), 2.41(d, 6H, J=2Hz)

[0056] Furthermore, the intermediate TAM phenol 1 The 1H-NMR spectrum is shown in Figure 4, and the chemical shift values, couplings, and hydrogen atom ratios of each peak are as follows. δ(ppm):9.36(s,2H), 8.54(s,2H), 7.98(s, 4H), 7.03-7.05(d, 2H, J=8.8Hz), 6.58-6.65(m,4H), 2.28(s, 6H)

[0057] About this intermediate 1 Considering the 1H-NMR spectrum and the IR spectrum shown in Figure 2, which show absorption based on ether bonding, it can be concluded that the TAM phenol VB modified compound is represented by formula (6).

[0058] [Example 2] 0.05 moles (6.7 g) of terephthalaldehyde, 0.1 moles (10.9 g) of 4-aminophenol, 0.01 g of zinc chloride, and 130 g of solvent (Solmix AP-7, manufactured by Nippon Alcohol Sales Co., Ltd.) were placed in a 300 mL reactor and reacted at 80°C for 2 hours. A yellow solid precipitated. After thoroughly washing the obtained solid with the solvent, 14.0 g of the compound was recovered by drying under reduced pressure at 80°C for 3 hours. The obtained compound is terephthalylidenebis(4-aminophenol), a compound in general formula (3) where p, q, and r are all 0, and this compound will be referred to as TA phenol (TA-phenol) below.

[0059] 0.035 moles (11.1 g) of TA phenol, 18.5 g of dimethyl sulfoxide (DMSO), and 46.1 g of toluene were added to a 300 mL reactor, and the TA phenol was dissolved at 75°C. Next, 0.093 moles (14.2 g) of chloromethylstyrene (AGC Seimi Chemical Co., Ltd. "CMS-P", a mixture of meta and para isomers), 0.4 g of tetrabutylammonium bromide, and 19.8 g of 48% sodium hydroxide aqueous solution were added to the reactor, and the mixture was reacted at 75°C for 3 hours. The solid was then removed by filtration, thoroughly washed with a mixed solvent of 75 mL of distilled water and 75 mL of methanol, and then dried under reduced pressure at 60°C for 3 hours to recover 9.0 g of a yellow powdery solid.

[0060] Regarding the obtained yellow solid, IR, 1 ¹H-NMR and DSC measurements confirmed that the compound is represented by the following formula (7). Hereafter, this compound will be referred to as TA-phenol VB modified compound (TA-phenol VB modified compound). In formula (7), the bonding positions of the vinyl groups (-CH=CH2) to the benzene rings at both ends are a mixture of meta and para isomers of chloromethylstyrene used for terminal modification, resulting in a mixture of meta and para isomers relative to the methylene group. That is, it is thought that the compound includes those with both ends in the meta position, those with both ends in the para position, and / or those with one end in the meta position and the other in the para position. [ka]

[0061] The DSC chart of the TA phenol VB modified product is shown in Figure 5, and its melting point was 197.4°C.

[0062] The IR spectrum of the TA phenol VB modified product is shown in Figure 6, at 1634 cm⁻¹. -1 Absorption based on the vinyl group C=C is observed at 1618 cm². -1 Absorption based on the imino group C=N is observed at 1114 cm⁻¹. -1 Absorption based on the ether bond CH2-O-Ar was observed. This indicates that a vinylbenzyl group has been introduced into the intermediate TA phenol.

[0063] TA phenol VB modified 1 The 1H-NMR spectrum is shown in Figure 7, and the chemical shift values, couplings, and hydrogen atom ratios of each peak are as follows. δ(ppm):8.52(d, 2H, J=1.6Hz), 7.97(s, 4H), 7.34-7.51(m, 8H), 7.24-7.28(m, 4H), 6.98-7.03(m, 4H), 6.69-6.77(m, 2H), 5.73-5.80(m, 2H), 5.24-5.28(m, 2H),5.08(d, 4H, J=2.8Hz) The peak at 7.24–7.28 (m, 4H) overlapped with the peak of the solvent, deuterated chloroform, as shown in an enlarged view in Figure 7.

[0064] Furthermore, the intermediate TA phenol 1 The 1H-NMR spectrum is shown in Figure 8, and the chemical shift values, couplings, and hydrogen atom ratios of each peak are as follows. δ(ppm):9.53(s,2H), 8.64(s,2H), 7.96(s, 4H), 7.20-7.23(m, 4H), 6.76-6.80(m,4H)

[0065] About this intermediate 1 Considering the 1H-NMR spectrum and the IR spectrum shown in Figure 6, which show absorption based on ether bonding, it can be concluded that the TA phenol VB modified compound is represented by formula (7).

[0066] [Example 9] 0.05 moles (6.7 g) of isophthalaldehyde, 0.1 moles (12.3 g) of 4-amino-3-methylphenol, 0.01 g of zinc chloride, and 90 g of solvent (Solmix AP-7, manufactured by Nippon Alcohol Sales Co., Ltd.) were placed in a 300 mL reactor and reacted at 80°C for 2 hours. A yellow solid precipitated. After thoroughly washing the obtained solid with the solvent, 9.62 g of 4,4'-[1,3-phenylenebis](methylidinenitrilo)bis[4-amino-3-methylphenol] was recovered by vacuum drying at 80°C for 3 hours. Hereinafter, this compound will be referred to as PMAMphenol.

[0067] 0.026 moles (8.9 g) of PMAM phenol, 30.0 g of dimethyl sulfoxide (DMSO), and 34.7 g of toluene were added to a 300 mL reactor, and the PMAM phenol was dissolved at 75°C. Next, 0.069 moles (10.5 g) of chloromethylstyrene (AGC Seimi Chemical Co., Ltd. "CMS-P", a mixture of meta and para isomers), 0.3 g of tetrabutylammonium bromide, and 14.8 g of 48% sodium hydroxide aqueous solution were added to the reactor, and the reaction was carried out at 75°C for 3 hours. Subsequently, the reaction solution was cooled to room temperature, and a yellow solid precipitated. The precipitated yellow solid was removed by filtration and dried under reduced pressure at 80°C for 3 hours to recover 3.3 g of powdered yellow solid.

[0068] Regarding the obtained yellow solid, IR, 1¹H-NMR and DSC measurements confirmed that the compound is represented by formula (8) below. Hereinafter, this compound will be referred to as PMAM phenol VB modified compound. In formula (8), the bond positions of the vinyl groups (-CH=CH2) to the benzene rings at both ends are mixed, with both meta and para positions relative to the methylene group, because the chloromethylstyrene used for end modification is a mixture of meta and para isomers. That is, it is thought that the compound includes those with both ends in the meta position, those with both ends in the para position, and / or those with one end in the meta position and the other in the para position. [ka]

[0069] The DSC chart for the PMAM phenol VB modified compound is shown in Figure 9, and its melting point was 130.8°C.

[0070] The IR spectrum of the PMAM phenol VB modified compound is shown in Figure 10, at 1638 cm⁻¹. -1 Absorption based on the vinyl group C=C is observed at 1622 cm². -1 Absorption based on the imino group C=N is observed at 1116 cm⁻¹. -1 Absorption based on the ether bond CH2-O-Ar was observed. This indicates that a vinylbenzyl group has been introduced into the intermediate PMAM phenol.

[0071] PMAM phenol VB modified compound 1 The 1H-NMR spectrum is shown in Figure 11, and the chemical shift values, couplings, and hydrogen atom ratios of each peak are as follows. δ(ppm):8.45(s, 2H), 8.35(s, 1H), 8.01-8.03(d, 2H, J=7.6Hz), 7.48-7.57(t, 1H,J=7.6Hz), 7.35-7.44(m, 8H), 6.96-6.98(m, 2H), 6.88-6.90(m, 2H), 6.80-6.84(m, 2H),6.69-6.77(m, 2H), 5.73-5.81(m, 2H), 5.24-5.28(m, 2H), 5.05(s, 4H), 2.38(s, 6H)

[0072] Furthermore, the intermediate PMAM phenol 1 The 1H-NMR spectrum is shown in Figure 12, and the chemical shift values, couplings, and hydrogen atom ratios of each peak are as follows. δ(ppm):9.31(s, 2H), 8.56(s, 2H), 8.41(s, 1H), 7.97-7.99(d, 2H, J=8.0Hz), 7.55-7.60(t,1H, J=7.6Hz), 7.05-7.08(d, 2H, J=11.6Hz), 6.58-6.64(m, 4H), 2.27(s, 6H)

[0073] About this intermediate 1 Considering the 1H-NMR spectrum and the IR spectrum shown in Figure 10, which show absorption based on ether bonding, it can be concluded that the PMAM phenol VB modified compound is represented by formula (8).

[0074] [Comparative Example 1] 0.035 moles (59.5 g) of polyphenylene ether (SA-90, manufactured by SABIC Innovative Plastics, with 2 terminal hydroxyl groups and a weight-average molecular weight of Mw1700), 0.07 moles (10.7 g) of a mixture of p-chloromethylstyrene and m-chloromethylstyrene in a mass ratio of 50:50 (Tokyo Chemical Industries, Ltd.), 0.56 g of tetra-n-butylammonium bromide as a phase transfer catalyst, and 230 g of toluene were charged and stirred. The mixture was then stirred until the polyphenylene ether, chloromethylstyrene, and tetra-n-butylammonium bromide dissolved in the toluene. The mixture was gradually heated until the final temperature reached 75°C. Then, an aqueous sodium hydroxide solution (5.6 g sodium hydroxide / 5.1 g water) was added dropwise to the solution over 30 minutes as an alkali metal hydroxide. The mixture was then stirred at 75°C for a further 4 hours. Next, the contents of the flask were neutralized with 35% by mass hydrochloric acid, and then a large amount of methanol was added. This caused the product to precipitate in the flask. The precipitate was then removed by filtration and dried under reduced pressure at 60°C for 3 hours to obtain modified PPE (polyphenylene ether modified at both ends with vinyl benzyl ether).

[0075] [evaluation] The reaction products of Examples 1, 2, and 9 and Comparative Example 1, along with additional comparative materials, were used to evaluate the dielectric loss tangent (dielectric properties), heat transfer coefficient (heat dissipation), average linear expansion coefficient, and moldability.

[0076] In detail, as shown in Table 1 below, the curable compound used was the TAM phenol VB modified compound from Example 1 used alone in Example 3, the TA phenol VB modified compound from Example 2 used alone in Example 4, the PMAM phenol VB modified compound from Example 9 used alone in Example 10, and the modified PPE from Comparative Example 1 used alone in Comparative Example 2. In addition, in Examples 5 to 8, the TAM phenol VB modified compound and the modified PPE were used in combination in the mass ratios shown in Table 1.

[0077] In Comparative Example 3, a liquid crystal polymer (Zyder M-350, manufactured by ENEOS Sun Energy Co., Ltd.), a thermoplastic resin with excellent heat dissipation properties, was used as the comparative material. This resin is a fully aromatic polyester made from parahydroxybenzoic acid, biphenol, and terephthalic acid.

[0078] In Comparative Example 4, a typical epoxy resin (main component: bisphenol A diglycidyl ether, curing agent: diaminodiphenylmethane) was used as a comparative material. Specifically, bisphenol A type epoxy resin "jER828" manufactured by Mitsubishi Kelcal Co., Ltd. and diaminodiphenylmethane manufactured by Tokyo Chemical Industry Co., Ltd. were used in a blending ratio (stoichiometric amount) in which one active hydrogen reacts with one epoxy group.

[0079] The evaluation method is as follows: [Dielectric Loss Tangent Df (Dielectric Properties)] Using a single-acting compression molding machine (manufactured by Yasuda Seiki Seisakusho), 1.5 g of the sample was pressed for 5 to 15 minutes at a pressure of 10 MPa and a temperature of 200 to 250°C to produce a flat plate measuring 30 mm × 30 mm × 1 mm thick. The obtained flat plate was cut to produce test specimens measuring 2 mm in width, 1 mm in thickness, and 30 mm in length. The dielectric loss tangent Df of these test specimens was measured at 10 GHz using a cavity resonator dielectric constant measuring device (manufactured by KEYSIGHT), and the dielectric properties were evaluated according to the following criteria. A: Dielectric loss tangent is less than 0.01 B: Dielectric loss tangent is 0.01 or greater and less than 0.02 C: Dielectric loss tangent is 0.02 or higher

[0080] [Thermal conductivity (heat dissipation)] Using a single-acting compression molding machine (manufactured by Yasuda Seiki Seisakusho), 1.5 g of the sample was pressed for 5 to 15 minutes at a pressure of 10 MPa and a temperature of 200 to 250°C to produce a 30 mm x 30 mm x 1 mm thick flat plate. For these test pieces, the thermal conductivity was measured using C-Therm (manufactured by Rigaku Corporation), with polymer as the measurement file and water as the contact agent, and the heat dissipation performance was evaluated according to the following criteria. A: Thermal conductivity of 0.35 W / mK or higher B: Thermal conductivity of 0.30 W / mK or more and less than 0.35 W / mK C: Thermal conductivity of 0.25 W / mK or more and less than 0.30 W / mK D: Thermal conductivity of 0.20 W / mK or more and less than 0.25 W / mK E: Thermal conductivity less than 0.20 W / mK

[0081] [Average coefficient of linear expansion] Using a single-acting compression molding machine (manufactured by Yasuda Seiki Seisakusho), a 1.5g sample was pressed for 5-15 minutes at a pressure of 10MPa and a temperature of 200-250°C to produce a 30mm x 30mm x 1mm thick flat plate. The obtained flat plate was cut to produce test specimens with a width of 5mm, a thickness of 1mm, and a length of 24mm. For these test specimens, the average coefficient of linear expansion (CTE, α1) in the glassy state (50°C-200°C) was calculated using the tensile load method under a nitrogen atmosphere using TMA8311 (manufactured by Rigaku Corporation).

[0082] [Molding workability] The sample was placed in an aluminum cup, which was then placed on a 300°C hot plate. The melting of the sample was visually confirmed, and samples that melted were rated "P" for excellent moldability, while samples that did not melt were rated "F" for poor moldability.

[0083] [Table 1]

[0084] As shown in Table 1, Examples 3-8 and 10, using the TAM phenol VB modified material of Example 1, the TA phenol VB modified material of Example 2, or the PMAM phenol VB modified material of Example 9, exhibited good dielectric properties with a dielectric loss tangent Df of less than 0.02, and good heat dissipation with a thermal conductivity of 0.20 W / mK or higher. Therefore, they achieved a balance between dielectric properties and heat dissipation. Furthermore, in Examples 3-8 and 10, the samples were all meltable at 300°C and exhibited excellent moldability. In particular, the TAM phenol VB modified material and the PMAM phenol VB modified material had superior dielectric properties compared to the TA phenol VB modified material, as well as a lower average coefficient of linear expansion and superior heat resistance. On the other hand, the TA phenol VB modified material was slightly inferior to the TAM phenol VB modified material and the PMAM phenol VB modified material in terms of dielectric properties and heat resistance, but it had superior heat dissipation.

[0085] In contrast, Comparative Example 2, which used the modified PPE from Comparative Example 1 alone, exhibited excellent dielectric properties but had low thermal conductivity and poor heat dissipation. Comparative Example 3, which used the liquid crystal polymer M-350, had excellent heat dissipation and dielectric properties, but did not melt at 300°C, resulting in poor moldability. Furthermore, Comparative Example 4, which used a typical epoxy resin, had a high dielectric loss tangent, poor dielectric properties, and low thermal conductivity, resulting in poor heat dissipation.

[0086] Furthermore, the various numerical ranges described in the specification can be any combination of their upper and lower limits, and all such combinations are described herein as preferred numerical ranges. Also, the description of a numerical range as "X~Y" means X or greater and Y or less.

[0087] Although several embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their omissions, substitutions, and modifications are included in the scope and spirit of the invention, as well as in the claims and their equivalents.

Claims

1. It is expressed by the following general formula (1), 【Chemistry 1】 In formula (1), R １ and R ２ A compound in which each of the following independently represents a monovalent organic group having 2 to 15 carbon atoms and containing a radical polymerizable group, and p, q, and r independently represent integers from 0 to 4.

2. The compound according to claim 1, wherein the radical polymerizable group is a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group.

3. The compound according to claim 1, wherein p, q, and r in formula (1) are each independently 0 or 1.

4. A curable composition comprising the compound described in any one of claims 1 to 3.

5. A sealing material comprising the compound described in any one of claims 1 to 3.

6. An electrical and electronic component sealed in resin using the sealing material described in claim 5.

7. A printed circuit board material comprising the compound described in any one of claims 1 to 3.

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