Compound having mesogen skeleton, curable composition, sealing material, printed board material, and electric / electronic component

Abstract

The present invention obtains a cured product having both heat dissipating ability and dielectric properties.　This compound is represented by general formula (1). In formula (1), R1 and R2 each independently represent a monovalent organic group that includes a radical polymerizable group and that has 2-15 carbon atoms, and p, q, and r each independently represent an integer of 0-4.

Description

Compound having a mesogen skeleton, curable composition, sealing material, printed circuit board material, and electric / electronic component

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

[0002] As the density and integration of electric and electronic components continue to increase, there is a demand for improved reliability of the electric and electronic components. To achieve this, various studies have been conducted on encapsulants for protecting electric and electronic components from external factors such as heat, moisture, and dust.

[0003] For example, Patent Document 1 discloses an encapsulating resin composition containing a specific maleimide resin and another thermosetting resin, as well as an inorganic filler and a heterocyclic compound. Patent Document 2 discloses that a liquid resin composition containing an epoxy resin including an alicyclic epoxy resin, an acid anhydride, a curing accelerator, an inorganic filler, and an anti-settling agent is used to encapsulate a power module including a power module substrate and a power semiconductor element by a casting method.

[0004] Substrate materials for forming printed circuit boards are also required to have excellent dielectric properties. For example, Patent Document 3 discloses a resin composition containing a modified polyphenylene ether compound, a cross-linking curing agent, and a flame retardant as a material for forming printed wiring boards. Patent Document 4 discloses a resin composition containing a radical polymerizable compound such as a polyphenylene ether compound and a phosphate ester compound having an alicyclic hydrocarbon structure as a material for forming wiring boards.

[0005] Japanese Patent No. 6885068 International Publication No. 2023 / 234201 Japanese Patent Application Laid-Open No. 2015-086330 International Publication No. 2022 / 259851

[0006] In recent years, with the miniaturization and high performance of electrical and electronic devices, there is an urgent need to improve the heat dissipation properties of materials used in electrical and electronic components. In addition, in the development of encapsulants and printed circuit boards for 5G and 6G communications, materials with low dielectric loss tangents are required to reduce transmission loss. In other words, increased signal transmission loss can lead to heat generation and electrical signal delays, which can lead to malfunctions and performance degradation. Therefore, reducing transmission loss is required, and materials with low dielectric loss tangents are required to achieve this.

[0007] Although there are materials with excellent heat dissipation properties and materials with excellent dielectric properties, the reality is that almost no materials have been developed that combine both heat dissipation and dielectric properties.

[0008] An object of an embodiment of the present invention is to provide a novel compound capable of giving a cured product that has both heat dissipation properties and dielectric properties, a curable composition using the compound, an encapsulant and a printed circuit board material, and an electric / electronic component.

[0009] The present invention includes the following embodiments: [1] A compound represented by the following general formula (1): (In formula (1), R １ and R ２ each independently represent a monovalent organic group having 2 to 15 carbon atoms and containing a radical 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 the compound according to any one of [1] to [3]. [5] An encapsulant comprising the compound according to any one of [1] to [3]. [6] An electric / electronic component resin-encapsulated using the encapsulant according to [5]. [7] A printed circuit board material comprising the compound according to any one of [1] to [3].

[0010] The compound according to the embodiment of the present invention can provide a cured product that has both heat dissipation properties and dielectric properties.

[0011] DSC chart of the compound obtained in Example 1 IR spectrum of the compound obtained in Example 1 １ H-NMR spectrum of the intermediate (TAM phenol) in Example 1 １ H-NMR spectrum DSC chart of the compound obtained in Example 2 IR spectrum of the compound obtained in Example 2 １ H-NMR spectrum of the intermediate (TA phenol) in Example 2 １ H-NMR spectrum DSC chart of the compound obtained in Example 9 IR spectrum of the compound obtained in Example 9 １ H-NMR spectrum of the intermediate (PMAM phenol) in Example 9 １ H-NMR spectrum

[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 crystallinity due to its highly planar mesogenic skeleton that exhibits π-π interactions, and therefore is thought to be able to give a cured product with excellent heat dissipation properties through the formation of an ordered structure. Furthermore, since the radically polymerizable groups introduced at both ends serve as curing reactive groups, it is thought that the generation of a highly polar structure in the cured product, as in epoxy resins, can be prevented, thereby lowering the dielectric loss tangent. Therefore, it is possible to achieve both heat dissipation and dielectric properties. Furthermore, compound (1) is cured by radical polymerization and can be molded at relatively low temperatures, resulting in excellent molding workability.

[0013]

[0014] In general formula (1), R １ and R ２ R each independently represents a monovalent organic group having 2 to 15 carbon atoms and containing a radical polymerizable group. １ and R ２ may be the same or different, and are preferably the same.

[0015] R １ and R ２Each of the groups preferably has 2 to 12 carbon atoms, and more preferably has 3 to 10 carbon atoms.

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

[0017] When the monovalent organic group containing a radical polymerizable group contains atoms other than the radical polymerizable group, it is preferable that the atoms do not contain heteroatoms, that is, the atoms other than the radical polymerizable group are composed only of carbon atoms and hydrogen atoms, from the viewpoint of dielectric properties. Specific examples of the monovalent organic group containing a radical polymerizable group include a vinylbenzyl group, an allyl group (-CH ２ -CH=CH ２ ), an acryloyl group (—C(═O)—CH═CH ２ ), a methacryloyl group (—C(═O)—C(CH ３ ) = CH ２ The optionally substituted vinylbenzyl group is preferably a group represented by the following general formula (2):

[0018] In the general formula (2), n represents an integer of 0 to 4, 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. ２ The bonding position of R may be the ortho position, meta position, or para position relative to the methylene group, and is preferably the meta position or para position. １ and R ２ In the formula (I), one of them may be in the meta position and the other in the para position.

[0019] In formula (1), 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 positions, preferably meta or para positions, and more preferably para positions. 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)." R in general formulas (1A) and (1D) １ , R ２ , p, q and r are R in general formula (1), １ , R ２ , p, q and r.

[0021] In the general formula (1), -O-R １ and -O-R ２ The bonding positions of each of the groups may be independently ortho, meta, or para relative to the imino group C═N, and these may be mixed in one molecule. １ and -O-R ２ 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), -O-R １ and -O-R ２ are preferably bonded at the para position to the imino group. Hereinafter, the compound represented by general formula (1B) according to 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] R in general formulas (1B) and (1E) １ , R ２ , p, q and r are R in general formula (1), １ , R ２ , p, q and r.

[0023] In a preferred embodiment, compounds (1), (1A), (1B), (1D) and (1E) are represented by general formulas (1), (1A), (1B), (1D) and (1E), respectively, 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 p, q, and r each independently represent an integer of 0 to 2. More preferably, in general formulas (1), (1A), and (1B), R １ and R ２ each 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; p, q, and r each independently represent 0 or 1.

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

[0025] In general formulas (1C) and (1F), R １ and R ２ are R in the general formula (1) above. １ and R ２ That is, each independently represents a monovalent organic group having 2 to 15 carbon atoms and containing a radical polymerizable group, and the preferred number of carbon atoms and specific examples are the same as those of R in general formula (1). １ and R ２ In formulae (1C) and (1F), q and r each independently represent 0 or 1.

[0026] Compound (1) may be produced by any method, and the production method is not particularly limited. For example, 1 mole of substituted or unsubstituted benzenedicarbaldehyde 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)"). Next, 1 mole of intermediate (3) is reacted with 2 moles of an organic halogen compound represented by general formula (4). This gives compound (1).

[0027] In general formula (3), 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. The bonding positions of the two imino groups C═N to the central benzene ring may be ortho, meta, or para positions, and are preferably para or meta positions. Furthermore, the bonding positions of the -OH groups at both ends to the benzene ring may each independently be ortho, meta, or para positions relative to the imino group C═N, and are preferably both para positions.

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

[0029] The intermediate (3) can be produced, for example, by dehydration condensation of a substituted or unsubstituted benzenedicarbaldehyde with a substituted or unsubstituted aminophenol in the presence of an acid catalyst. The reaction of the intermediate (3) with an organohalogen 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 a value measured by the method described in the Examples section.

[0031] The compound (1) has radical polymerizable groups at both ends and is therefore a thermosetting resin (curable compound) that can be cured (thermoset) by radical polymerization. Therefore, the compound (1) can be a constituent of a curable composition as a curable component that cures by radical polymerization. That is, the curable composition according to the embodiment contains the compound (1).

[0032] The curable composition may use compound (1) alone as the curable component, or may use other curable compounds together with compound (1). In this 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 of compound (1).

[0033] The other curable compound to be used in combination with compound (1) is not particularly limited, but is preferably a compound having multiple radically polymerizable groups in one molecule, such as a compound in which radically polymerizable groups are introduced at both ends of polyphenylene ether (hereinafter referred to as "modified PPE").

[0034] Examples of modified PPE include polyphenylene ether (meth)acrylate, polyphenylene ether in which the terminals of hydroxyl-terminated polyphenylene ether are modified with vinylbenzyl ether using chloromethylstyrene or the like.

[0035] Modified PPE is a curable compound that provides a cured product with excellent dielectric properties. Therefore, by using modified PPE in combination, the dielectric properties can be further improved. In one embodiment of the curable composition, 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 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 the present embodiment may contain, in addition to the curable component, various additives such as a thermoplastic resin, a polymerization initiator, a curing accelerator, an inorganic filler, an organic filler, a flame retardant, and a colorant, as necessary.

[0037] The form of the curable composition is not particularly limited, and examples thereof include powder, granules, tablets, etc. This allows the composition to be molded into a predetermined shape using a known molding method such as transfer molding, injection molding, or compression molding. Here, the term "granules" refers to an aggregate formed by solidifying powder of the curable composition, and the term "tablets" refers to a curable composition molded into a predetermined shape by tableting.

[0038] When the curable composition is used to form a cured product having a predetermined shape, for example, the curable composition containing compound (1) is melted by heating the curable composition, and the molten curable composition is thermally cured in a mold, thereby obtaining a cured product having a predetermined shape.

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

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

[0041] In one embodiment, the encapsulant for electric and electronic components is a material for protecting the electric and electronic components from external factors such as heat, moisture, dust, etc. The manner in which the encapsulant is used is not particularly limited, and for example, an electronic element such as a semiconductor element or an electronic substrate may be entirely or partially embedded inside the encapsulant, or an electronic element on an electronic substrate may be entirely or partially covered with the encapsulant.

[0042] The electric and electronic components to be encapsulated are not particularly limited, and examples thereof include semiconductor elements such as general semiconductor elements and power semiconductors, electronic control units, electronic substrates, capacitors, transformers, and sensors.

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

[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, and film- or sheet-like flexible printed circuit board materials.

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

[0046] IR (infrared absorption spectroscopy) in the following examples 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 measurement by the KBr method using a Nicolet 6700 manufactured by Thermo Fisher Scientific.

[0048] [ １ The products obtained in Examples 1, 2 and 9 were dissolved in deuterated chloroform and analyzed by nuclear magnetic resonance (JEOL, 399.78 MHz). １ H-NMR measurement was carried out.

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

[0050] Example 1 0.05 mol (6.7 g) of terephthalaldehyde, 0.1 mol (12.3 g) of 4-amino-3-methylphenol, 0.01 g of zinc chloride, and 130 g of a solvent ("Solmix AP-7" manufactured by Japan Alcohol Sales Co., Ltd.) were placed in a 300 mL reactor and reacted at 80°C for 2 hours. This resulted in the precipitation of a yellow solid. The resulting solid was thoroughly washed with the solvent and then dried under reduced pressure at 80°C for 3 hours, recovering 14.2 g of a compound represented by the following formula (5) (terephthalylidenebis(4-amino-3-methylphenol)). Hereinafter, this compound will be referred to as TAM-phenol.

[0051] 0.035 moles (12.04 g) of TAM phenol, 18.5 g of dimethyl sulfoxide (DMSO), and 46.1 g of toluene were placed in 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% aqueous sodium hydroxide solution were placed in the reactor, and the reaction was allowed to proceed for 3 hours at 75 ° C. Next, the solid was removed by filtration, and the reaction solution was cooled at room temperature to precipitate a yellow solid. The precipitated yellow solid was removed by filtration and dried under reduced pressure at 80 ° C. for 3 hours, and 7.0 g of a powdery yellow solid was recovered.

[0052] The obtained yellow solid was analyzed by IR, １ H-NMR and DSC measurements were carried out, and it was confirmed that the compound was represented by the following formula (6). Hereinafter, this compound will be referred to as a TAM phenol VB modified product (TAM-phenol VB modified product). In formula (6), vinyl groups (-CH=CH ２ The bonding positions of the chloromethylstyrenes used for terminal modification are a mixture of meta and para isomers, so that the meta and para positions relative to the methylene group are present. In other words, it is believed that the polymers include those in which both terminals are meta positions, those in which both terminals are para positions, and / or those in which one terminal is meta and the other terminal is para.

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

[0054] The IR spectrum of the modified TAM phenol VB is shown in FIG. －１ The absorption due to the vinyl group C=C is observed at 1620 cm －１ Absorption due to the imino group C=N is observed at 1107 cm －１ ether bond CH ２ Absorption due to —O—Ar was observed, which indicates that a vinylbenzyl group has been introduced into the intermediate TAM phenol.

[0055] TAM phenol VB modified １ The H-NMR spectrum is shown in Figure 3, and the chemical shift values, couplings, and hydrogen atom number ratios of each peak are as follows: δ (ppm): 8.43 (d, 2H, J = 1.6 Hz), 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 = 2.4 Hz), 2.41 (d, 6H, J = 2 Hz).

[0056] In addition, the intermediate TAM phenol １ The H-NMR spectrum is shown in Figure 4, and the chemical shift values, couplings, and hydrogen atom number 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 = 8.8 Hz), 6.58-6.65 (m, 4H), 2.28 (s, 6H).

[0057] For this intermediate １ Considering that absorption due to ether bonds is observed in the H-NMR spectrum and the IR spectrum shown in FIG. 2, it is clear that the TAM phenol VB modified product is the compound represented by formula (6).

[0058] Example 2 0.05 mol (6.7 g) of terephthalaldehyde, 0.1 mol (10.9 g) of 4-aminophenol, 0.01 g of zinc chloride, and 130 g of a solvent (Solmix AP-7, manufactured by Japan Alcohol Sales Co., Ltd.) were placed in a 300 mL reactor and reacted at 80°C for 2 hours. This resulted in the precipitation of a yellow solid. The resulting solid was thoroughly washed with the solvent and then dried under reduced pressure at 80°C for 3 hours, recovering 14.0 g of a compound. The resulting compound was terephthalylidenebis(4-aminophenol), which is a compound represented by general formula (3) in which p, q, and r are all 0. Hereinafter, this compound will be referred to as TA-phenol.

[0059] 0.035 moles (11.1 g) of TA phenol, 18.5 g of dimethyl sulfoxide (DMSO), and 46.1 g of toluene were charged into 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% aqueous sodium hydroxide solution were charged into the reactor and reacted at 75 ° C. for 3 hours. Next, the solid was removed by filtration, and the removed solid was 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, and 9.0 g of a powdery yellow solid was recovered.

[0060] The obtained yellow solid was analyzed by IR, １ H-NMR and DSC measurements confirmed that the compound was the compound represented by the following formula (7). Hereinafter, this compound will be referred to as TA-phenol VB modified product (TA-phenol VB modified product). In formula (7), vinyl groups (-CH=CH ２ The bonding positions of the chloromethylstyrenes used for terminal modification are a mixture of meta and para isomers, so that the meta and para positions relative to the methylene group are present. In other words, it is believed that the polymers include those in which both terminals are meta positions, those in which both terminals are para positions, and / or those in which one terminal is meta and the other terminal is para.

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

[0062] The IR spectrum of the TA phenol VB modified product is shown in FIG. －１ Absorption due to the vinyl group C=C is observed at 1618 cm －１ Absorption due to the imino group C=N is observed at 1114 cm －１ ether bond CH ２ Absorption due to —O—Ar was observed, which indicates that a vinylbenzyl group has been introduced into the intermediate TA phenol.

[0063] TA phenol VB modified １ The H-NMR spectrum is shown in Figure 7. The chemical shift values, couplings, and hydrogen atom ratios of each peak are as follows: δ (ppm): 8.52 (d, 2H, J = 1.6 Hz), 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 = 2.8 Hz). As shown enlarged in Figure 7, the peak at 7.24-7.28 (m, 4H) overlaps with the peak of deuterated chloroform, the solvent.

[0064] In addition, the intermediate TA phenol １ The H-NMR spectrum is shown in Figure 8, and the chemical shift values, couplings, and hydrogen atom number 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] For this intermediate １ Considering that absorption due to ether bonds is observed in the H-NMR spectrum and the IR spectrum shown in FIG. 6, it is clear that the TA phenol VB modified product is the compound represented by formula (7).

[0066] Example 9 0.05 mol (6.7 g) of isophthalaldehyde, 0.1 mol (12.3 g) of 4-amino-3-methylphenol, 0.01 g of zinc chloride, and 90 g of a solvent ("Solmix AP-7" manufactured by Japan Alcohol Sales Co., Ltd.) were placed in a 300 mL reactor and reacted at 80°C for 2 hours. This resulted in the precipitation of a yellow solid. The resulting solid was thoroughly washed with the solvent and then dried under reduced pressure at 80°C for 3 hours, recovering 9.62 g of 4,4'-[1,3-phenylenebis](methylidynenitrilo)bis[4-amino-3-methylphenol]. 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 placed in 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% aqueous sodium hydroxide solution were placed in the reactor, and the reaction was carried out at 75 ° C. for 3 hours. Next, 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, and 3.3 g of a powdery yellow solid was recovered.

[0068] The obtained yellow solid was analyzed by IR, １ H-NMR and DSC measurements confirmed that the compound was the compound represented by the following formula (8). Hereinafter, this compound will be referred to as PMAM phenol VB modified product. In formula (8), vinyl groups (-CH=CH ２ The bonding positions of the chloromethylstyrenes used for terminal modification are a mixture of meta and para isomers, so that the meta and para positions relative to the methylene group are present. In other words, it is believed that the polymers include those in which both terminals are meta positions, those in which both terminals are para positions, and / or those in which one terminal is meta and the other terminal is para.

[0069] The DSC chart of the PMAM phenol VB modified product is shown in FIG. 9, and the melting point was 130.8°C.

[0070] The IR spectrum of the PMAM phenol VB modified product is shown in FIG. －１ Absorption due to the vinyl group C═C is observed at 1622 cm －１ Absorption due to the imino group C=N is observed at 1116 cm －１ ether bond CH ２ Absorption due to —O—Ar was observed, which indicates that a vinylbenzyl group has been introduced into the intermediate PMAM phenol.

[0071] PMAM phenol VB modified １ The H-NMR spectrum is shown in FIG. 11, and the chemical shift values, couplings, and hydrogen atom number ratios of the respective peaks 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] In addition, the intermediate PMAM phenol １ The H-NMR spectrum is shown in Figure 12, and the chemical shift values, couplings, and hydrogen atom number 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 = 8.0 Hz), 7.55-7.60 (t, 1H, J = 7.6 Hz), 7.05-7.08 (d, 2H, J = 11.6 Hz), 6.58-6.64 (m, 4H), 2.27 (s, 6H).

[0073] For this intermediate １Considering that absorption due to ether bonds is observed in the H-NMR spectrum and the IR spectrum shown in FIG. 10, it is clear that the PMAM phenol VB modified product is the compound represented by formula (8).

[0074] Comparative Example 1 0.035 mol (59.5 g) of polyphenylene ether (SA-90 manufactured by SABIC Innovative Plastics, number of terminal hydroxyl groups: 2, weight average molecular weight Mw: 1700), 0.07 mol (10.7 g) of a 50:50 mass ratio mixture of p-chloromethylstyrene and m-chloromethylstyrene (Tokyo Chemical Industry Co., 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 were dissolved in toluene. The mixture was gradually heated, and finally heated until the liquid temperature reached 75°C. An aqueous sodium hydroxide solution (5.6 g of sodium hydroxide / 5.1 g of water) was added dropwise to the solution as an alkali metal hydroxide over 30 minutes. The mixture was then further stirred at 75°C for 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 filtered and dried under reduced pressure at 60°C for 3 hours to obtain a modified PPE (polyphenylene ether, both ends of which were modified with vinylbenzyl ether).

[0075] [Evaluation] The reaction products of Examples 1, 2, and 9 and Comparative Example 1, as well as additional comparative materials, were evaluated for dielectric loss tangent (dielectric properties), heat transfer coefficient (heat dissipation), average linear expansion coefficient, and molding workability.

[0076] In detail, as shown in Table 1 below, in Example 3, the TAM phenol VB modified product of Example 1 was used alone as the curable compound, in Example 4, the TA phenol VB modified product of Example 2 was used alone, in Example 10, the PMAM phenol VB modified product of Example 9 was used alone, and in Comparative Example 2, the modified PPE of Comparative Example 1 was used alone. In Examples 5 to 8, the TAM phenol VB modified product 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 (Zaidar M-350 manufactured by ENEOS SunEnergy Corporation), a thermoplastic resin with excellent heat dissipation properties, was used as a comparative material. This resin is a wholly aromatic polyester made from parahydroxybenzoic acid, biphenol, terephthalic acid, etc.

[0078] In Comparative Example 4, a typical epoxy resin (base: bisphenol A diglycidyl ether, curing agent: diaminodiphenylmethane) was used as a comparative material. Specifically, bisphenol A type epoxy resin "jER828" manufactured by Mitsubishi Kelcal Corporation and diaminodiphenylmethane manufactured by Tokyo Chemical Industry Co., Ltd. were used in a compounding 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-action compression molding machine for testing (manufactured by Yasuda Seiki Seisakusho), 1.5 g of sample was pressed at a pressure of 10 MPa and a temperature of 200 to 250°C for 5 to 15 minutes to prepare a flat plate of 30 mm x 30 mm x 1 mm thickness. The obtained flat plate was cut to prepare test pieces of 2 mm width, 1 mm thickness, and 30 mm length. The dielectric loss tangent Df of the test pieces at 10 GHz was measured 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 less than 0.01 B: Dielectric loss tangent 0.01 or more but less than 0.02 C: Dielectric loss tangent 0.02 or more

[0080] [Thermal Conductivity (Heat Dissipation)] Using a test single-action compression molding machine (manufactured by Yasuda Seiki Seisakusho), 1.5 g of 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. The thermal conductivity of the test piece was measured using a C-Therm (manufactured by Rigaku Corporation) with a polymer measurement file and water as the contact agent, and the heat dissipation was evaluated according to the following criteria: A: Thermal conductivity of 0.35 W / mK or more B: Thermal conductivity of 0.30 W / mK or more but less than 0.35 W / mK C: Thermal conductivity of 0.25 W / mK or more but less than 0.30 W / mK D: Thermal conductivity of 0.20 W / mK or more but less than 0.25 W / mK E: Thermal conductivity less than 0.20 W / mK

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

[0082] [Molding workability] A sample was placed in an aluminum cup and placed on a hot plate at 300°C. It was visually confirmed whether the sample melted or not, and samples that melted were evaluated as having excellent moldability and given a grade of "P," and samples that did not melt were evaluated as having poor moldability and given a grade of "F."

[0083]

[0084] As shown in Table 1, Examples 3 to 8, and 10, which used the TAM phenol VB modified product of Example 1, the TA phenol VB modified product of Example 2, or the PMAM phenol VB modified product of Example 9, had a dielectric dissipation factor Df of less than 0.02, exhibiting good dielectric properties, and a thermal conductivity of 0.20 W / mK or higher, exhibiting good heat dissipation. Therefore, both dielectric properties and heat dissipation were achieved. Furthermore, in all of Examples 3 to 8, and 10, the samples could be melted at 300°C, demonstrating excellent molding workability. In particular, the TAM phenol VB modified product and the PMAM phenol VB modified product had superior dielectric properties compared to the TA phenol VB modified product, a low average linear expansion coefficient, and excellent heat resistance. On the other hand, the TA phenol VB modified product was slightly inferior to the TAM phenol VB modified product and the PMAM phenol VB modified product in terms of dielectric properties and heat resistance, but had superior heat dissipation properties.

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

[0086] The various numerical ranges described in this specification can be arbitrarily combined with their respective upper and lower limit values, and all such combinations are considered to be preferred numerical ranges described in this specification. Furthermore, a numerical range described as "X to Y" means from X to Y.

[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, modifications, etc. are included within the scope and spirit of the invention, as well as within the scope of the invention described in the claims and their equivalents.

Claims

1. Represented by the following general formula (1): In formula (1), R １ and R ２ each independently represents a monovalent organic group having 2 to 15 carbon atoms and containing a radical polymerizable group; and p, q, and r each independently represent an integer of 0 to 4.

2. The compound of claim 1, wherein the radically 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 according to any one of claims 1 to 3.

5. An encapsulant comprising the compound according to any one of claims 1 to 3.

6. An electric / electronic component resin-sealed using the sealing material according to claim 5.

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

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