JP7725880B2 - Epoxy resin compositions, compositions for electronic components, materials for electronic components - Google Patents

Description

The present invention relates to a composition for electronic components that efficiently conducts heat generated inside electronic devices, and to a polymerizable compound with liquid crystal properties used therein.

In recent years, there has been a demand for packaging materials with high thermal conductivity to prevent the temperature of the internal semiconductors from becoming too high, such as in semiconductor elements used to control the power of hybrid and electric vehicles, and in CPUs for high-speed computers. In other words, the ability to effectively dissipate heat generated by the semiconductor chip to the outside has become important.

One way to solve this heat dissipation problem is to contact the heat-generating area with a highly thermally conductive material (heat dissipation component), which then guides the heat to the outside and dissipates it. Examples of highly thermally conductive materials include inorganic materials such as metals and metal oxides. However, these inorganic materials have problems with processability and insulation, making them very difficult to use alone as fillers for semiconductor packages. For this reason, efforts are underway to develop highly thermally conductive heat dissipation components that combine these inorganic materials with resins.

Increasing the thermal conductivity of composite materials has generally been achieved by adding large amounts of inorganic fillers, such as metal fillers, to general-purpose resins such as polyethylene resin, polyamide resin, polystyrene resin, acrylic resin, and epoxy resin. However, the thermal conductivity of inorganic fillers is a substance-specific value and has a set upper limit. Therefore, there have been many attempts to achieve this by improving the thermal conductivity of the resin. One known way to actually achieve this is to use an epoxy compound with liquid crystal properties.

Patent Document 1 discloses a terphenyl compound having two glycidyloxy groups. Patent Document 2 discloses a terphenyl compound having three glycidyloxy groups. However, the compounds disclosed in these patent documents do not have a liquid crystal temperature and have high melting points of 117°C or higher.

WO 2005/61473 WO 2016/6649

The objective of the present invention is to provide an epoxy resin with high thermal conductivity and heat resistance. It is also to provide an epoxy resin composition that provides such an epoxy resin.

The inventors have discovered that a composition containing at least one of component A as an epoxy compound and component B as a curing agent, and a cured product thereof, can solve the above-mentioned problems, and have thus completed the present invention.

Component A: A compound having two or more oxiranyl groups and 2 to 5 aromatic rings, in which 1 to 3 hydrogen atoms of the aromatic rings have been replaced by groups derived from vinyl.
Component B: A compound having two or more phenolic hydroxyl groups or two or more cyanate esters and having two to five aromatic rings, in which one to three hydrogen atoms of the aromatic rings have been replaced by groups derived from vinyl.

The above composition is likely to exhibit liquid crystallinity either by itself or when cured. As a result, the cured product has high thermal conductivity. The cured product also has high heat resistance. Therefore, it can be suitably used as a heat dissipation material for power semiconductors, etc.

The following describes in detail an embodiment of the present invention. Note, however, that the present invention is not limited to the embodiment.

The present invention includes the following items:

[1] A composition containing an epoxy compound and a curing agent, the composition containing at least one of component A as the epoxy compound and component B as the curing agent.
Component A: A compound having two or more oxiranyl groups and 2 to 5 aromatic rings, in which 1 to 3 hydrogen atoms of the aromatic rings have been replaced by groups derived from vinyl.
Component B: A compound having two or more phenolic hydroxyl groups, groups in which the hydroxyl groups are acylated, or two or more cyanate esters, and having two to five aromatic rings, in which one to three hydrogen atoms of the aromatic rings have been replaced by groups derived from vinyl.

[2] The composition described in item [1], wherein component A or component B is a compound having a skeleton in which aromatic rings are linearly linked.

[3] The composition according to item [2], containing component A, wherein component A is a compound represented by formula (A).
In formula (A),
R ^ep independently represents a group having 3 to 12 carbon atoms including oxiranyl;
X independently represents a single bond, alkylene having 1 to 12 carbon atoms, —CH ₂ O—, —CH═CH—, or —C≡C—;
At least one R ¹ is a group represented by formula (1), and other R ^1s are independently hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms;
n is an integer from 0 to 2.

In formula (1), R ² is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the bonding position to the aromatic ring.

[4] The composition according to item [2], containing component B, wherein component B is a compound represented by formula (BI).
In formula (BI),
X independently represents a single bond, alkylene having 1 to 12 carbon atoms, —CH ₂ O—, —CH═CH—, or —C≡C—;
At least one R ¹ is a group represented by formula (1), and other R ^1s are independently hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms;
n is an integer from 0 to 2.
In formula (1), R ² is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the bonding position to the aromatic ring.

[5] The composition according to item [2], containing component B, wherein component B is a compound represented by formula (B-II).
In formula (B-II),
X independently represents a single bond, alkylene having 1 to 12 carbon atoms, —CH ₂ O—, —CH═CH—, or —C≡C—;
At least one R ¹ is a group represented by formula (1), and other R ^1s are independently a group represented by hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms;
^R3 is independently alkyl having 1 to 6 carbon atoms or phenyl;
n is an integer from 0 to 2.
In formula (1), R ² is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the bonding position to the aromatic ring.

[6] The composition according to [2], which contains component B, and component B is a compound represented by formula (B-III).
In formula (B-III),
X independently represents a single bond, alkylene having 1 to 12 carbon atoms, —CH ₂ O—, —CH═CH—, or —C≡C—;
At least one R ¹ is a group represented by formula (1), and other R ^1s are independently a group represented by hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms;
n is an integer from 0 to 2.
In formula (1), R ² is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the bonding position to the aromatic ring.

[7] The composition according to item [3], wherein in the compound represented by formula (A), X is a single bond or -C≡C-.

[8] The composition according to item [4], wherein in the compound represented by formula (BI), X is a single bond or -C≡C-.

[9] The composition according to item [5], wherein in the compound represented by formula (B-II), X is a single bond or -C≡C-.

[10] The composition according to item [6], wherein in the compound represented by formula (B-III), X is a single bond or -C≡C-.

[11] The composition described in items [1] to [10], further comprising a curing accelerator.

[12] The composition described in item [11], further comprising an inorganic filler.

[13] The composition described in item [12], wherein the inorganic filler is aluminum oxide, boron nitride, or aluminum nitride.

[14] A cured product obtained by curing the composition described in any one of items [1] to [13].

[15] A material for electronic components using the cured product of item [14].

[16] A compound represented by formula (A1):
In formula (A1),
R ^ep independently represents a group having 3 to 12 carbon atoms including oxiranyl;
X independently represents a single bond, alkylene having 1 to 12 carbon atoms, —CH ₂ O—, —CH═CH—, or —C≡C—;
At least one R ¹ is a group represented by formula (1), and other R ^1s are independently hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms;
n is an integer from 0 to 2.

In formula (1),
^R2 is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the position of attachment to the aromatic ring.

[17] A compound represented by formula (B1):
In formula (B1),
X independently represents a single bond, alkylene having 1 to 12 carbon atoms, —CH ₂ O—, —CH═CH—, or —C≡C—;
At least one R ¹ is a group represented by formula (1), and other R ^1s are independently hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms;
n is an integer from 0 to 2.
In formula (1), R ² is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the bonding position to the aromatic ring.
However, the compound represented by formula (B1) is not a compound represented by formula (B1-1).

[18] A compound represented by formula (B2):

In formula (B2),
X independently represents a single bond, alkylene having 1 to 12 carbon atoms, —CH ₂ O—, —CH═CH—, or —C≡C—;
At least one R ¹ is a group represented by formula (1), and other R ^1s are independently hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms;
^R3 is independently alkyl having 1 to 6 carbon atoms or phenyl;
n is an integer from 0 to 2.
In formula (1), R ² is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the bonding position to the aromatic ring.

[19] A compound represented by formula (B3):

In formula (B3),
X independently represents a single bond, alkylene having 1 to 12 carbon atoms, —CH ₂ O—, —CH═CH—, or —C≡C—;
At least one R ¹ is a group represented by formula (1), and other R ^1s are independently hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms;
n is an integer from 0 to 2.
In formula (1), R ² is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the bonding position to the aromatic ring.

[20] In the compound represented by formula (A1), R ^ep is independently a group having 3 to 12 carbon atoms containing oxiranyl, X is a single bond, one of R ¹ is a group represented by formula (1), the other R ¹ is hydrogen, and n is an integer of 0 or 1. The compound according to item [16].

[21] In the compound represented by formula (B1), X is a single bond, one of R ¹ is a group represented by formula (1), the other R ¹ is hydrogen, and n is an integer of 0 or 1. The compound according to item [17].

[22] In the compound represented by formula (B2), X is a single bond, one of R ¹ is a group represented by formula (1), the other R ¹ is hydrogen, and n is an integer of 0 or 1. The compound according to item [18].

[23] In the compound represented by formula (B3), X is a single bond, one of R ¹ is a group represented by formula (1), the other R ¹ is hydrogen, and n is an integer of 0 or 1. The compound according to item [19].

The phrase "at least one hydrogen atom in the ring may be replaced by alkyl having 1 to 10 carbon atoms" means, for example, an embodiment in which at least one hydrogen atom at the 2-, 3-, 5-, and 6-positions of 1,4-phenylene is replaced by a substituent such as fluorine or methyl.
"Compound (1)" means a compound represented by formula (1), and may also mean at least one compound represented by formula (1).

[Component A and Component B]
As described above, the problem of the present application can be solved by using a composition containing Component A as an epoxy compound and at least one of Component B below as a curing agent.

Component A: A compound having two or more oxiranyl groups and 2 to 5 aromatic rings, in which 1 to 3 hydrogen atoms of the aromatic rings have been replaced by groups derived from vinyl.
Component B: A compound having two or more phenolic hydroxyl groups or two or more cyanate esters and having two to five aromatic rings, in which one to three hydrogen atoms of the aromatic rings have been replaced by groups derived from vinyl.

The vinyl-derived group is a vinyl or a group in which the H of a vinyl has been replaced with a monovalent organic group. There is no limit to the number of vinyl substituents, but to improve heat resistance, it is preferable that the vinyl be unsubstituted or monosubstituted. There is also no limit to the position of the vinyl substituents.

The number of vinyl-derived groups in the compound of component A or component B is 1 to 3, but in order to improve the liquid crystal properties of the composition, 1 to 2 is preferred, and 1 is most preferred.

In order to further improve the heat resistance of the epoxy resin cured product, it is preferable to use a composition containing both Component A and Component B of the present invention. On the other hand, in order to adjust the physical properties of the cured product, such as adjusting the linear expansion coefficient, it is also preferable to use a composition containing either Component A or Component B of the present invention. Furthermore, for the same purpose, other known epoxy resin compositions may be added to the composition of the present invention.

To improve thermal conductivity after curing, it is preferable to arrange the molecular skeleton in a highly orderly manner in the cured epoxy resin. Therefore, it is preferable to enhance liquid crystallinity in the epoxy resin composition or during its curing. To enhance liquid crystallinity, it is preferable that the structure of the compound in component A or component B has a structure in which aromatic rings are linked together.

It is also preferable to impart liquid crystallinity to the compounds of components A and B themselves in order to enhance the liquid crystallinity of the epoxy resin composition or its curing state. In this case, to impart liquid crystallinity to the compound, it is preferable that the core has a structure in which aromatic rings are connected in a linear fashion, with flexible substituents such as alkyls attached to both ends of the core. The core of a compound with liquid crystallinity refers to a structure in which aromatic rings or alicyclic rings are linked by bonding groups with relatively fixed conformations. Examples of such bonding groups include single bonds, ethylene, oxymethylene, double bonds, and triple bonds. In this case, the above-mentioned "straight line" does not have to be strictly linear; it can be bent at an angle of approximately 45 degrees.

For the above-mentioned compounds with liquid crystallinity, it is preferable that the core have two to five aromatic rings in order to expand the liquid crystal temperature range. To improve compatibility between components or to reduce material costs, it is more preferable that the core have two to four aromatic rings. Furthermore, to satisfy both the above-mentioned liquid crystallinity and compatibility characteristics, it is most preferable that the core have three aromatic rings.

In order to impart high thermal conductivity and heat resistance to the cured epoxy resin, the component A of the present invention is preferably a compound represented by formula (A).

In formula (A), R ^ep is independently a group having 3 to 12 carbon atoms including oxiranyl. X is independently a single bond, alkylene having 1 to 12 carbon atoms, -CH ₂ O-, -CH═CH-, or -C≡C-. At least one R ¹ is a group represented by formula (1), and the other R ^1s are independently hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms, and n is an integer of 0 to 2.
In formula (1), R ² is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the bonding position to the aromatic ring.

In the structure of formula (A), from the viewpoint of improving liquid crystallinity and heat resistance and ease of production, X is preferably a single bond, -( _CH2 ) _2- , -( _CH2 ) _4- , -( _CH2 ) _6- , -( _CH2 ) _8- , -( _CH2 ) _10- , -( _CH2 ) _12- , or -C≡C-, more preferably a single bond, -( _CH2 ) _2- , -(CH2) _{4- ,} or -C≡C-, and most preferably a single bond. Preferred examples of such formula (A) include compounds represented by formulae (A-1) to (A-11).

In formulas (A-1) to (A-11), R ^ep represents a group having 3 to 12 carbon atoms including oxiranyl, R ¹⁰ and R ¹¹ each independently represent hydrogen or alkyl having 1 to 6 carbon atoms, and at least one of R ¹⁰ and R ¹¹ represents hydrogen.

In the above formulas (A-1) to (A-11), R ^ep is preferably glycidyl, and R ¹⁰ and R ¹¹ are preferably hydrogen or alkyl having 1 to 3 carbon atoms, since this provides high liquid crystallinity and reduces production costs.

It is somewhat difficult to synthesize component B, which has a structure in which flexible substituents are bonded to both ends of the core. Such compounds are unlikely to exhibit liquid crystallinity. However, when the component B compound of the present invention is mixed with another compound having an aromatic ring, it readily interacts with that compound. Therefore, if the component A compound or other known epoxy compounds exhibit liquid crystallinity, the liquid crystallinity of the epoxy compound is not impaired. As a result, the composition of the present invention exhibits high liquid crystallinity.

In order to impart high thermal conductivity and heat resistance to the cured epoxy resin, the component B of the present invention is preferably a compound having a structure represented by formula (BI).
In formula (BI), X is independently a single bond, alkylene having 1 to 12 carbon atoms, -CH ₂ O-, -CH=CH-, or -C≡C-. At least one R ¹ is a group represented by formula (1), and the other R ^1s are independently hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms, and n is an integer of 0 to 2.
In formula (1), R ² is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the bonding position to the aromatic ring.

Alternatively, the component B of the present invention is preferably a compound having a structure represented by formula (B-II).
In formula (B-II),
X independently represents a single bond, alkylene having 1 to 12 carbon atoms, —CH ₂ O—, —CH═CH—, or —C≡C—;
At least one R ¹ is a group represented by formula (1), and other R ^1s are independently a group represented by hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms;
^R3 is independently alkyl having 1 to 6 carbon atoms or phenyl;
n is an integer from 0 to 2.

Furthermore, the component B of the present invention is preferably a compound having a structure represented by formula (B-III).

In formula (B-III), X is independently a single bond, alkylene having 1 to 12 carbon atoms, —CH ₂ O—, —CH═CH—, or —C≡C—. At least one R ¹ is a group represented by formula (1), and the other R ^1s are independently hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms, and n is an integer of 0 to 2.

In the compounds represented by formula (B-I), formula (B-II), and formula (B-III), from the viewpoint of improving liquid crystallinity and heat resistance and ease of production, X is preferably a single bond, -(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -, -(CH ₂ ) ₆ -, -(CH ₂ ) ₈ -, -(CH ₂ ) ₁₀ -, -(CH ₂ ) ₁₂ -, or -C≡C-, more preferably a single bond, -(CH ₂ ) ₂ -, -(CH ₂ ) ₄ -, or -C≡C-, and most preferably a single bond. Preferred examples of such compounds (B-I), (B-II), and (B-III) include the compounds represented by the following formulas (B-1) to (B-13).

In formulas (B-1) to (B-13), R ¹² independently represents a hydroxyl group, a group in which the hydroxyl group is acylated, or cyanato; R ¹⁰ and R ¹¹ independently represent hydrogen or alkyl having 1 to 6 carbon atoms, and at least one of R ¹⁰ and R ¹¹ is hydrogen.

In the above formulas (B-1) to (B-13), R ¹⁰ and R ¹¹ are preferably hydrogen or alkyl having 1 to 3 carbon atoms, as this provides high liquid crystallinity and reduces production costs.

The desired properties can be obtained by using one or more of the compounds of component A or component B used in the composition of the present invention. Furthermore, other known epoxy compounds and curing agents can be used in combination, as long as they do not impair the liquid crystallinity of the composition. When using these components in combination, there are no particular restrictions on the content of the compound of component A or component B. However, to achieve the effects of the present invention, the content of component A or component B is preferably 30% to 100% by weight, and more preferably 50% to 100% by weight, of the total amount of the epoxy compound or curing agent, respectively.

[Epoxy compounds other than component A]
As such an epoxy compound, liquid crystalline epoxy compounds represented by formulas (LC-1) to (LC-12) can be preferably used.

As the other epoxy compounds, non-liquid crystal epoxy compounds represented by formulas (o-1) to (o-15) are preferably used.

In formula (o-6), Z ¹⁰ is a single bond, —CH ₂ —, —O—, —S—, —CH(CH ₃ )—, —C(CH ₃ ) ₂ —, —SO ₂ —, or —C(CF ₃ ) ₂ —.

In the formula (o-7) and the formula (o-8), Z ¹¹ is >CH— or >CCH ₃ —.

In addition, resins composed of compounds represented by formulas (o-20) to (o-24) are also preferably used as the other epoxy compounds.

In formula (o-20), Z ¹² and Z ¹³ are independently a single bond, —CH ₂ —, —O—, —S—, —CH(CH ₃ ) —, —C(CH ₃ ) ₂ —, —SO ₂ —, or —C(CF ₃ ) ₂ —, and n21 is an integer of 1 or more and 5,000 or less.
In formula (o-21) and formula (o-22), n21 is an integer of 1 or more and 5000 or less. n22 and n23 are independently 0 or 1, and when n21 is 2 or more, they may be different for each repeat.
R ¹⁰ and R ¹¹ are 1,4-phenylene, 4,4′-biphenylene, or cyclopentadienylene.
In addition, hydrogen on the aromatic ring in formulae (o-20) to (o-22) may be replaced with methyl.

In formula (o-23) and formula (o-24), Z ¹⁴ independently represents a single bond, —CH(CH ₃ )—, or —C(CH ₃ ) ₂ —, and n21 represents an integer of 1 or more and 5,000 or less.
In addition, hydrogen on the aromatic ring in formula (o-23) and formula (o-24) may be replaced by methyl.

There are no particular restrictions on the content of such known epoxy compounds in the composition of the present invention, so long as the composition or its cured product exhibits the desired properties. That is, they can be used in an amount between 0.1 and 70% by weight, based on the total weight of the epoxy compounds. In this case, to achieve the effects of the present invention, they are preferably used in an amount between 0.1 and 60% by weight, more preferably between 0.1 and 55% by weight, and most preferably between 0.1 and 50% by weight.

[Other curing agents]
The curing agent that can be used in combination with the composition of the present invention other than component B may be any known compound such as a phenol, phenol ester, cyanate ester, amine, carboxylic acid, carboxylic acid ester, acid anhydride, or thiol. In this case, it is preferable to use a phenol-based or cyanate ester-based curing agent in order to suppress curing of the composition at room temperature and improve storage stability.

The phenol-based curing agent is preferably at least one compound represented by the following formulas (p-1) to (p-6), as it does not significantly impair the liquid crystallinity of the composition and is readily available.

In formula (p-1), n31 represents an integer of 2 or more and 4 or less;
Ring B is benzene, naphthalene, anthracene, fluorene, or 9,9-diphenylfluorene, and in these rings B, at least one hydrogen may be replaced by alkyl having 1 to 3 carbon atoms or alkoxy having 1 to 3 carbon atoms.
In formula (p-2), n32 and n33 independently represent an integer of 1 to 3;
Z ³⁰ represents a single bond, an alkylene having 1 to 10 carbon atoms, —CH(CH ₃ )—, —C(CH ₃ ) ₂ —, —C(CF ₃ ) ₂ —, —O—, —S—, or —SO ₂ —;
At least one hydrogen atom on the benzene ring may be replaced by an alkyl group having 1 to 3 carbon atoms.
In formula (p-3) and formula (p-4), n34 is an integer of 1 or more and 5000 or less, n35 and n36 are independently 0 or 1, and when n34 is 2 or more, it may be different for each repetition.
In formula (p-4), R ¹⁰ and R ¹¹ are 1,4-phenylene, 4,4′-biphenylene, or cyclopentadienylene;
In formula (p-5), n34 represents an integer of 1 or more and 5000 or less,
In formula (p-6), n34 represents an integer of 1 or more and 5000 or less,
Z ³¹ independently represents a single bond, —CH(CH ₃ )—, or —C(CH ₃ ) ₂ —; n34 represents an integer of 1 or more and 5,000 or less.
In addition, hydrogen on the aromatic ring in formulas (p-3) to (p-6) may be replaced with methyl.

The amine-based curing agent is preferably at least one compound represented by the following formula (a-1) or (a-2), since it does not significantly impair the liquid crystallinity of the composition and is easily available.
E ¹ -Z-(L-Z)n-E ¹ (a-1)
L ¹ -Z-E (a-2)

In formulae (a-1) and (a-2), Z independently represents a single bond, —O—, —NH—, —S—, —SO ₂ —, —CO ₂ —, or alkylene having 1 to 12 carbon atoms;
In formula (a-1),
E ¹ is independently amino, alkylamino having 1 to 10 carbon atoms, hydroxyl group, or carboxy, and at least one E is amino or alkylamino having 1 to 10 carbon atoms;
L is independently a single bond, cyclohexylene, phenylene, or naphthalene, and at least one hydrogen atom in these rings may be replaced by an alkyl group having 1 to 10 carbon atoms;
n is an integer from 0 to 7.
In formula (2-2),
L ¹ is hydrogen, cyclohexyl, phenyl, or naphthyl, and at least one hydrogen atom in these rings may be replaced by alkyl having 1 to 10 carbon atoms;
E is amino or alkylamino having 1 to 10 carbon atoms.

Such compounds represented by formula (a-1) include aliphatic polyamines having 2 to 12 carbon atoms, such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, p-xylenediamine, and m-xylenediamine, p-phenylenediamine, N-methyl-p-phenylenediamine, N-ethyl-p-phenylenediamine, N-propyl-p-phenylenediamine, N-butyl-p-phenylenediamine, 2,5-diaminotoluene, m-phenylenediamine, N-methyl-m-phenylenediamine, N-ethyl-m-phenylenediamine, N-propyl-m-phenylenediamine, and N-butyl-m-phenylenediamine. Examples of suitable amines include aromatic polyamines such as 2,4-diaminotoluene, 2,6-diaminotoluene, o-phenylenediamine, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 1,1-bis(4-aminophenyl)cyclohexane, 4,4'-diaminodiphenylsulfone, bis(4-aminophenyl)phenylmethane, m-tolidine, and o-tolidine; and alicyclic polyamines such as 1,4-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,2-cyclohexyldiamine, and 1,3-bis(aminomethyl)cyclohexane.

Among these, p-phenylenediamine, N-methyl-p-phenylenediamine, N-ethyl-p-phenylenediamine, N-propyl-p-phenylenediamine, N-butyl-p-phenylenediamine, 2,5-diaminotoluene, m-phenylenediamine, N-methyl-m-phenylenediamine, N-ethyl-m-phenylenediamine, N-propyl-m-phenylenediamine, N-butyl-m-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfone are particularly preferred due to their good compatibility when formed into compositions and excellent storage stability.

Examples of compounds represented by formula (a-2) include aliphatic amines having 2 to 12 carbon atoms, such as n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, and n-dodecylamine; aromatic amines, such as aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,6-dimethylaniline, 2,4,6-trimethylaniline, 2-ethylaniline, 1-naphthylamine, and 1-amino-2-methylnaphthalene; and alicyclic amines, such as cyclohexylamine and 2-methylcyclohexylamine. Among these, aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,6-dimethylaniline, 2,4,6-trimethylaniline, and 2-ethylaniline are particularly suitable due to their good compatibility when made into compositions and excellent storage stability.

Preferred carboxy-containing curing agents include phthalic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and benzophenone-4,4'-dicarboxylic acid.

There are no particular restrictions on the content of such known curing agents in the composition of the present invention, so long as the composition or its cured product exhibits the desired properties. In other words, they can be used in an amount between 0.1 and 70% by weight based on the total weight of the curing agent. In this case, to achieve the effects of the present invention, they are preferably used in an amount between 0.1 and 60% by weight, more preferably between 0.1 and 55% by weight, and most preferably between 0.1 and 50% by weight.

In the composition of the present invention, there are no particular restrictions on the ratio of the epoxy compound containing component A to the curing agent containing component B. To efficiently promote the reaction and improve heat resistance, it is preferable to use equivalent amounts of reactive groups in the epoxy compound and the curing agent. For example, in the case of epoxy:phenol, the ratio is 1:1, and in the case of epoxy:amine, the ratio is 2:1.

[Curing accelerator]
The composition of the present invention contains an epoxy compound as component A or a curing agent as component B. To improve heat resistance, the composition of the present invention preferably further contains a curing accelerator. Examples of such curing accelerators include imidazole-based curing accelerators such as 2-ethyl-4-methyl-1H-imidazole, 2-phenyl-4-methyl-1H-imidazole, 1,2-dimethylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphorus-based curing accelerators such as triphenylphosphine; amine-based curing accelerators such as 2,4,6-tris(dimethylaminomethyl)phenol, triethylenediamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 4-dimethylaminopyridine; and tetraalkylammonium salts. Among these curing accelerators, it is preferable to use imidazole-based curing accelerators because they have a curing temperature of 200° C. or less and have high curability.

In order to efficiently promote the reaction and improve heat resistance, the concentration of the curing accelerator in the composition of the present invention is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more, based on the weight of the polymerizable compound of the present invention. Furthermore, in order to avoid deterioration in reliability due to sublimation of the curing accelerator, the concentration is preferably 5% by weight or less, and more preferably 3% by weight or less, based on the weight of the polymerizable compound of the present invention.

[Inorganic filler]
The composition for electronic devices of the present invention may contain an inorganic filler.
The inorganic filler contained in the composition for electronic components may be a highly thermally conductive filler, such as a nitride such as aluminum nitride, boron nitride, or silicon nitride. Diamond, graphite, silicon carbide, silicon, beryllia, magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, copper oxide, titanium oxide, cerium oxide, yttrium oxide, tin oxide, holminium oxide, bismuth oxide, cobalt oxide, calcium oxide, aluminum nitride, boron nitride, silicon nitride, magnesium hydroxide, aluminum hydroxide, gold, silver, copper, platinum, iron, tin, lead, nickel, aluminum, magnesium, tungsten, molybdenum, or stainless steel. Boron nitride, aluminum nitride, or aluminum oxide is preferred. Boron nitride and aluminum nitride are preferred because they have extremely high thermal conductivity in the planar direction, a low dielectric constant, and high insulating properties. Hexagonal boron nitride (h-BN) and aluminum nitride are particularly preferred.

The shape of the inorganic filler may be spherical, amorphous, fibrous, rod-like, cylindrical, plate-like, or tetrapod-like. The type, shape, size, and amount of inorganic filler added can be selected appropriately depending on the purpose. For example, if the cured product (electronic component material) formed from the composition for electronic components requires insulation, a conductive inorganic filler may be used as long as the desired insulation properties are maintained.

The average particle size of the inorganic filler is preferably, for example, 0.1 to 200 μm. It is more preferably 1 to 100 μm. A particle size of 0.1 μm or more provides good thermal conductivity, while a particle size of 200 μm or less allows for a higher filling rate. Note that the average particle size in this specification is based on particle size distribution measured using laser diffraction and scattering methods. In other words, using analysis based on the Fraunhofer diffraction theory and Mie scattering theory, when powder is divided into two particles at a certain particle size using a wet method, the median diameter is the diameter at which the larger and smaller particles are equal in volume (based on volume).

When used in heat dissipation components, the amount of inorganic filler added is preferably 20 to 95% by weight of the total amount of nonvolatile matter in the composition for electronic components. It is more preferably 50 to 95% by weight. Amounts of 20% by weight or more are preferred because they increase thermal conductivity. Amounts of 95% by weight or less are preferred because they do not make the heat dissipation component brittle.

Unmodified inorganic fillers may be used as is. Alternatively, fillers whose surfaces have been treated with a coupling agent may be used. For example, boron nitride (h-BN) may be treated with a silane coupling agent. Since boron nitride particles have no reactive groups on their surface, the silane coupling agent bonds only to their periphery. Boron nitride treated with a coupling agent can form bonds with polymerizable compounds in electronic component compositions, and these bonds are thought to contribute to thermal conductivity. Therefore, coupling agents that react with oxiranyl, oxetanyl, or groups possessed by curing agents are preferred. For example, amine-based agents or those containing oxiranyl or oxetanyl are preferred. Specific examples include Sila-Ace S310, S320, S330, S360, S510, and S530 manufactured by JNC Corporation.

The inorganic filler may be treated with a coupling agent and then surface-modified with a compound having a polymerizable group (polymerizable compound) such as epoxy. For example, boron nitride (h-BN) treated with a silane coupling agent is surface-modified with a polymerizable compound. If boron nitride surface-modified with a polymerizable compound can form a bond with the polymerizable compound or curing agent in the composition for electronic components, this bond is thought to contribute to thermal conductivity. For example, the polymerizable compound may be the polymerizable compound of the present invention represented by formula (1), or any other polymerizable compound.

[Other components]
Other components that can be contained in the composition of the present invention are not particularly limited, and examples thereof include a polymerizable compound having a polymerizable group other than epoxy, a non-polymerizable compound, a polymerization initiator, and a solvent.

The polymerizable compound having a polymerizable group other than epoxy is not particularly limited as long as it does not deteriorate the properties of the electronic material of the present invention, and any known polymerizable compound can be used. Among them, compounds that undergo radical polymerization, such as acrylic compounds and styrene-based compounds, can be preferably used, and these compounds that have liquid crystallinity can be more preferably used.
Examples of polymerization initiators include thermal polymerization initiators, photocationic polymerization initiators, and photoanionic polymerization initiators. Examples of thermal cationic polymerization initiators include sulfonium salts, boron trifluoride-amine complexes, dicyanazide, organic acid hydrazides, and toluenesulfonate esters. Known examples of photocationic initiators include sulfonium salts, iodonium salts, and nonionic initiators. Known examples of photoanionic initiators include oximes, carbamates, guanidinium carboxylates, and nifedipine.

When the composition of the present invention contains a compound that undergoes radical polymerization, such as an acrylic compound or a styrene-based compound, a radical polymerization initiator may be used.

The composition of the present invention may contain a solvent. Polymerization of the composition may be carried out in a solvent or without a solvent. Preferred solvents include, for example, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, dipropylene glycol methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol diethyl ether. Examples of suitable solvents include dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, diethyl carbonate, ethyl methyl carbonate, γ-butyrolactone, methyl lactate, ethyl lactate, butyl lactate, 2-ethylhexanol, 1-propanol, isobutyl alcohol, n-butanol, 2-pentanone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, and ethylene glycol. These solvents may be used alone or in combination.

Because the composition of the present invention has high polymerizability, a stabilizer may be added to facilitate handling. Known stabilizers can be used without restriction. Examples include hydroquinone, 4-ethoxyphenol, and 3,5-di-t-butyl-4-hydroxytoluene (BHT).

Additives (oxides, etc.) may also be added to adjust the viscosity and color of the composition for electronic components. Examples include titanium oxide to produce a white color, carbon black to produce a black color, and silica fine powder to adjust viscosity. To further increase mechanical strength, inorganic fibers such as glass or carbon fiber, or their cloth, or synthetic fibers such as polyvinyl formal, polyvinyl butyral, polyester, polyamide, or polyimide, or supramolecules may also be added.

[Electronic component materials]
The material for electronic components of the present invention is obtained by curing the composition for electronic components according to the second embodiment and molding the cured product according to the purpose. For example, the material for electronic components can be used as a heat dissipation member.

The material for electronic components is a polymer obtained by polymerizing (curing) the composition of the present invention. This polymer has high thermal conductivity and excellent chemical stability, heat resistance, hardness, and mechanical strength. The mechanical strength mentioned here refers to Young's modulus, tensile strength, tear strength, flexural strength, flexural modulus, impact strength, etc.

The composition of the present invention is a thermosetting resin. Thermosetting resins are cured by heating the raw material composition, polymerizing the monomers contained in the composition and further three-dimensionally crosslinking the monomers. The heating temperature is preferably within a temperature range in which the composition of the present invention exhibits a liquid crystal phase. Furthermore, the liquid crystal temperature range of the composition of the present invention may increase as the curing proceeds to a certain extent. In such cases, the composition may be cured within the increased liquid crystal temperature range.

The curing temperature may be constant, or may be increased or decreased in stages. In the latter case, the initial curing temperature is preferably a temperature at which the composition or its cured product exhibits a liquid crystal phase, in order to improve the heat dissipation characteristics of the material. It is also preferable to heat at a temperature higher than the initial curing temperature in order to improve heat resistance. When curing in stages at different temperatures, it is preferable to use multiple heating devices set to constant but different temperatures to shorten the production time of the cured product.

The thermosetting temperature for thermal polymerization is in the range of 20°C to 350°C, preferably 20°C to 250°C, and more preferably 50°C to 200°C. The curing time is in the range of 5 seconds to 10 hours, preferably 1 minute to 8 hours, and more preferably 5 minutes to 5 hours. After polymerization, slow cooling is preferred to suppress stress distortion, etc. Reheating may also be performed to relieve distortion, etc.

A crosslinking agent may be added to further crosslink the polymer. This results in a polymer (cured product) with excellent chemical and heat resistance. Any known crosslinking agent can be used, and examples include trimethylolpropane tris(3-mercaptopropionate).

The electronic component material of the present invention can be used in the form of a sheet, film, thin film, fiber, molded product, or the like. Films and thin films are preferred. Films and thin films can be obtained by polymerizing the electronic component composition in a state where it is applied to a substrate or sandwiched between substrates. Alternatively, the electronic component composition can be obtained by applying a solvent-containing electronic component composition to a substrate and then removing the solvent. Furthermore, films can also be obtained by press molding the polymer. In this specification, the thickness of a sheet is 1 mm or more, the thickness of a film is 5 μm or more, preferably 10 to 900 μm, and more preferably 20 to 800 μm, and the thickness of a thin film is less than 5 μm. The thickness may be adjusted as appropriate depending on the application.

The electronic component material of the present invention not only has high thermal conductivity, but also excellent properties such as chemical stability, heat resistance, hardness, and mechanical strength. Therefore, it is useful for heat sinks, heat dissipation sheets, heat dissipation films, heat dissipation coatings, heat dissipation adhesives, and heat dissipation molded products.

Although the electronic component material formed from the polymerizable compound of the present invention has been described above as being used as a heat dissipation material, the use of the electronic component material is not limited to heat dissipation materials. For example, the electronic component material may also be used as a sealant or adhesive material.

[Method of manufacturing a composition for electronic components]
The composition for electronic components refers to the heat dissipation material, which is the composition of the present invention, and may contain an inorganic filler to enhance thermal conductivity, regardless of whether the inorganic filler is subjected to a coupling treatment. As a production example of the composition for electronic components, a production method in which the inorganic filler is subjected to a coupling treatment will be described. A known method can be used for the coupling treatment.

As an example, first add inorganic filler particles and a coupling agent to a solvent. Stir using a stirrer or similar device and then leave to stand. After the solvent dries, heat treatment is performed under vacuum conditions using a vacuum dryer or similar device. Solvent is added to these inorganic filler particles, and they are pulverized using ultrasonic treatment. This solution is separated and purified using a centrifuge. After discarding the supernatant, solvent is added and the same procedure is repeated several times. The purified inorganic filler particles are then dried in an oven.

Next, the coupling-treated inorganic filler particles and polymerizable compound are mixed using an agate mortar or similar, and then kneaded using a two-axis roll or similar. The mixture is then separated and purified by ultrasonic treatment and centrifugation.

An amine-based curing agent is then added, and the mixture is mixed using an agate mortar or similar, and then kneaded using a two-screw roll or similar. This produces a solvent-free composition for electronic components.

[Method of manufacturing materials for electronic components]
As an example, a method for producing a film as a material for electronic components using a solvent-free composition for electronic components will be described.

The solvent-free composition for electronic components is sandwiched between heating plates using a compression molding machine and compressed to form a molded product. The polymerizable compound polymerizes at a predetermined temperature and time to form a polymer. Post-curing may also be performed for an appropriate time and temperature. The pressure during compression molding is preferably 50 to 500 kgf/ ^cm2 , and more preferably 70 to 250 kgf/ ^cm2 . Generally, higher pressures during curing are preferable. However, it is preferable to apply an appropriate pressure, adjusting it as needed depending on the fluidity of the mold and the desired physical properties (such as which direction of thermal conductivity is most important).

The composition for electronic components is easier to handle if it is partially cured (semi-cured). For example, the semi-cured composition can be formed into a sheet, cut into the desired shape, and then placed between suitable components for bonding.

This article describes a method for producing a film as a material for electronic components using a solvent-containing composition for electronic components.

The composition for electronic components is applied to a substrate, and the solvent is then dried and removed to form a coating layer of uniform thickness. Coating methods include, for example, spin coating, roll coating, caten coating, flow coating, printing, microgravure coating, gravure coating, wire bar coating, slit coating, dip coating, spray coating, and meniscus coating.

The solvent can be removed by drying, for example, air drying at room temperature, drying on a hot plate, drying in a drying oven, or blowing warm or hot air. There are no particular restrictions on the conditions for solvent removal; drying should be continued until the solvent is mostly removed and the coating layer loses its fluidity.

[Electronic Components]
An example of an electronic component is an electronic device having a heat-generating portion. When the material for electronic components of the present invention is used as a heat dissipation member, the heat dissipation member is placed on the electronic device so as to contact the heat-generating portion. The heat dissipation member may be in the form of a heat dissipation plate, a heat dissipation sheet, a heat dissipation film, a heat dissipation adhesive, a heat dissipation molded product, or the like. In this way, the heat dissipation member dissipates heat generated in the electronic device, preventing heat-related breakdowns and extending the life of electronic devices incorporating the electronic device.

One example of an electronic device is a semiconductor element. Heat dissipation components have high thermal conductivity, as well as high heat resistance and insulation. Therefore, they are particularly effective for insulated gate bipolar transistors (IGBTs), which require a more efficient heat dissipation mechanism due to their high power consumption. An IGBT is a type of semiconductor element, a bipolar transistor with a MOSFET built into the gate, and is used for power control. Electronic devices equipped with IGBTs include the main conversion element of a high-power inverter, uninterruptible power supplies, variable voltage and variable frequency control devices for AC motors, control devices for railway vehicles, electric transportation equipment such as hybrid cars and electric cars, and induction cookers.

[Method for synthesizing compounds represented by formula (A1), formula (B1), and formula (B2)]
The compounds represented by formula (A1), formula (B1), and formula (B2) can be synthesized by combining known methods in organic synthetic chemistry. Methods for introducing the desired polymerizable group and ring structure into starting materials are described in, for example, Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John Wiley & Sons, Inc., Organic Reactions, John Wiley & Sons, Inc., Comprehensive Organic Synthesis, Pergamon Press, and New Experimental Chemistry Lectures (Maruzen). Japanese Patent Application Laid-Open No. 2006-265527 may also be referenced. Some of these methods are also disclosed in the Examples.

The present invention will be explained in detail below using examples. However, the present invention is not limited to the contents described in the examples. Unless a temperature is specified, measurements were made at 23°C.

[Measuring the phase transition temperature of compounds and identifying liquid crystal phases]
Measurements were performed using a polarizing microscope (Nikon) equipped with a hot stage (Mettler Toledo) and a differential scanning calorimeter (Perkin Elmer, Diamond DSC). Polarizing microscope measurements were performed under crossed Nicols. The heating rate for both measurements was 3°C/min. C indicates crystal, S indicates smectic phase, N indicates nematic phase, I indicates isotropic liquid, and () indicates monotropic liquid crystal phase.

[NMR measurement]
NMR was measured using a VARIAN NMR SYSTEM manufactured by VARIAN. The magnetic field strength for ^1H NMR measurement was 500 MHz, the sample was dissolved in a deuterated solvent such as _CDCl3 , and the measurement was carried out at room temperature. The number of accumulations was 8. The internal standard was tetramethylsilane. In the NMR symbols, s means singlet, d means doublet, t means triplet, m means multiplet, and br means broad.

[Confirmation of liquid crystal properties of the composition]
The composition was sandwiched between glass plates, melted, and then rapidly cooled to ensure uniform adhesion between the glass plates. The resulting sample was heated to 200°C at a heating rate of 5°C/min and then rapidly cooled to room temperature. The sample was observed under crossed Nicols using the polarizing microscope described above. The magnifications of the eyepiece and objective lens were 10x10. If light leakage due to scattering was observed in 50% or more of the observation area, the composition was determined to have liquid crystallinity. Alternatively, if the composition gave a vertically aligned cured product, a dark field was observed under the microscope. Therefore, light leakage caused by fanning the sample under crossed Nicols was visually confirmed.

[Evaluation of heat resistance by measuring the glass transition temperature (Tg)]
Measurement was performed using a Rigaku Thermo Plus EVO2 DSC-8231 high-sensitivity DSC-type differential scanning calorimeter. The composition placed in an aluminum pan was heated to 150°C at a heating rate of 10°C/min and maintained at that temperature for 30 minutes. It was then cooled to 40°C at a heating rate of 10°C/min and heated again to 200°C at a heating rate of 10°C/min. The glass transition temperature was determined from the DSC curve obtained during the second heating process.

[Measurement of thermal conductivity]
Samples consisting only of resin: The thermal diffusivity (α, m ² /s) of the samples was determined using an LFA467 HyperFlash manufactured by NETZSCH Co., Ltd. The thermal diffusivity was measured in both the in-plane direction and the thickness direction of the sample. The thermal conductivity (W/(Km)) was calculated from the specific heat (c, J/(Kg)) and density (ρ, g/m ³ ) of the sample according to the following formula:
κ = α x c x ρ
The specific heat was measured using a DSC-type high-sensitivity differential scanning calorimeter Thermo Plus EVO2 DSC-8231 manufactured by Rigaku Corp. The specific gravity was measured using a specific gravity balance type hydrometer DME-220 manufactured by Shinko Denshi Co., Ltd.
Filler-containing sample: The thermal diffusivity in the thickness direction of the sample was measured using an ai-Phase Mobile 1u thermal diffusivity measuring device manufactured by ai-Phase Corporation. The specific heat and density of the sample were also measured in the same manner as above. From these values, the thermal conductivity was calculated in the same manner as above.

[Epoxy compound and curing agent]
As the epoxy compound represented by formula (A), compounds represented by the following formulas (A-1-1), (A-7-1), (A-7-2), and (A-10-1) were used in the examples. These compounds were synthesized as described below.
The epoxy compound other than component A was the epoxy compound represented by YX4000H (manufactured by Mitsubishi Chemical Corporation). Furthermore, epoxy compounds represented by the following formulas (LC-6) and (LC-10) were also used. These compounds were synthesized in accordance with Japanese Patent Application No. 2021-083058.
As the curing agent represented by formula (B-I), compounds represented by the following formulas (B-1-1), (B-1-2), (B-1-3), (B-1-4), (B-9-1), (B-9-2), and (B-12-1) were used. In addition, as a curing agent other than component B, DHTP-M (manufactured by Honshu Chemical Industry Co., Ltd.), a curing agent described in JP 2015-209529 A, was used.

[Commercially available curing agents]
As the amine curing agents, 1,3-phenylenediamine (PDA) and 3,5-dimethylaniline (DMA) manufactured by Tokyo Chemical Industry Co., Ltd. were used as they were without purification. Furthermore, as the phenolic curing agent, 4,4'-dihydroxybiphenyl (BPOH) was used as it was without purification.

[Curing accelerator]
Curesol 2PZ-PW (manufactured by Shikoku Chemicals Corporation), an imidazole-based curing accelerator, was used as is without purification.

[Reference example 1]
Synthesis of compound represented by formula (B-9-1)
In the above formula, THPO is tetrahydro-2H-pyran-2-yloxy, and PPTS represents pyridinium p-toluenesulfonate.

A mixture of 1.00 g (3.81 mmol) of 2,5-dibromostyrene, 1.86 g (8.38 mmol) of 4-(Tetrahydro-2H-pyran-2-yloxy)phenylboronic Acid, 0.220 g (0.190 mmol) of tetrakistriphenylphosphine palladium(0), and 1.62 g (15.3 mmol) of Na ₂ CO ₃ was refluxed in dimethoxyethane (20 ml) under a nitrogen stream for 3 hours. 2,5-Dibromostyrene was synthesized according to the method described in Journal of American Chemical Society, vol. 134, p. 16131 (2012). After completion of the reaction, the reaction solution was cooled, and 60 ml each of pure water and toluene were added. The organic layer was separated, washed twice with the same amount of pure water, and dried over anhydrous _MgSO4 . After filtration and distillation of the solvent under reduced pressure, the resulting product was purified by column chromatography (silica gel, toluene/ethyl acetate = 10/1) to obtain compound (B-9-1-a). Yield: 1.26 g (72%).

A mixture of 1.57 g (3.43 mmol) of compound (B-9-1-a) and 346 mg (1.38 mmol) of pyridinium p-toluenesulfonate was stirred at room temperature for 2 days in a tetrahydrofuran (THF)/methanol (10 ml/10 ml) mixed solvent. Ethyl acetate (30 ml) and pure water (30 ml) were added, and the mixture was separated. The organic layer was washed with pure water (20 ml) and then dried over anhydrous MgSO _4. After filtration and distillation under reduced pressure, the resulting product was purified by recrystallization (ethanol/toluene) to obtain compound (B-9-1). Yield: 833 mg (84%).

Melting point (°C): 191-194.
¹ H-NMR (ppm, CDCl ₃ ); 7.77 (d, 1H, J = 2.50Hz), 7.56-7.54 (m, 2H), 7.49 (dd, 1H, J = 8.00, 2.50Hz), 7.32 (d, 1H, J = 8.00Hz), 7.28-7.25 (m, 2H ), 6.95-6.88 (m, 4H), 6.80-6.75 (m, 1H), 5.76 (dd, 1H, J = 17.50, 1.50Hz), 5.23 (dd, 1H, J = 11.0, 1.00Hz), 4.82 (brs, 2H)

[Example 1]
Synthesis of compound represented by formula (A-7-1)

A mixture of 1.00 g (3.47 mmol) of the compound represented by formula (B-9-1), 4.73 g (34.5 mmol) of epibromohydrin, and 1.92 g (13.9 mmol) of K ₂ CO ₃ was refluxed in methyl ethyl ketone (10 ml) for 10 hours. After cooling, toluene (30 ml) and pure water (30 ml) were added to the reaction solution, and the mixture was separated. The organic layer was washed with pure water (20 ml) and then dried over anhydrous MgSO _4. After filtration and distillation under reduced pressure, the resulting product was purified by column chromatography (toluene:ethyl acetate=10:1) to obtain compound (A-7-1). Yield: 1.03 g (74%).
Phase transition point (°C): C 130.6 I
¹ H-NMR (ppm, CDCl ₃ ); 7.79 (d, 1H, J = 2.00Hz), 7.59-7.57 (m, 2H), 7.49 (dd, 1H, J = 8.00, 2.00H z), 7.33-7.29 (m, 3H), 7.03-7.95 (m, 4H), 6.78-6.72 (m, 1H), 5.75 (dd, 1H , J=17.50, 1.50Hz), 5.22 (dd, 1H, J=10.5, 1.00Hz), 4.29-4.25 (m, 2H), 4. 03-3.99 (m, 2H), 3.40-3.38 (m, 2H), 2.94-2.91 (m, 2H), 2.79-2.77 (m, 2H).

Example 2: Synthesis of compound represented by formula (B-9-2)
In the above formula, THPO and PPTS have the same meanings as above.

The compound represented by formula (B-9-2-a) was synthesized in the same manner as in Example 1, except that 1,4-dibromo-2-isopropenylbenzene was used instead of 2,5-dibromostyrene. The raw material, 1,4-dibromo-2-isopropenylbenzene, was synthesized according to DE 2431144. The resulting product was purified by column chromatography (silica gel, toluene) to obtain compound (B-9-2-a). Yield: 67%.

Compound (B-9-2-a) was de-THPedicated using the same method as in Reference Example 1. The resulting product was purified by recrystallization (ethyl acetate/heptane) to obtain compound (B-9-2). Yield: 90%.

Melting point (°C): 140.5
¹ H-NMR (ppm, CDCl ₃ ); 7.55-7.52 (m, 2H), 7.50-7.48 (m, 1H), 7.60 (d, 1H, J = 2.00Hz), 7.36-7.31 (m, 3H), 6.93-6.90 (m, 2H), 6.8 7-6.84 (m, 2H), 5.11 (dd, 1H, J=1.50, 1.50Hz), 5.07 (brs, 1H), 4.84 (brs, 1H), 4.80 (brs, 1H), 1.70 (s, 3H).

Example 3 Synthesis of Compound Represented by Formula (A-7-2)
The compound represented by formula (B-9-2) was used to synthesize the compound in the same manner as in Example 1. The resulting product was purified by column chromatography (toluene:ethyl acetate=40:1) to obtain compound (A-7-2). The yield was 85%.

Phase transition point (°C): C 131.9 I
¹ H-NMR (ppm, CDCl ₃ ); 7.59-7.56 (m, 2H), 7.51-7.49 (m, 2H), 7.47 (d, 1H, J = 2.00Hz), 7.40-7.38 ( m, 2H), 7.33 (d, 2H, J = 8.00Hz), 7.02-6.99 (m, 2H), 6.95-6.92 (m, 2H), 5.11 (d d, 1H, J=1.50, 1.50Hz), 5.07 (brs, 1H), 4.29-4.25 (m, 2H), 4.04-3.99 (m, 2H) , 3.41-3.38 (m, 2H), 2.94 (t, 2H, J=4.50Hz), 2.80-2.78 (m, 2H), 1.70 (s, 3H).

[Example 4] Synthesis of compound represented by formula (B-12-1)
In the above formula, Tf is trifluoromethanesulfonyl, and THP and PPTS have the same meanings as above.

3.4 ml (20.7 mmol) of trifluoromethanesulfonic anhydride was added to a solution of 2.00 g (9.34 mmol) of 3-formyl-4,4'-dihydroxybiphenyl and 6.6 ml of pyridine in methylene chloride (20 ml) at room temperature or below. After stirring overnight, the reaction mixture was poured into 50 ml of purified water and extracted with 50 ml of toluene. The organic layer was washed with dilute hydrochloric acid, purified water, and aqueous sodium bicarbonate (50 ml each) and then dried over anhydrous magnesium sulfate. The organic layer was filtered, the solvent was removed under reduced pressure, and the resulting product was purified by column chromatography (toluene) to obtain compound (B-12-1-a). Yield: 3.66 g (82%). In the above reaction, 3-formyl-4,4'-dihydroxybiphenyl was prepared according to the method described in Journal of Medicinal Chemistry, vol. 52, p. 858 (2009).

2.00 g (4.18 mmol) of compound (B-12-1-a) was reacted with 4-(Tetrahydro-2H-pyran-2-yloxy)phenylboronic Acid in the same manner as in Reference Example 1. The resulting product was purified by column chromatography (silica gel, toluene) to obtain compound (B-12-1-b). Yield: 1.45 g (65%).

A solution of 294 mg (2.62 mmol) of t-BuOK in 10 ml of THF was added to a solution of 868 mg (2.43 mmol) of methyltriphenylphosphonium bromide in 10 ml of THF at temperatures below 0°C. After stirring at 0°C for 30 minutes, the mixture was cooled to -20°C, and 1.00 g (1.87 mmol) of compound (B-12-1-b) was added. After stirring at room temperature for 2 hours, the mixture was poured into 50 ml of purified water and extracted with 50 ml of toluene. The organic layer was washed with 50 ml of purified water and then dried over anhydrous magnesium sulfate. The organic layer was filtered, the solvent was removed under reduced pressure, and the resulting product was purified by column chromatography (toluene) to obtain compound (B-12-1-c). Yield: 857 mg (86%).

(B-12-1) was synthesized using 850 mg (1.60 mmol) of compound (B-12-1-c) in the same manner as in Reference Example 1. The product was purified by recrystallization (ethanol/toluene) to obtain compound (B-12-1). Yield: 512 mg (88%).

Melting point: 250°C or higher
¹ H-NMR (ppm, CDCl ₃ ); 7.87 (d, 1H, J=1.50Hz), 7.73-7.70 (m, 2H), 7.66-7.62 (m, 2H), 7. 58 (dd, 1H, J = 7.50, 2.00Hz), 7.57-7.54 (m, 2H), 7.37 (d, 1H, J = 8.00H z), 7.30-7.27 (m, 2H), 6.95-6.89 (m, 4H), 6.79 (dd, 1H, J = 17.0, 11.0 Hz), 5.79 (d, 1H, J=17.0Hz), 5.26 (d, 1H, J=11.5Hz), 4.80 (brs, 2H).

[Example 5] Synthesis of compound represented by formula (A-10-1)
It was synthesized from the compound represented by formula (B-12-1) in the same manner as in Example 1. Yield: 78%.

Phase transition point (°C): C 169.2 S > 300 I
¹ H-NMR (ppm, CDCl ₃ ); 7.87 (d, 1H, J = 1.50Hz), 7.73-7.70 (m, 2H), 7.66-7.64 (m, 2H), 7.61-7.57 (m, 3 H), 7.37 (d, 1H, J = 8.00Hz), 7.34-7.32 (m, 2H), 7.05-6.98 (m, 4H), 6.79 (dd, 1H, J = 17.0, 11.0Hz), 5.79 (d, 1H, J = 17.0Hz), 5.25 (d, 1H, J = 11.0Hz), 4.31-4.27 (m, 2 H), 4.05-4.01 (m, 2H), 3.43-3.38 (m, 2H), 2.96-2.93 (m, 2H), 2.81-2.79 (m, 2H).

[Example 6] Synthesis of compound represented by formula (B-1-1)
A mixture of 2.00 g (9.34 mmol) of 3-formyl-4,4'-dihydroxybiphenyl, 4.7 g (56 mmol) of 3,4-dihydro-2H-pyran, and 0.47 g (1.9 mmol) of PPTS was stirred in 20 ml of CH ₂ Cl ₂ at room temperature overnight. 30 ml of saturated aqueous sodium bicarbonate was added to the reaction mixture, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and then filtered. The solvent was evaporated under reduced pressure, and the resulting product was purified by column chromatography (toluene:ethyl acetate=10:1) to obtain compound (B-1-1-a). Yield: 244 mg (7.9%).

Compound (B-1-1-a) was converted to compound (B-1-1-b) using a method similar to that described in Example 5 above. The crude product was purified by column chromatography (heptane:toluene = 1:1 → toluene). Yield: 86%.

Compound (B-1-1-b) was converted to compound (B-1-1) using a method similar to that described in Example 5 above. The crude product was purified by column chromatography (toluene:ethyl acetate = 2:1). Yield: 100%.

Melting point (°C): 138.0-145.7.
¹ H-NMR (ppm, CDCl ₃ ); 7.54 (d, 1H, J = 2.50Hz), 7.44-7.41 (AA'BB', 2H), 7.31 (dd, 1H, J = 8.00, 2.50Hz), 6.97 (dd, 1H, J = 17.50, 10.50Hz), 6.91 -6.87 (AA'BB', 2H), 6.85 (d, 1H, J = 8.50Hz), 5.80 (d, 1H, J = 18.00Hz), 5.41 (d, 1H, J = 11.00Hz), 4.99 (s, 1H), 4.76 (s, 1H).

[Example 7]
Synthesis of compound represented by formula (A-1-1)
A mixture of 320 mg (1.51 mmol) of the compound represented by formula (B-1-1), 4.18 g (30.2 mmol) of epibromohydrin, and 1.25 g (9.05 mmol) of K ₂ CO ₃ was refluxed in DMF (10 ml) for 2 hours. After cooling, ethyl acetate (40 ml) and pure water (40 ml) were added to the reaction solution, and the layers were separated. The organic layer was washed with saturated brine (40 ml) and then dried over anhydrous MgSO _4. After filtration and distillation of the solvent under reduced pressure, the resulting product was purified by column chromatography (toluene:ethyl acetate=9:1) to obtain compound (A-1-1). Yield: 440 mg (90%).
Melting point (°C): 60.0-77.1.
¹ H-NMR (ppm, CDCl ₃ ); 7.65 (d, 1H, J = 2.00Hz), 7.50-7.47 (m, 2H), 7.39 (dd, 1H, J = 8.50, 2.50Hz), 7 .11 (dd, 1H, J = 18.0, 11.0Hz), 7.00-6.97 (m, 2H), 6.92 (d, 1H, J = 8.50Hz), 5.82 ( dd, 1H, J=17.50, 1.50Hz), 5.32 (dd, 1H, J=11.0, 1.50Hz), 4.30-4.25 (m, 2H), 4. 05-3.99 (m, 2H), 3.42-3.37 (m, 2H), 2.93 (t, 2H, J=4.50Hz), 2.80-2.78 (m, 2H).

[Example 8] Synthesis of compound represented by formula (B-1-2)
To a solution of 1.00 g (4.71 mmol) of compound (B-1-1) and 0.96 g (12.1 mmol) of pyridine in 20 ml of CH ₂ Cl ₂ solvent, 1.16 g (11.4 mmol) of acetic anhydride was added at room temperature. The reaction solution was stirred overnight. Purified water (20 ml) was added to the reaction solution, and the organic layer was separated. The organic layer was washed twice with purified water (10 ml) and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the resulting product was purified by column chromatography (toluene:ethyl acetate=10:1) to obtain compound (B-1-2). Yield: 1.21 g (87%).

Melting point (°C): 95.0-98.1.
¹ H-NMR (ppm, CDCl ₃ ); 7.72 (d, 1H, J = 2.00Hz), 7.60-7.56 (AA'BB', 2H), 7.45 (dd, 1H, J = 9.00, 2.50Hz), 7.18-7.15 (AA'BB', 2H), 7.12 (d, 1H, J = 8.00Hz), 6.79 (dd, 1H, J = 17.5, 11.0Hz), 5.82 (d, 1H, J = 18.0Hz), 5.38 (d, 1H, J = 10Hz)
2.36 (s, 3H), 2.34 (s, 3H).

[Example 9] Synthesis of compound represented by formula (B-1-3)
A solution of 2.7 ml (30.9 mmol) of propionic acid chloride in 10 ml of CH ₂ Cl ₂ was added to a solution of 3.00 g (14.1 mmol) of compound (B-1-1) and 3.5 ml (43.4 mmol) of triethylamine in 30 ml of CH ₂ Cl ₂ at a temperature below 10°C. The reaction solution was stirred at room temperature for 7 hours, and then toluene (70 ml) and pure water (50 ml) were added. The organic layer was separated and washed three times with pure water. After drying over anhydrous magnesium sulfate, it was filtered and the solvent was distilled off under reduced pressure. The resulting product was purified by column chromatography (toluene → toluene:ethyl acetate = 10:1) to obtain compound (B-1-3). Yield: 4.26 g (93%). Compound (B-1-3) was a liquid at room temperature.

¹ H-NMR (ppm, CDCl ₃ ); 7.72 (d, 1H, J = 2.50Hz), 7.58-7.55 (AA'BB', 2H), 7.46 (dd, 1H, J = 9.00, 2.50Hz), 7.17-7.15 (AA'BB', 2H), 7.11 (d, 1H, J = 9. 00Hz), 6.78 (dd, 1H, J = 17.0, 10.5Hz), 5.81 (d, 1H, J = 17.5Hz), 5.37 (d, 1H, J = 11.5Hz), 2.68-2.60 (m, 4H), 1.33-1.27 (m, 6H).

[Example 10] Synthesis of compound represented by formula (B-1-4)
A diethyl ether solution of 500 mg (2.36 mmol) of compound (B-1-1) and 0.7 mL of triethylamine was added to a diethyl ether solution of 526 mg (4.96 mmol) of cyanogen bromide (3 mL) at −30° C. over 15 minutes. After stirring at room temperature for 1.5 hours, ethyl acetate (40 mL) and purified water (40 mL) were added to the reaction solution, and the organic layer was separated. The organic layer was washed once with saturated brine (40 mL) and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the resulting product was purified by recrystallization (toluene:ethanol = 4:1) to obtain compound (B-1-4). Yield: 300 mg (49%).

Melting point (°C): 157 (decomposition)
¹ H-NMR (ppm, CDCl ₃ ); 7.72 (d, 1H, J = 2.50Hz), 7.66-7.62 (AA'BB', 2H), 7.57 (d, 1H, J = 8.50Hz), 7.52 (dd, 1H, J = 8.5, 2.5Hz ) 7.43-7.40 (AA'BB', 2H), 6.91 (dd, 1H, J = 17.5, 11.0Hz), 5.91 (d, 1H, J = 18.0Hz), 5.54 (d, 1H, J = 11Hz).

[Example 11]
Preparation of Composition and Measurement of Glass Transition Point (Tg) 29.30 mg (0.1016 mmol) of the compound represented by formula (B-9-1), 36.09 mg (0.1018 mmol) of YX4000H as an epoxy compound, and 0.89 mg of 2PZ-PW as a curing accelerator were mixed, and THF (1 ml) was added to completely dissolve the mixture. The solvent was removed from this solution under vacuum to obtain Composition 11. 26.7 mg of this composition was weighed, and the glass transition point was measured, which was found to be >200°C.

[Comparative Example 1]
Except for changing the compound represented by formula (B-9-1) to DHTP-M, a composition ref1 was obtained in the same manner as in Example 11. 25.4 mg of this composition was weighed, and the glass transition temperature was measured, resulting in a value of 115°C.

[Examples 12 to 17 and Comparative Example 2]
Compositions 12 to 17 and ref. 2 shown in Table 1 were prepared in the same manner as in Example 11, and Tg was measured. Example 11 and Comparative Example 1 are listed again in Table 1. The value in parentheses for Example 16 in the table is the molar ratio of each curing agent to the total curing agent.
Table 1. Glass transition temperature (Tg) of the composition

A comparison of the above examples and comparative examples shows that the composition according to the present technology has a high glass transition point and excellent heat resistance.

[Example 18]
0.500 g (1.249 mmol) of the compound represented by formula (A-7-1) synthesized in Example 2 and 0.0675 g (0.625 mmol) of PDA were placed in a sample bottle, and tetrahydrofuran (5 mml) was added to dissolve the solids. This solution was vacuum dried at room temperature for 2 hours to obtain a composition of the present invention (composition 18) as a viscous liquid. When this composition was observed under a polarizing microscope on a hot plate, light leakage due to scattering was observed over almost the entire observation area. Furthermore, the glass transition temperature of this sample was measured and found to be 200°C or higher.

[Example 19]
0.500 g (1.249 mmol) of the compound represented by formula (A-7-1) synthesized in Example 2, 0.0545 g (0.504 mmol) of PDA, and 0.0303 g (0.250 mmol) of DMA were placed in a sample bottle, and tetrahydrofuran (5 mml) was added to dissolve the solids. This solution was vacuum dried at room temperature for 2 hours to obtain a composition of the present invention (composition 19) as a viscous liquid. When this composition was observed under a polarizing microscope on a hot plate, light leakage due to scattering was observed over almost the entire observation area. Furthermore, the glass transition temperature of this sample was measured and found to be 200°C or higher.

[Example 20]
The liquid crystallinity and alignment of Compositions 15 to 17 prepared in Examples 15 to 17 were confirmed. As a result, it was confirmed that the compositions had liquid crystallinity and were cured in a vertically aligned state for all cured products.

[Comparative Example 3]
The liquid crystallinity of composition ref. 2 prepared in Comparative Example 2 was confirmed. Microscopic observation revealed that the cured product contained a mixture of regions that were considered to be crystalline and regions that were considered to be amorphous. When this cured product sample was measured at various temperatures, it was confirmed that in the regions that were considered to be amorphous, there were parts that exhibited liquid crystallinity at temperatures of 110°C or higher. This suggests that in composition ref. 2, the curing agent was not compatible with the epoxy compound, and therefore curing was insufficient.

A comparison of Example 20 and Comparative Example 3 shows that the composition of the present invention has high compatibility.

[Example 21]
Measurement of thermal conductivity of cured product prepared from composition 11 Composition 11 was placed in an aluminum container with a diameter of 2.4 cm and held on a hot plate heated to 150°C for 120 minutes, and a circular piece with a thickness of 1.5 mm was taken out. The thermal conductivity of this cured product (cured product 11) was 0.73 W/m K and 0.30 W/m K in the in-plane direction and thickness direction of the sample, respectively.

[Example 22] to [Example 29]
The thermal conductivity of compositions 12 to 19 in Table 2 was measured in the same manner as in Example 21. The values in parentheses for Examples 26 and 28 in the table represent the molar ratio of each curing agent to the total curing agent. Example 21 is also shown here again.

Table 2. Liquid crystallinity and thermal conductivity of the composition

[Example 30]
Preparation of Filler-Containing Sample 0.100 g of Composition 11 and 0.9000 g of boron nitride particles (PolarTherm PTX-25, manufactured by Momentive Performance Materials Japan, Inc.) were weighed out and mixed thoroughly, sandwiched between stainless steel plates, and held for 45 minutes at a pressure of 20 MPa in a compression molding machine (IMC-19EC, manufactured by Imoto Machinery Co., Ltd.) heated to 150°C, and a square piece with a thickness of 768 μm was taken out as a heat dissipation member. The thermal conductivity of this sample (filler-containing sample 11) was 8.9 W/m K.

[Example 31] to [Example 38]
Filler-containing compositions 12 to 19 were molded in the same manner as in Example 30 above, except that compositions 12 to 19 were used instead of composition 11. The thermal conductivity of these samples was measured, and the results are shown in Table 3. Example 30 is also listed in the table.

Table 3. Thermal conductivity of samples containing filler

[Example 39] and [Example 40]
0.1 g of Composition 15 or Composition 16 and 0.90 g of aluminum oxide particles (DAW-10, manufactured by Denka) were weighed out and mixed thoroughly, and filled samples 15 _AO and 16 _AO were prepared in the same manner as in Example 30, and their thermal conductivities were measured. The results are shown in Table 4.

Table 4. Thermal conductivity of filler-containing samples 2


As noted above, the compositions of the present invention are found to provide high thermal conductivity.

The technology of the present invention can be suitably used as a packaging material for semiconductor devices. It can also be used as an alternative to other epoxy resins, such as in adhesives.

Claims (10)

In a composition containing an epoxy compound and a curing agent,
A composition containing at least one of component A as an epoxy compound and component B as a curing agent.
Component A: A compound having two oxiranyl groups and two to four aromatic rings, in which one to three hydrogen atoms of the aromatic rings are replaced by groups derived from vinyl, and which is represented by formula (A).

In formula (A),
R ^ep independently represents a group having 3 to 12 carbon atoms including oxiranyl;
X is independently a single bond, —CH ₂ O—, —CH═CH—, or —C≡C—;
At least one R ¹ is a group represented by formula (1), and other R ^1s are independently hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms;
n is an integer from 0 to 2.

In formula (1), R ² is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the bonding position to the aromatic ring.
Component B: A compound having two phenolic hydroxyl groups, groups in which the hydroxyl groups are acylated, or two cyanate esters, and having two to four aromatic rings, in which one to three hydrogen atoms on the aromatic rings have been replaced with groups derived from vinyl, represented by formula (BI), formula (B-II), or formula (B-III).

In formula (BI),
X is independently a single bond, —CH ₂ O—, —CH═CH—, or —C≡C—;
At least one R ¹ is a group represented by formula (1) (excluding 1-propenyl), and other R ^1s are independently hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms;
n is an integer from 0 to 2.

In formula (1), R ² is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the bonding position to the aromatic ring.

In formula (B-II),
X is independently a single bond, —CH ₂ O—, —CH═CH—, or —C≡C—;
At least one R ¹ is a group represented by formula (1), and other R ^1s are independently a group represented by hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms;
^R3 is independently alkyl having 1 to 6 carbon atoms or phenyl;
n is an integer from 0 to 2.

In formula (1), R ² is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the bonding position to the aromatic ring.


In formula (B-III),
X is independently a single bond, —CH ₂ O—, —CH═CH—, or —C≡C—;
At least one R ¹ is a group represented by formula (1), and other R ^1s are independently a group represented by hydrogen, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms;
n is an integer from 0 to 2.

In formula (1), R ² is independently hydrogen or alkyl having 1 to 12 carbon atoms, and * indicates the bonding position to the aromatic ring. The composition of claim 1, wherein in the compound represented by formula (A), X is a single bond or -C≡C-. The composition of claim 1, wherein in the compound represented by formula (BI), X is a single bond or -C≡C-. The composition of claim 1, wherein in the compound represented by formula (B-II), X is a single bond or -C≡C-. The composition of claim 1, wherein in the compound represented by formula (B-III), X is a single bond or -C≡C-. The composition of any one of claims 1 to 5, further comprising a cure accelerator. The composition of claim 6, further comprising an inorganic filler. The composition of claim 7, wherein the inorganic filler is aluminum oxide, boron nitride, or aluminum nitride. A cured product obtained by curing the composition described in any one of claims 1 to 8. A material for electronic components using the cured product of claim 9.