JP2022008092A - Polymerizable compounds, compositions for electronic components, materials for electronic components - Google Patents

Abstract

[Problem] The object of the present invention is to provide a liquid crystalline epoxy compound that has liquid crystallinity and a low melting point. Also, to provide an epoxy resin material with high thermal conductivity using said epoxy compound. [Solution] A liquid crystalline epoxy compound having two or more oxiranyls and 2 to 5 aromatic rings, in which the oxiranyls are bonded to the aromatic rings and at least one oxiranyl is bonded to the aromatic ring via a carbon atom, is provided as an epoxy resin material with high thermal conductivity. [Selected Figure] None.

Description

The present invention relates to a composition for a heat radiating member that efficiently conducts heat generated inside an electronic device, and a polymerizable compound having liquid crystallinity used therein.

In recent years, in semiconductor elements for power control such as hybrid vehicles and electric vehicles, CPUs for high-speed computers, and the like, it has been desired to increase the thermal conductivity of packaging materials so that the temperature of internal semiconductors does not become too high. That is, the ability to efficiently release the heat generated from the semiconductor chip to the outside is important.

As a method for solving such a heat dissipation problem, there is a method in which a high thermal conductive material (heat dissipation member) is brought into contact with a heat generating portion to guide heat to the outside and dissipate heat. Examples of the material having high thermal conductivity include inorganic materials such as metals and metal oxides. However, such an inorganic material has problems in processability and insulating property, and it is very difficult to use it alone as a filler for a semiconductor package. Therefore, a heat radiating member which is made of a composite of these inorganic materials and a resin and has high thermal conductivity is being developed.

High thermal conductivity of composite materials has generally been achieved by adding a large amount of inorganic fillers such as metal fillers to general-purpose resins such as polyethylene resins, polyamide resins, polystyrene resins, acrylic resins and epoxy resins. rice field. However, the thermal conductivity of the inorganic filler is a value peculiar to the substance and the upper limit is set. Therefore, a method for performing this in a composite material by improving the thermal conductivity of the resin has been widely attempted. As a means for actually performing this, for example, a method using an epoxy compound having a liquid crystallinity is known.

Patent Document 1 discloses a terphenyl compound having two glycidyloxy. Further, Patent Document 2 discloses a terphenyl compound having three glycidyloxy. However, the compound disclosed in the patent document has no liquid crystal temperature and has a melting point as high as 117 ° C. or higher.

International Publication No. 2005/6473 International Publication No. 2016/6649

An object of the present invention is to provide a liquid crystalline epoxy compound having a liquid crystallinity and a low melting point. Another object of the present invention is to provide an epoxy resin material having high thermal conductivity using the epoxy compound. Further, another object of the present invention is to provide a liquid crystal epoxy compound having high solubility in a solvent.

In a liquid crystal epoxy compound having two or more oxylanyls and two to five aromatic rings, the group having the oxylanyl is bonded to the aromatic ring, and at least one oxylanyl is an aromatic ring and methylene. The present invention was completed by finding that the compound bonded in 1 solves the above-mentioned problems.

A composition made from the above compound tends to exhibit liquid crystallinity when it is cured by itself or when the composition is cured. Therefore, the cured product has high thermal conductivity. Further, the compound has low crystallinity, and a composition using the compound as a raw material is easy to be made into a paste. Therefore, it can be suitably used as a heat dissipation material for power semiconductors and the like.

Hereinafter, embodiments of the present invention will be described in detail. Further, the present invention is not limited to the embodiments.

The present invention includes the following items.

[1] In a liquid crystal epoxy compound having two or more oxylanyls and two to five aromatic rings, the group having the oxylanyl is bonded to the aromatic ring, and at least one oxylanyl is attached to the aromatic ring via carbon. Bound, compound.

[2] The compound according to Item [1], wherein the liquid crystalline epoxy compound is a rod-shaped molecule.

式（１）中、Ｒ^ｅｐは独立して、オキシラニルを有する炭素数２から１２の基であり、少なくとも１つのオキシラニルが、炭素を介して芳香環と結合し、Ｘは独立して、単結合、－ＣＨ_２ＣＨ_２－、－ＣＨ_２Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、または－ＣＯＯ－であり、Ｒ^１は独立して、水素、炭素数１から８のアルキル、炭素数１から８のアルコキシ、またはＲ^ｅｐであり、これらアルキルおよびアルコキシの少なくとも１つの－ＣＨ_２－は－Ｃ（＝Ｏ）－で置き換えられてもよく、ｎは０から２である。 [3] The compound according to the item [2] represented by the formula (1).

In formula (1), ^Rep is independently a group having 2 to 12 carbon atoms having an oxylanyl, at least one oxylanyl is bonded to an aromatic ring via carbon, and X is independently and single bonded. , -CH ₂ CH _2- , -CH ₂ O-, -CH = CH-, -C≡C-, or -COO-, R ¹ is independently hydrogen, alkyl with 1 to 8 carbon atoms, It is an alkoxy or ^Rep having 1 to 8 carbon atoms, and at least one of these alkyl and alkoxy -CH _2- may be replaced with -C (= O)-, and n is 0 to 2.

[4] The compound according to item [3], wherein X is a single bond or —C≡C— in the liquid crystal epoxy compound represented by the formula (1).

[5] A composition containing the compound according to any one of Items [1] to [4] and a curing agent.

[6] The composition according to item [5], further comprising a curing accelerator.

[7] The curing agent is an aromatic amine having two or more aromatic primary amines, an aliphatic primary amine, and a secondary amino in the molecular skeleton, or an aliphatic amine having two or more secondary aminos in the molecular skeleton. , Item [5] or [6].

[8] The composition according to item [7], wherein the curing agent is at least one compound represented by the formula (2-1) or (2-2).
EZ- (LZ) n-E (2-1)
L1 ^- Z-E (2-2)
In equations (2-1) and (2-2),
L is independently a single bond, cyclohexylene, phenylene, or naphthalene, and at least one hydrogen in these rings may be replaced by an alkyl having 1 to 10 carbon atoms.
L ¹ is hydrogen, cyclohexyl, phenyl, or naphthyl, and at least one hydrogen in these rings may be replaced with an alkyl having 1 to 10 carbon atoms.
Z is independently a single bond, -O-, -NH-, -S-, -SO _2- , -CO _2- , or an alkylene with 1-12 carbon atoms.
E is independently an amino, an alkylamino having 1 to 10 carbon atoms, a hydroxyl group, or a carboxy, and at least one of E is an amino or an alkylamino having 1 to 10 carbon atoms.
n is an integer from 0 to 7.

式中Ｒ^１３は、メチル、エチル、プロピル、ブチル、ペンチル、またはヘキシル基を表し、プロピル、ブチル、ペンチル、またはヘキシル基は、分岐鎖であっても良い。） [9] Item [5] or [6], wherein the curing agent is a phenol having two or more -OH in the molecular skeleton, or a compound in which at least one of -OH in the phenol is a short-chain ester. The composition according to.
(The short-chain ester is a structure in which the group represented by (3-E) below is replaced with H of the OH group.

In the formula, R ¹³ represents a methyl, ethyl, propyl, butyl, pentyl, or hexyl group, and the propyl, butyl, pentyl, or hexyl group may be a branched chain. )

式（３－１）中、
環Ｂは、ベンゼン、ナフタレン、アントラセン、フルオレン、または９，９‐ジフェニルフルオレンであり、これら環Ｂにおいて、少なくとも１つの水素は、炭素数１～３のアルキル、または炭素数１～３のアルコキシで置き換えられてもよく；
ｎ３１は２以上４以下の整数である。
式（３－２）中、ｎ３２およびｎ３３は独立して、１～３の整数であり；
Ｚ^３０は、単結合、炭素数１～１０のアルキレン、－ＣＨ（ＣＨ_３）－、－Ｃ（ＣＨ_３）_２－、－Ｃ（ＣＦ_３）_２－、－Ｏ－、－Ｓ－、または－ＳＯ_２－であり、
ベンゼン環上の、少なくとも１つの水素は、炭素数１～３のアルキルまたは炭素数２～３のアルケニルで置き換えられてもよく；

式（３－３）および式（３－４）中、
ｎ３４は１以上５０００以下の整数であり、ｎ３５およびｎ３６は独立して、０または１であり、ｎ３４が２以上の場合、繰り返し毎に異なってもよく、
Ｒ^１０およびＲ^１１は独立して、１，４－フェニレン、４，４’－ビフェニレン、またはシクロペンタジエニレンであり、
式（３－５）中、
ｎ３４は１以上５０００以下の整数であり、
式（３－６）中、
Ｚ^３１は独立して単結合、－ＣＨ（ＣＨ_３）－、または－Ｃ（ＣＨ_３）_２－であり、ｎ３４は１以上５０００以下の整数である。
式（３－７）中、
ｎ３４は１以上５０００以下の整数であり、Ｒ^１２は水素またはメチルである。
短鎖のエステルとは、以下の（３－E）で表される基が、ＯＨ基のＨに置換した構造である。

式中Ｒ^１３は、メチル、エチル、プロピル、ブチル、ペンチル、またはヘキシル基を表し、プロピル、ブチル、ペンチル、またはヘキシル基は、分岐鎖であっても良い。
また、これら式（３－３）から式（３－７）中の芳香環上の少なくとも１つの水素はメチルで置き換えられてもよい。 [10] The composition according to Item [9], wherein the curing agent is at least one compound represented by the formulas (3-1) to (3-7), or an ester thereof.

In equation (3-1),
Ring B is benzene, naphthalene, anthracene, fluorene, or 9,9-diphenylfluorene, in which at least one hydrogen is an alkyl having 1 to 3 carbon atoms or an alkoxy having 1 to 3 carbon atoms. May be replaced;
n31 is an integer of 2 or more and 4 or less.
In equation (3-2), n32 and n33 are independently integers of 1 to 3;
Z ³⁰ is 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 -and
At least one hydrogen on the benzene ring may be replaced with an alkyl having 1-3 carbon atoms or an alkenyl having 2-3 carbon atoms;

In equations (3-3) and (3-4),
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 iteration.
R ¹⁰ and R ¹¹ are independently 1,4-phenylene, 4,4'-biphenylene, or cyclopentadienylene.
In equation (3-5),
n34 is an integer of 1 or more and 5000 or less,
In equation (3-6),
Z ³¹ is an independently single bond, -CH (CH ₃ )-, or -C (CH ₃ ) _2- , and n34 is an integer of 1 or more and 5000 or less.
In equation (3-7),
n34 is an integer of 1 or more and 5000 or less, and ^R12 is hydrogen or methyl.
The short-chain ester has a structure in which the group represented by (3-E) below is replaced with H of the OH group.

In the formula, R ¹³ represents a methyl, ethyl, propyl, butyl, pentyl, or hexyl group, and the propyl, butyl, pentyl, or hexyl group may be a branched chain.
Further, at least one hydrogen on the aromatic ring in these formulas (3-3) to (3-7) may be replaced with methyl.

[11] The composition according to item [5] or [6], wherein the curing agent is a compound containing a cyanate ester.

[12] The composition according to item [5] or [6], wherein the curing agent is a compound containing a carboxylic acid, a carboxylic acid ester, an acid anhydride, or a thiol.

[13] The composition according to any one of Items [5] to [12], further comprising an inorganic filler.

[14] The composition according to item [13], wherein the inorganic filler is aluminum oxide or boron nitride.

[15] A material for electronic components obtained by curing the composition according to any one of items [5] to [14].

式（１’）中、Ｒ^ｅｐ’は独立して、オキシラニルを有する炭素数４から１２の基であり、Ｒ^１は独立して水素またはメチルである。
[16] A compound represented by the formula (1').

In formula (1'), R ^ep'is independently a group of 4 to 12 carbon atoms having oxylanyl, and R ¹ is independently hydrogen or methyl.

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

[Liquid crystal epoxy compound]
As described above, in a liquid crystal epoxy compound having two or more oxylanyls and two to five aromatic rings, the group having the oxylanyl is bonded to the aromatic ring, and at least one oxylanyl is aromatic via carbon. By using a compound bonded to a ring, the problem of the present application can be solved. At this time, the term “via carbon” indicates that the atom at a position directly connected to the aromatic ring may be substituted with methylene, carbon constituting oxylanyl, or the like.

The liquid crystal epoxy compound is preferably rod-shaped because it suppresses crystallinity and is easy to form into a paste. For such rod-shaped liquid crystal compounds, it is preferable that the liquid crystal core has 3 to 5 aromatic rings in order to expand the liquid crystal temperature range.

The core of the liquid crystal display shows a structure in which aromatic rings and alicyclic rings are linked by a bonding group having a relatively fixed conformation. At this time, examples of the bonding group include a single bond, ethylene, oxymethylene, a double bond, a triple bond, an ester and the like.

The rod-shaped liquid crystal compound has a structure in which aromatic rings and alicyclic rings are linearly connected as a liquid crystal core, and flexible substituents such as alkyl are bonded to both ends of the core. At this time, the straight line does not have to be a strict straight line and may be bent to an angle of about 45 degrees.

It is preferable that such a rod-shaped liquid crystal compound does not contain an ester in its molecular structure in order to prevent decomposition at a temperature of 200 ° C. or higher.

As the rod-shaped liquid crystal compound, the compound represented by the formula (1) is selected because it has a wide temperature range showing liquid crystal properties, is easy to manufacture, and has high heat resistance when it is used as a cured product. It is more preferable to do so.

式（１）中、Ｒ^ｅｐは独立して、オキシラニルを有する炭素数２から１２の基であり、Ｘは、それぞれ独立して、単結合、－ＣＨ_２ＣＨ_２－、－ＣＨ_２Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、または－ＣＯＯ－であり、Ｒ^１は独立して、水素、炭素数１から８のアルキル、炭素数１から８のアルコキシ、またはＲ^ｅｐであり、これらアルキルおよびアルコキシの少なくとも１つの－ＣＨ_２－は－Ｃ（＝Ｏ）－で置き換えられてもよく、ｎは０から２である。

In formula (1), R ^ep is an independent group having 2 to 12 carbon atoms having an oxylanyl, and X is an independent single bond, -CH ₂ CH _2- , -CH ₂ O-, respectively. -CH = CH-, -C≡C-, or -COO-, where R ¹ is independently a hydrogen, an alkyl having 1 to 8 carbon atoms, an alkoxy having 1 to 8 carbon atoms, or R ^ep . At least one of these alkyl and alkoxy —CH ₂ − may be replaced with —C (= O) −, where n is 0 to 2.

In the compound of formula (1), ^Reps are independently groups having 2 to 12 carbon atoms containing oxylanyl. At this time, the structure of R ^ep other than oxylanyl is not particularly limited, but in order to give high heat resistance when made into a cured product, it is preferable that the group contains oxylanyl having 2 to 10 carbon atoms, and the carbon number is preferably. It is particularly preferable that the group contains 2 to 8 oxylanyl. Further, -CH _2- of these oxylanyl-containing groups may be substituted with -O-. Compounds having a structure in which —O— is directly bonded to an aromatic ring are particularly easy to synthesize. However, in order to suppress the crystallinity of the compound and improve the liquid crystallinity, at least one ^Rep needs to be bonded to the aromatic ring via carbon. On the other hand, when both ^Reps are bonded to the aromatic ring via carbon, the liquid crystallinity tends to decrease. Therefore, it is preferable that at least one ^Rep is bonded to the aromatic ring via —O—.

In the compound of formula (1), the linking group X is independently single-bonded, -CH ₂ CH _2- , -CH ₂ O-, -CH = CH-, -C≡C-, or -COO-. Is. In these linking groups, the direction of bonding is arbitrary. At this time, in order to improve the heat resistance of the cured product, it is preferable to select single bond, -CH ₂ CH _2- , -CH ₂ O-, or -C≡C- as X, and a wide liquid crystal display for the compound. It is particularly preferred to select single bond or -C≡C- to provide a temperature range. Moreover, it is most preferable to select a single bond because of the ease of synthesis.

In the compound of formula (1), R ¹ is independently hydrogen, an alkyl having 1 to 8 carbon atoms, an alkoxy having 1 to 8 carbon atoms, or R ^ep . Also, one of these alkyl and alkoxy -CH _2- may be substituted with -CO-. At this time, since the liquid crystal temperature range of the compound can be expanded, it is preferable to select alkyl or alkoxy as these ^R1 , and it is particularly preferable to select alkyl. Further, when R ^ep and X are not the same group, it is also preferable to select hydrogen for the same reason. In order to expand the liquid crystal temperature range of the compound, it is most preferable to select methyl as ^R1 . Further, in order to improve the heat resistance of the cured product, it is preferable to select R ^ep as R ¹ .

In the compound of formula (1), n is 0 to 2. At this time, n is preferably 1 or 2 because the liquid crystal temperature range of the compound can be expanded.

Preferable examples of the liquid crystal epoxy compound represented by the formula (1) include compounds of the formulas (1-1) to (1-48).

From formula (1-1) to formula (1-48), R ^ep1 and R ^ep2 are independent except for oxylanyl, and are all composed of a carbon-carbon single bond and hydrogen bonded to carbon, and have 2 to 12 carbon atoms. Represents the basis of.

In the compounds represented by the above formulas (1-1) to (1-48), in order to solve the problem of the present invention, formulas (1-11) to formulas (1-18) and formulas (1-48) are used. It is most preferable to select one of the compounds represented by the formula (1-23) from 20). These compounds have a wide liquid crystal temperature range and are in a temperature range suitable for curing.

The compound represented by the formula (1') of the present invention has high solubility in a solvent. Therefore, when a composition containing these compounds is used for printing, the generation of crystals can be suppressed, so that the printability is excellent.

式（１’）中、Ｒ^ｅｐ’は独立して、オキシラニルを有する炭素数４から１２の基であり、Ｒ^１は独立して水素またはメチルである。

In formula (1'), R ^ep'is independently a group of 4 to 12 carbon atoms having oxylanyl, and R ¹ is independently hydrogen or methyl.

In formula (1'), R ^ep'is an independent group of 4 to 12 carbon atoms with oxylanyl. Since oxylanyl consists of two Cs and one O, ^Rep'has 2 to 10 hydrocarbons in addition to oxylanyl. At this time, in order to increase the solubility in the solvent, it is preferable to have 3 to 10 hydrocarbons in addition to oxylanyl. For the same purpose, it is preferable that ^Rep'has a branched chain. On the other hand, when the number of hydrocarbon groups and branched chains increases, the liquid crystallinity decreases and the heat resistance of the cured product decreases. In order to prevent this, it is preferable to have 3 to 5 hydrocarbons in addition to oxylanyl.

The compounds of formula (1') are highly soluble in solvents, including compounds in which the two R ^ep'are both attached to the aromatic ring via —O—. However, a compound in which at least one ^Rep'is bonded to an aromatic ring via carbon is more soluble and liquid crystal-like, and is preferable.

In formula (1'), R ¹ is independently hydrogen or methyl. At this time, it is preferable not to select or select one CH ₃ as R ¹ in order to improve the liquid crystallinity, and it is preferable to select one in order to improve the solubility in the solvent.

As a suitable example of the compound represented by the formula (1'), in the compounds represented by the above formulas (1-1) to (1-48), R ^ep1 and R ^ep2 have oxylanyl and have 4 carbon atoms. From 12 compounds are mentioned. In these compounds, in order to further solve the problem of the present invention, the compounds represented by the formulas (1-11) to (1-18) and the formulas (1-20) to (1-23) are used. It is most preferable to select one. These compounds have a wide liquid crystal temperature range and are in a temperature range suitable for curing.

Another suitable example of the compound represented by the formula (1') is a compound represented by the following formulas (1'-1) to (1'-24).

These compounds have high solubility in a solvent and can be produced at low cost. Among these compounds, the compounds represented by the formulas (1'-1) to (1'-16) are more suitable because the liquid crystal temperature range is wide.

The composition of the present invention is characterized by containing the polymerizable compound of the present invention, a curing agent, and a curing accelerator added as needed. Such a composition of the present invention tends to exhibit liquid crystallinity. Further, by curing while maintaining this state, the entanglement between the molecular skeletons in the cured product is alleviated. As a result, it provides a material that conducts heat efficiently.

The composition of the present invention is characterized by containing the compound represented by the above formula (1). One kind or a plurality of compounds of the formula (1) may be used. Further, other known epoxy compounds can be used in combination as long as the liquid crystal property of the composition is not lost. As such a compound, a liquid crystal epoxy compound represented by the formulas (o-1) to (o-6) can be preferably used.

Further, as the above-mentioned other epoxy compound, a non-liquid crystal epoxy compound represented by the formulas (o-7) to (o-21) is also preferably used.

In formula (o-12), Z ¹⁰ is a single bond, -CH _2- , -O-, -S-, -CH (CH ₃ )-, -C (CH ₃ ) _2- , -SO _2- , or. -C (CF ₃ ) ₂ -represents.

In equations (o-13) and (o-14), Z ¹¹ represents CH or CCH ₃ .

Further, as the above-mentioned other epoxy compound, a resin having a structure represented by the formulas (o-23) to (o-27) is also preferably used.

In formula (o-23), Z ¹² and Z ¹³ are independently single-bonded, -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 5000 or less.
In equations (o-24) and (o-25), 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, every iteration. May be different,
R ¹⁰ and R ¹¹ are independently 1,4-phenylene, 4,4'-biphenylene, or cyclopentadienylene.
Further, the hydrogen on the aromatic ring in the formulas (o-24) to (o-25) may be replaced with methyl.

In formulas (o-26) and (o-27), Z ¹⁴ is independently a single bond, -CH (CH ₃ )-, or -C (CH ₃ ) _2- , and n21 is 1 or more and 5000. Represents the following integers.
Further, hydrogen on the aromatic ring in these formulas (o-26) and (o-27) may be substituted with methyl.

The content of such a known epoxy compound with respect to the compound of the formula (1) is not particularly limited as long as the composition or a cured product thereof exhibits desired properties. That is, it can be used between 0.1% by weight and 99.9% by weight based on the total weight of the epoxy compound. At this time, in order to exhibit the effect of the present invention, it is preferable to use it between 0.1% by weight and 90% by weight, and it is more preferable to use it between 0.1% by weight and 80% by weight.

[Curing agent]
As the curing agent that can be used in combination with the composition of the present invention, all known compounds such as amines, phenols, cyanate esters, carboxylic acids, carboxylic acid esters, acid anhydrides, and thiols can be used.

The amine-based curing agent is at least one compound represented by the following formula (2-1) or (2-2) because it is easily available without significantly impairing the liquid crystallinity of the composition. Is preferable.
EZ- (LZ) n-E (2-1)
L1 ^- Z-E (2-2)
In equations (2-1) and (2-2),
L is independently a single bond, cyclohexylene, phenylene, or naphthalene, and at least one hydrogen in these rings may be replaced by an alkyl having 1 to 10 carbon atoms.
L ¹ is hydrogen, cyclohexyl, phenyl, or naphthyl, and at least one hydrogen in these rings may be replaced with an alkyl having 1 to 10 carbon atoms.
Z is independently a single bond, -O-, -NH-, -S-, -SO _2- , -CO _2- , or an alkylene with 1-12 carbon atoms.
E is independently an amino, an alkylamino having 1 to 10 carbon atoms, a hydroxyl group, or a carboxy, and at least one of E is an amino or an alkylamino having 1 to 10 carbon atoms.
n is an integer from 0 to 7.

Examples of the compound represented by the formula (2-1) include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, p-xylenediamine, m-xylenediamine and the like. 2-12 aliphatic polyvalent diamines, 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, o-phenylenediamine, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane , 4,4'-Diaminodiphenyl ether, 1,1-bis (4-aminophenyl) cyclohexane, 4,4'-diaminodiphenyl sulfone, bis (4-aminophenyl) phenylmethane, m-tridine, o-tridine, etc. Examples thereof include alicyclic polyvalent amines such as aromatic polyvalent diamines, 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-because they have good compatibility when made into a composition and are excellent in storage stability. 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'-diaminodiphenyl Propane, 4,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfone are particularly suitable.

Examples of the compound represented by the formula (2-2) include n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, n-dodecylamine and the like having 2 to 12 carbon atoms. Aliphatic amines, aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,6-dimethylaniline, 2,4,6-trimethylaniline, 2- Examples include aromatic amines such as 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, and 2,4-dimethylaniline are excellent in compatibility and storage stability when made into a composition. , 2,6-Dimethylaniline, 2,4,6-trimethylaniline, 2-ethylaniline are particularly suitable.

As the phenolic curing agent, at least one phenolic compound represented by the following formulas (3-1) to (3-7), or at least one phenolic compound represented by the following formulas (3-1) to (3-7), can be easily obtained without significantly impairing the liquid crystallinity of the composition. It is preferably the short chain ester.

In equation (3-1),
Ring B is benzene, naphthalene, anthracene, fluorene, or 9,9-diphenylfluorene, in which at least one hydrogen is an alkyl having 1 to 3 carbon atoms or an alkoxy having 1 to 3 carbon atoms. May be replaced;
n31 is an integer of 2 or more and 4 or less.

In equation (3-2), n32 and n33 are independently integers of 1 to 3;
Z ³⁰ is 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 -and
At least one hydrogen on the benzene ring may be replaced with an alkyl having 1-3 carbon atoms and an alkenyl having 2-3 carbon atoms;

In equations (3-3) and (3-4),
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 iteration.
R ¹⁰ and R ¹¹ are independently 1,4-phenylene, 4,4'-biphenylene, or cyclopentadienylene.
In equation (3-5),
n34 is an integer of 1 or more and 5000 or less,
In equation (3-6),
Z ³¹ is an independently single bond, -CH (CH ₃ )-, or -C (CH ₃ ) _2- , and n34 is an integer of 1 or more and 5000 or less.
In equation (3-7),
n34 is an integer of 1 or more and 5000 or less, and ^R12 is hydrogen or methyl.
Further, at least one hydrogen on the aromatic ring in these formulas (3-3) to (3-7) may be replaced with methyl.

The short-chain ester of the phenol compound represented by the above formulas (3-1) to (3-7) has a structure in which the group represented by the following (3-E) is replaced with H of the OH group. be.

式中Ｒ^１３は、メチル、エチル、プロピル、ブチル、ペンチル、またはヘキシル基を表し、プロピル、ブチル、ペンチル、またはヘキシル基は、分岐鎖であっても良い。これらＲ^１３のうち、メチルを選択すると、化合物の結晶性が増大するため、組成物の液晶性を損なう場合がある。そのような場合には、より長鎖のアルキルを有する（３－Ｅ）を選択する事が好ましい。一方長鎖アルキルの場合、硬化物とした際の耐熱性が低下する場合がある。そのような場合には、より短鎖のアルキルを有する（３－Ｅ）を選択する事が好ましい。

In the formula, R ¹³ represents a methyl, ethyl, propyl, butyl, pentyl, or hexyl group, and the propyl, butyl, pentyl, or hexyl group may be a branched chain. When methyl is selected from these ^R13 , the crystallinity of the compound is increased, which may impair the liquid crystallinity of the composition. In such a case, it is preferable to select (3-E) having a longer chain alkyl. On the other hand, in the case of long-chain alkyl, the heat resistance of the cured product may decrease. In such a case, it is preferable to select (3-E) having a shorter chain alkyl.

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, and the like. Examples thereof include 4,4'-biphenyldicarboxylic acid and benzophenone-4,4'-dicarboxylic acid.

The curing agent that can be used in the composition of the present invention is not limited to the above-mentioned known compounds such as amine, phenol, cyanate ester, carboxylic acid, carboxylic acid ester, acid anhydride, and thiol. For example, in order to prepare a semi-cured sheet or the like, it is also preferable to add dicyandiamide or the like for the purpose of curing the composition at a higher temperature.

In the composition of the present invention, the ratio of the compound of the formula (1) to the curing agent is not particularly limited. At this time, in order to efficiently proceed the reaction in order to improve the heat resistance, it is preferable to use an equivalent amount of the reactive group of the compound of the formula (1) and the curing agent. For example, in the case of epoxy: amine, it is 2: 1 and in the case of epoxy: phenol, it is 1: 1.

One type of the curing agent may be used, or a plurality of types may be used.

[Curing accelerator]
In the composition of the present invention, particularly when a phenol-based curing agent is used, it is preferable to add a curing accelerator to the composition in order to efficiently proceed the reaction in order to improve heat resistance. Examples of such a curing accelerator include 2-ethyl-4-methyl-1H-imidazole, 2-phenyl-4-methyl-1H-imidazole, 1,2-dimethylimidazole, 2-undecylimidazole, and 1-benzyl-2. -Imidazole-based curing accelerators such as methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole, phosphorus-based curing accelerators such as triphenylphosphine, 2,4 , 6-Tris (dimethylaminomethyl) phenol, triethylenediamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] undec-7-ene, etc. Accelerators and the like can be mentioned. Among such curing accelerators, it is preferable to use an imidazole-based curing accelerator because the curing temperature is 200 ° C. or lower and the curing property is high.

The concentration of the curing accelerator in the composition of the present invention is preferably 0.1% by weight or more with respect to the weight of the polymerizable compound of the present invention in order to efficiently proceed the reaction in order to improve the heat resistance. It is more preferably 0.5% by weight or more. Further, in order to avoid deterioration of reliability due to sublimation of the curing accelerator, the content is preferably 5% by weight or less, 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 components of the present invention may contain an inorganic filler.
Examples of the inorganic filler contained in the composition for electronic components include nitrides such as aluminum nitride, boron nitride, and silicon nitride as a filler having high thermal conductivity. Diamond, graphite, silicon carbide, silicon, beryllia, magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, copper oxide, titanium oxide, cerium oxide, yttrium oxide, tin oxide, forminium oxide, bismuth oxide, cobalt oxide, calcium oxide, Inorganic fillers and metal fillings such as aluminum nitride, boron nitride, silicon nitride, magnesium hydroxide, aluminum hydroxide, gold, silver, copper, platinum, iron, tin, lead, nickel, aluminum, magnesium, tungsten, molybdenum, and stainless steel. It may be a material. Boron nitride, aluminum nitride and aluminum oxide are preferable. Boron nitride and aluminum nitride are preferable because they have a very high thermal conductivity in the plane direction, a low dielectric constant, and a high insulating property. Hexagonal boron nitride (h-BN) and aluminum nitride are particularly preferable.

Examples of the shape of the inorganic filler include spherical, amorphous, fibrous, rod-shaped, tubular, plate-shaped, and quadruped-shaped. The type, shape, size, addition amount, etc. of the inorganic filler can be appropriately selected according to the purpose. For example, when a cured product (material for electronic components) formed from a composition for electronic components requires insulating properties, an inorganic filler having conductivity may be used as long as the desired insulating properties are maintained.

The average particle size of the inorganic filler is preferably 0.1 to 200 μm, for example. More preferably, it is 1 to 100 μm. When it is 0.1 μm or more, the thermal conductivity is good, and when it is 200 μm or less, the filling rate can be increased. In the present specification, the average particle size is based on the particle size distribution measurement by the laser diffraction / scattering method. That is, when the powder is divided into two from a certain particle size by the wet method using the analysis by Franhofer diffraction theory and Mie's scattering theory, the large side and the small side have the same amount (volume basis). Was taken as the median diameter.

The amount of the inorganic filler added is preferably 20 to 95% by weight when used for a heat radiating member, for example. More preferably, it is 50 to 95% by weight. When it is 20% by weight or more, the thermal conductivity becomes high, which is preferable. When it is 95% by weight or less, the heat radiating member is not brittle and is preferable.

As the inorganic filler, an unmodified one may be used as it is. Alternatively, a material whose surface is treated with a coupling agent may be used. For example, boron nitride (h-BN) is treated with a silane coupling agent. In the case of boron nitride, since there is no reactive group on the plane of the particles, the silane coupling agent is bonded only around the reaction group. Boron nitride treated with the coupling agent can form a bond with the polymerizable compound in the composition for electronic components, and this bond is considered to contribute to heat conduction. Therefore, the coupling agent is preferably one that reacts with the group of oxylanyl, oxetanyl, or a curing agent. For example, amine-based ones or those having oxylanyl or oxetanyl are preferable. Specifically, in the case of JNC Co., Ltd., Sila Ace S310, S320, S330, S360, S510, S530 and the like can be mentioned.

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 a polymerizable compound or a curing agent in a composition for electronic components, this bond is considered to contribute to heat conduction. For example, the polymerizable compound may be the polymerizable compound of the present invention represented by the formula (1), or may be another polymerizable compound.

[Other components]
The other components that can be contained in the composition of the present invention are not particularly limited. Examples thereof include polymerizable compounds having a polymerizable group other than epoxy, non-polymerizable compounds, polymerization initiators, solvents and the like.

The polymerizable compound having a polymerizable group other than the epoxy is not particularly limited as long as the characteristics of the electronic material of the present invention are not deteriorated, and a known polymerizable compound can be used. Among them, radically polymerizing compounds such as acrylic compounds and styrene compounds can be preferably used, and these compounds having liquid crystallinity can be more preferably used.
Examples of the polymerization initiator include a thermal polymerization initiator, a photocationic polymerization initiator, a photoanionic polymerization initiator, and the like. Examples of the thermal cationic polymerization initiator include sulfonium salts, boron trifluoride-amine complexes, dicyan azide, organic acid hydrazide, and toluene sulfonic acid esters. Further, as the photocation initiator, a sulfonium salt type, an iodonium salt type, a nonionic type and the like are known. Further, as the photoanion initiator, an oxime type, a carbamate type, a guanidium-carboxylate type, a nifedipine type and the like are known.

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. 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, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, N-Methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, diethyl carbonate, ethylmethyl 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 Examples include alcohol and ethylene glycol. The solvent may be used alone or in combination of two or more.

Since the composition of the present invention has high polymerizable properties, a stabilizer may be added for ease of handling. As such a stabilizer, known ones can be used without limitation. For example, hydroquinone, 4-ethoxyphenol, 3,5-di-t-butyl-4-hydroxytoluene (BHT) and the like can be mentioned.

Further, an additive (oxide or the like) may be added to adjust the viscosity or color of the composition for electronic components. For example, titanium oxide for whitening, carbon black for blackening, and fine powder of silica for adjusting the viscosity can be mentioned. Further, in order to further increase the mechanical strength, for example, inorganic fibers such as glass and carbon fiber, cloths thereof, synthetic fibers such as polyvinyl formal, polyvinyl butyral, polyester, polyamide and polyimide, supermolecules and the like are added. You may.

It is known that the thermal conductivity of a material can be further improved by controlling the orientation of the liquid crystal display. For this purpose, it is also preferable to add a so-called orientation control agent that controls the orientation of the liquid crystal display to the composition of the present invention. As an example of a vertical alignment agent that orients a liquid crystal-like composition perpendicularly to a substrate plane, for example, it has a hydrocarbon structure having 10 or more and 50 or less carbon atoms, and a hydroxyl group, amino, or the like at one end of the structure. Alternatively, a compound having a carboxyl can be mentioned.

[Materials for electronic components]
The material for electronic parts of the present invention is obtained by molding a cured product obtained by curing the composition for electronic parts according to the second embodiment, according to the intended use. For example, a material for electronic parts can be applied as a heat dissipation member.

The material for electronic parts is a polymer obtained by polymerizing (curing) the composition of the present invention. This polymer has high thermal conductivity and is excellent in chemical stability, heat resistance, hardness, mechanical strength and the like. The mechanical strength includes Young's modulus, tensile strength, tear strength, bending strength, flexural modulus, impact strength, and the like.

The composition of the present invention is a thermosetting resin. The thermosetting resin is cured by heating the composition as a raw material to polymerize the monomer contained in the composition, and further by three-dimensionally cross-linking the monomer. The heating temperature at this time is preferably in the temperature range in which the composition of the present invention exhibits a liquid crystal phase. Further, in the composition of the present invention, the liquid crystal temperature range may be increased by advancing the curing to some extent. In such a case, it may be cured in an increased liquid crystal temperature range.

The curing temperature may be constant and may be gradually increased or decreased. 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. Further, in order to improve heat resistance, it is preferable to heat at a temperature higher than the initial curing temperature.

The thermosetting temperature by 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 the polymerization, it is preferable to slowly cool the mixture in order to suppress stress-strain and the like. Further, the strain may be relaxed by performing a reheat treatment.

A cross-linking agent may be added for further cross-linking. As a result, a polymer (cured product) having extremely excellent chemical resistance and heat resistance can be obtained. As such a cross-linking agent, known ones can be used without limitation, and examples thereof include trimethylolpropane tris (3-mercaptopropionate).

The material for electronic parts of the present invention can be used in the form of a sheet, a film, a thin film, a fiber, a molded body or the like. Preferred shapes are films and thin films. The film and the thin film are obtained by polymerizing the composition for electronic components in a state of being applied to a substrate or in a state of being sandwiched between the substrates. It can also be obtained by applying a composition for electronic components containing a solvent to a substrate and removing the solvent. Further, the film can also be obtained by press-molding the polymer. In the present specification, the film thickness of the sheet is 1 mm or more, the film thickness of the film is 5 μm or more, preferably 10 to 900 μm, more preferably 20 to 800 μm, and the film thickness of the thin film is less than 5 μm. .. The film thickness may be appropriately changed according to the intended use.

In addition to high thermal conductivity, the material for electronic components of the present invention also has excellent properties such as chemical stability, heat resistance, hardness and mechanical strength. Therefore, it is useful for heat-dissipating plates, heat-dissipating sheets, heat-dissipating films, heat-dissipating coating films, heat-dissipating adhesives, heat-dissipating molded products, and the like.

Although it has been described above that the material for electronic parts formed from the polymerizable compound of the present invention is used as a heat radiating material, the use of the material for electronic parts is not limited to the heat radiating material. For example, it may be used as a sealing material or an adhesive material.

[Manufacturing method of composition for electronic parts]
The composition for electronic components refers to a heat-dissipating material which is the composition of the present invention, and may contain an inorganic filler in order to enhance thermal conductivity, and it does not matter whether the inorganic filler is coupled. As an example of manufacturing a composition for electronic parts, a manufacturing method when a coupling treatment is applied to an inorganic filler will be described below. A known method can be applied to the coupling treatment.

As an example, first, the inorganic filler particles and the coupling agent are added to the solvent. After stirring with a stirrer or the like, leave it to stand. After the solvent is dried, heat treatment is performed under vacuum conditions using a vacuum dryer or the like. A solvent is added to the inorganic filler particles, and the particles are pulverized by ultrasonic treatment. The solution is separated and purified using a centrifuge. After discarding the supernatant, add a solvent and perform the same operation several times. Dry the purified inorganic filler particles in an oven.

Next, the coupled inorganic filler particles and the polymerizable compound are mixed using an agate mortar or the like, and then kneaded using a biaxial roll or the like. Then, it is separated and purified by ultrasonic treatment and centrifugation.

Further, an amine-based curing agent is added, and the mixture is mixed using an agate mortar or the like, and then kneaded using a twin-screw roll or the like. As a result, a solvent-free composition for electronic components can be obtained.

[Manufacturing method of materials for electronic parts]
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 below.

A solvent-free composition for electronic components is sandwiched in a heating plate using a compression molding machine and molded by compression molding. The polymerizable compound polymerizes at a predetermined temperature and time to form a polymer. Further, post-curing may be performed at an appropriate time and temperature. The pressure during compression molding is preferably 50 to 500 kgf / cm ² , more preferably 70 to 250 kgf / cm ² . Basically, it is preferable that the pressure at the time of curing is high. However, it is preferable to appropriately change it according to the fluidity of the mold and the desired physical properties (which direction the thermal conductivity is emphasized, etc.) and apply an appropriate pressure.

It should be noted that the composition for electronic components becomes easier to handle when it is in a partially cured state (semi-cured state). For example, the composition in a semi-cured state may be formed into a sheet, cut into a desired shape, arranged between suitable members, and bonded together.

A method for producing a film as a material for electronic components by using a composition for electronic components containing a solvent will be described below.

The composition for electronic components is applied onto the substrate, and the solvent is dried and removed to form a coating film layer having a uniform film thickness. Examples of the coating method include spin coating, roll coating, cutane coating, flow coating, printing, micro gravure coating, gravure coating, wire bar coating, dip coating, spray coating, meniscus coating method and the like.

The solvent can be removed by drying, for example, by air-drying at room temperature, drying on a hot plate, drying in a drying oven, blowing warm air or hot air, or the like. The conditions for removing the solvent are not particularly limited, and the solvent may be generally removed and dried until the coating film layer loses its fluidity.

[Electronic components]
Examples of the electronic component include an electronic device having a heat generating portion. When the material for electronic parts of the present invention is used as a heat radiating member, the heat radiating member is arranged in the electronic device so as to be in contact with the heat generating portion. The shape of the heat radiating member may be any of a heat radiating plate, a heat radiating sheet, a heat radiating film, a heat radiating adhesive, a heat radiating molded product, and the like. In this way, the heat generated in the electronic device is dissipated by the heat radiating member, and the failure due to the heat is avoided, so that the life of the electronic device including the electronic device can be extended.

Examples of electronic devices include semiconductor devices. The heat radiating member has high heat resistance and high insulation in addition to high thermal conductivity. Therefore, it is particularly effective for an insulated gate bipolar transistor (IGBT), which requires a more efficient heat dissipation mechanism due to its high power among semiconductor elements. An IGBT is one of the semiconductor elements, which is a bipolar transistor in which a MOSFET is incorporated in a gate portion, and is used for power control. Electronic devices equipped with IGBTs include main conversion elements for high-power inverters, non-disruptive power supply devices, variable voltage variable frequency control devices for AC motors, control devices for railway vehicles, electric transport equipment such as hybrid cars and electric cars, and IH. Examples include cookers.

[Method for synthesizing the compound represented by the formula (1)]
The compound of formula (1) can be synthesized by combining known methods in synthetic organic chemistry. Methods for introducing the desired polymerizable group and ring structure into the starting material include, 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), New Experimental Chemistry Course (Maruzen), etc. Are listed. Further, Japanese Patent Application Laid-Open No. 2006-265527 may be referred to.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the contents described in the examples. When the temperature was not described, the measurement was performed at 23 ° C.

[Measurement of phase transition point of compound and identification of liquid crystal phase]
Measurements were made using a polarizing microscope and a differential scanning calorimeter. The polarizing microscope was manufactured by Nikon Corporation and was configured by attaching a polarizing plate to a VHX5000 digital microscope (KEYENCE). A hot stage system HS1 (manufactured by METTLER TOLEDO) was used for this, and the temperature was adjusted. Petrographic microscopy measurements were observed under cross Nicol. The magnification of the eyepiece and the objective lens was 10x20 times, respectively. As the differential scanning calorimeter, a Diamond DSC manufactured by PerkinElmer was used. At the time of measurement, the rate of temperature increase or decrease was 3 ° C./min in both measurements. In the examples, C is a crystal, S is a smectic phase, N is a nematic phase, I is an isotropic liquid, and () is a monotropic liquid crystal phase.

[Confirmation of liquid crystallinity of composition]
A few drops of the composition were dropped onto a glass slide and maintained at 80 ° C. for 10 minutes to evaporate the solvent. A cover glass was placed on this sample, sandwiched between glass plates, and the composition was once melted at a temperature equal to or higher than that of an isotropic liquid, then rapidly cooled, and evenly adhered between the glasses. The sample was observed under a cross Nicol using the above-mentioned polarizing microscope. If the presence or absence of orientation defects peculiar to the liquid crystal phase, the phase transition temperature range, the fluidity of the sample, and the light leakage due to the scattering phenomenon are visually observed in about half or more of the observation area, it is judged to be liquid crystal. Alternatively, when the composition is vertically oriented, the dark field area occupies most of the area, but when the composition is observed in a region where there is an orientation defect characteristic of the liquid crystal state, and when the defect is present, the liquid crystal property becomes liquid crystal. I decided that there was.

[NMR measurement]
NMR was measured by VARIAN NMR SYSTEM manufactured by VARIAN. ¹ The magnetic field strength in 1 H NMR measurement was 500 MHz, the sample was dissolved in a deuterated solvent such as CDCl ₃ , and the measurement was performed at room temperature. At this time, the total number of times is eight. The internal standard is tetramethylsilane. Among the NMR codes, s means singlet, d means doublet, t means triplet, m means multiplet, and br means broad.

[Measurement of thermal conductivity]
-A sample consisting only of a resin; the thermal diffusivity (α, m ² / s) of the sample was determined using LFA467 HyperFlash manufactured by NETZSCH Co., Ltd. The thermal diffusivity was measured in the in-plane direction and the thickness direction of the sample, respectively. From the specific heat (c, J / (Kg)) and density (ρ, g / m ³ ) of the sample, the thermal conductivity (W / (Km)) was determined according to the following formula.
κ = αxcxρ
At this time, the specific heat was measured with a DSC type high-sensitivity differential scanning calorimeter manufactured by Rigaku Co., Ltd., Thermo Plus EVO2 DSC-8231. The specific gravity was measured by a specific electron scale type hydrometer DME-220 manufactured by Shinko Denshi Co., Ltd.
-Sample containing filler; The thermal diffusivity in the thickness direction of the sample was measured by an ai-Phase Mobile 1u thermal diffusivity measuring device manufactured by iPhase Co., Ltd. In the same manner as above, the specific heat and density of the sample were measured. From these values, the thermal conductivity was determined in the same manner as above.

[Epoxy compound]
Examples of the polymerizable compound represented by the formula (1) include the following formulas (1-2-1), formulas (1-10-1), formulas (1-11-1), and formulas (1-13-1). The compounds represented by the formulas (1-14-1) to (1-14-4) and the formula (1'-21) were used in the examples. This compound was synthesized as described in the examples below. Further, as the comparative compound, a compound represented by the formula (ref. 1) described in International Patent Publication No. 2005/061473 was used. Further, a compound represented by the above formula (o-1) was also used. Compound (o-1) was synthesized in accordance with Japanese Patent No. 5862479. The phase transition point of compound (o-1) was C, 51.1, N, 64.6, I (° C.).

[Curing agent]
As 1,3-phenylenediamine (PDA) and 3,5-dimethylaniline (DMA) were manufactured by Tokyo Chemical Industry Co., Ltd. and used as they were without purification. Further, as the phenolic curing agent, bisphenol E and a compound represented by the following formula (3-2-1) were used. The bisphenol E manufactured by Tokyo Chemical Industry Co., Ltd. was used as it was without purification.

[Vertical alignment agent]
The following formula (p-1) was used. This compound was synthesized as described in Examples described below.

[Example 1] Synthesis of a compound represented by the formula (1-2-1)

Commercially available 2,5-dibromotoluene 1.29 g (5.16 mmol), 4- (3-butenyl) phenylboronic acid 2.00 g (11.3 mmol), tetrakistriphenylphosphine palladium (0) 0.238 g (0) A mixture of .206 mmol) and 1.44 g (13.6 mmol) of Na ₂ CO ₃ was refluxed in dimethoxyethane (20 ml) under a nitrogen stream for 3 hours. 4- (3-Butenyl) phenylboronic acid was synthesized according to JP-A-2014-313222. After completion of the reaction, the reaction solution was cooled, and 100 ml each of pure water and ruen was added. After separating the organic layer, it was washed twice with the same amount of pure water and dried with ו ₄ . After filtration and distillation of the solvent under reduced pressure, the obtained product was purified by column chromatography (silica gel, heptane / toluene = 1/1) to obtain compound (1-2-1-a). Yield 946 mg (yield 52%).

1.50 g (mCPBA, 65%, 5.65 mmol) of 3-chloroperbenzoic acid was added to a CH ₂ Cl ₂ (10 ml) solution of 1.00 g (2.83 mmol) of compound (1-2-1-a). The mixture was added at 10 ° C. or lower, and the mixture was stirred at room temperature overnight. After cooling the reaction solution in an ice bath, a 10% aqueous solution (5 ml) of sodium thiosulfate pentahydrate and a 10% aqueous sodium bicarbonate solution (5 ml) were added, and the mixture was stirred at room temperature for 30 minutes. The organic layer was separated from this reaction solution and washed with 10% aqueous sodium bicarbonate solution (5 ml) and pure water (5 ml). After separating the organic layer, it was dried with _Л4 . After filtration and distillation of the solvent under reduced pressure, the obtained product was purified by column chromatography (silica gel, toluene / ethyl acetate = 10/1) and recrystallized (ethanol) to compound (1-2-1). Got Yield 680 mg (yield 62%).

Phase transition point (° C); C ・ 67.3 ・ N ・ 76.4 ・ I
^{1 1} H-NMR (ppm, CDCl ₃ ); 7.59-7.28 (m, 11H), 3.07-2.97, 2.93-2.78 (m, 8H), 2.56-2 .51 (m, 2H), 2.36-2.35 (m, 3H), 1.99-1.82 (m, 4H).

Ｓｙｎｌｅｔｔ，Ｎｏ．１４，ｐ．２２９５（２００７）．と同様な方法で合成した、４－ブロモ－４’－（３－ブテニルオキシ）ビフェニル２．００ｇ（６．６０ｍｍｏｌ）を用い、実施例１と同様な方法で、４－（３－ブテニル）フェニルボロン酸とのカップリング反応を行った。得られた生成物をカラムクロマトグラフィー（シリカゲル、トルエン）および再結晶（トルエン）で精製することにより、化合物（１－１０－１－ａ）を得た。収量２．０２ｇ（収率８６％）。 [Example 2] Synthesis of the compound represented by the formula (1-10-1)

Synlett, No. 14, p. 2295 (2007). 4- (3-Butenyloxy) biphenyl 2.00 g (6.60 mmol) synthesized in the same manner as in Example 1 was used and 4- (3-butenyloxy) phenylboron was used in the same manner as in Example 1. A coupling reaction with an acid was carried out. The obtained product was purified by column chromatography (silica gel, toluene) and recrystallization (toluene) to obtain compound (1-10-1-a). Yield 2.02 g (yield 86%).

The compound represented by the formula (1-10-1-a) was oxidized using mCPBA in the same manner as in Example 1. The obtained product was purified by column chromatography (silica gel, toluene / ethyl acetate = 10/1) and recrystallization (toluene-ethanol) to obtain compound (1-10-1). Yield 0.58 g (yield 25%).

Phase transition point (° C); C ・ 250.2 ・ S
^{1 1} H-NMR (ppm, CDCl ₃ ); 7.64-7.61 (m, 4H), 7.59-7.56 (m, 4H), 7.31-7.25 (m, 2H), 7.02-6.98 (m, 2H), 4.21-4.15 (m, 2H), 3.19-3.17 (m, 1H), 3.02-2.98 (m, 1H) ), 2.91-2.77 (m, 4H), 2.62-2.60 (m, 1H), 2.53-2.50 (m, 1H), 2.18-2.11 (m) , 1H), 2.01-1.36 (m, 3H).

[Example 3] Synthesis of the compound represented by the formula (1-11-1)

Commercially available 4-bromo-3-methylphenol 1.00 g (5.35 mmol), 4- (3-butenyl) phenylboronic acid 1.27 g (7.21 mmol), tetrakistriphenylphosphine palladium (0) 0.127 g A mixture of (0.110 mmol) and 1.33 g (12.5 mmol) of Na ₂ CO ₃ was refluxed in dimethoxyethane (12 ml), water (4 ml) under a nitrogen stream for 6 hours. After completion of the reaction, the reaction solution was cooled, and 100 ml each of pure water and ruen was added. After separating the organic layer, it was washed twice with the same amount of pure water and dried with ו ₄ . After filtration and distillation of the solvent under reduced pressure, the obtained product was purified by column chromatography (silica gel, toluene) to obtain compound (1-11-1-a). Yield 1.01 g (yield 79.3%).

0.8 ml (4.89 mmol) of trifluoromethanesulfonic anhydride in a solution of 1.01 g (4.24 mmol) of compound (1-11-1-a) and 1.5 ml of pyridine in methylene chloride (10 ml) at room temperature or below. added. The reaction mixture was stirred overnight, poured into pure water (50 ml), and extracted with toluene (50 ml). The organic layer was washed with dilute hydrochloric acid, pure water, and aqueous sodium hydrogen carbonate (50 ml each), and then dried over anhydrous magnesium sulfate. The organic layer was filtered, the solvent was distilled off under reduced pressure, and the obtained product was purified by column chromatography (heptane) to obtain compound (1-11-1-b). Yield 1.39 g (yield 87%).

4- (3-Butenyloxy) -phenylboronic acid 940 mg (4.90 mmol), compound (1-9.1-b) 1.39 g (3.75 mmol), dichlorobistriphenylphosphine palladium (II) 66 mg (0. A mixture of 1.05 g (9.91 mmol) of Na ₂ CO ₃ (094 mmol) was refluxed in a mixed solvent of THF / pure water = 10/5 ml under a nitrogen stream for 2 hours. After cooling the reaction solution, pure water (50 ml) and toluene (50 ml) were added, and a liquid separation operation was performed. The organic layer was dried over anhydrous י ₄ , filtered, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, toluene) and recrystallization (ethanol) to obtain compound (1-11-1-c). Yield 1.12 g (yield 81%).

The compound represented by the formula (1-11-1-c) was oxidized using mCPBA in the same manner as in Example 1. The obtained product was purified by column chromatography (silica gel, toluene / ethyl acetate = 50/1) and recrystallization (ethanol) to obtain compound (1-11-1). Yield 585 mg (48% yield).

Phase transition point (° C); C ・ 67.3 ・ N ・ 100.1 ・ I
^{1 1} H-NMR (ppm, CDCl ₃ ); 7.58-7.55 (m, 2H), 7.46-7.42 (m, 2H), 7.33-7.29 (m, 5H), 7.01-6.98 (m, 2H), 4.21-4.14 (m, 2H), 3.20-3.17 (m, 1H), 3.03-2.99 (m, 1H) ), 2.96-2.79 (m, 4H), 2.63-2.60 (m, 1H), 2.54-2.50 (m, 1H), 2.35 (s, 1H) 2. .18-2.11 (m, 1H), 2.01-1.85 (m, 3H).

市販の４－ブロモ－３－メチルフェノール ２．５０ｇ（１３．４ｍｍｏｌ）、４－ブロモ－１－ブテン ２．３４ｇ（１７．３ｍｍｏｌ）、およびＫ_２ＣＯ_３ ２．７７ｇ（２０．０ｍｍｏｌ）の混合物を、メチルエチルケトン（２０ｍｌ）中、２０時間還流した。反応液を冷却後、純水（５０ｍｌ）およびトルエン（５０ｍｌ）を加え、分液操作を行った。有機層を無水ＭｇＳＯ_４で乾燥後、ろ過し、溶媒を減圧留去した。残渣をカラムクロマトグラフィー（シリカゲル、トルエン）で精製することにより、４－（３－ブテニルオキシ）－２－メチルブロモベンゼンを得た。収量２．５１ｇ（収率７８％）。 [Example 4] Synthesis of the compound represented by the formula (1-13-1)

A mixture of commercially available 4-bromo- _{3-methylphenol 2.50 g (13.4 mmol), 4-bromo-1-butene 2.34 g (17.3 mmol), and K2 CO 3 2.77} g (20.0 mmol). Was refluxed in methyl ethyl ketone (20 ml) for 20 hours. After cooling the reaction solution, pure water (50 ml) and toluene (50 ml) were added, and a liquid separation operation was performed. The organic layer was dried over anhydrous י ₄ , filtered, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, toluene) to obtain 4- (3-butenyloxy) -2-methylbromobenzene. Yield 2.51 g (yield 78%).

5th Edition Experimental Chemistry Course 18 Synthesis of Organic Compounds According to the method described in VI, page 101, Maruzen Co., Ltd., etc., 4- (3-butenyloxy) -2-methylbromobenzene was used and 4- (3-butenyloxy). -2-Methylphenylboronic acid was synthesized. Yield 2.51 g (yield 78%). This compound was used as it was in the next reaction without purification. Yield 1.97 g (yield 92%).

4- (3-Butenyloxy) -2-methylphenylboronic acid 930 mg (4.51 mmol), compound (1-13-1-a) 1.00 g (3.48 mmol), dichlorobistriphenylphosphine palladium (II) 61 mg , And Na ₂ CO ₃ 960 mg (9.06 mmol) were refluxed in a mixed solvent of THF / pure water = 20/20 ml under a nitrogen stream for 4 hours. After cooling the reaction solution, pure water (50 ml) and toluene (50 ml) were added, and a liquid separation operation was performed. The organic layer was dried over anhydrous י ₄ , filtered, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, heptane / toluene = 10/1 → 5/1) and recrystallization (heptane) to obtain compound (1-13-1-b). Yield 0.87 g (yield 68%). The above compound (1-13-1-a) was synthesized by the same method as EP1013649A.

The compound represented by the formula (1-13-1-b) was oxidized using mCPBA in the same manner as in Example 1. The obtained product was purified by column chromatography (silica gel, toluene / ethyl acetate = 20/1) and recrystallization (ethanol) to obtain compound (1-13-1). Yield 0.41 g (yield 90%).

Phase transition point (° C); C ・ 65.8 ・ N ・ 105.8 ・ I
^{1 1} H-NMR (ppm, CDCl ₃ ); 7.61, 7.58, 7.37, 7.30 (AA'BB', 8H), 7.20 (d, 1H, J = 8.50Hz), 6.85 (d, 1H, J = 3.00Hz), 6.81 (dd, 1H, J = 8.00, 2.50Hz), 4.20-4.13, 3.20-3.16, 3.01-3.00, 2.86-2.77, 2.62-2.60, 2.53-2,50 (m, 10H), 2.31 (s, 3H), 2.14- 2.10, 2.00-1.88 (m, 4H).

[Example 5] Synthesis of the compound represented by the formula (1-14-1)

4- (3-Butenyloxy) -3-methylphenylboronic acid and compound (1-13-1-a) synthesized in the same manner as in 4- (3-butenyloxy) -2-methylphenylboronic acid of Example 4. Was used to synthesize the compound (1-14-1-b) in the same manner as in Example 4 above. The product was purified by column chromatography (silica gel, heptane: toluene = 1: 1) and recrystallization (heptane). Yield 0.82 g (yield 64%).

Using compound (1-14-1-b), compound (1-14-1) was synthesized in the same manner as in Example 1 above. The product was purified by column chromatography (silica gel, toluene → toluene / ethyl acetate = 10/1) and recrystallization (ethanol). Yield 0.55 g (yield 62%).

Phase transition point (° C.); C ・ 144.1 ・ N ・ 183.4 ・ I
^{1 1} H-NMR (ppm, CDCl ₃ ); 7.64-7.62 (m, 4H), 7.57, 7.43 (AA'BB', 4H), 7.31-7.25 (m, 2H), 4.20-4.16 (m, 2H), 3.21-3.19, 3.01-3.00, 2.93-2.77, 2.64-2.60, 2. 55-2.51 (m, 8H), 2.30 (s, 3H), 2.18-1.83 (m, 4H).

[Example 6] Synthesis of the compound represented by the formula (1-14-2)

4- (4-Pentenyloxy) -3-methylphenylboronic acid and compound (1-13-1-a) synthesized in the same manner as in 4- (3-butenyloxy) -2-methylphenylboronic acid of Example 4. ) Was used to synthesize the compound (1-14-2-a) in the same manner as in Example 4 above. The product was purified by column chromatography (silica gel, toluene) and recrystallization (heptane). Yield 9.5 g (yield 82%).

Using compound (1-14-2-a), compound (1-14-2) was synthesized in the same manner as in Example 1 above. The product was purified by column chromatography (silica gel, toluene / ethyl acetate = 10/1) and recrystallization (ethanol). Yield 6.4 g (yield 62%).

Phase transition point (° C); C ・ 126.6 ・ N ・ 184.0 ・ I
^{1 1} H-NMR (ppm, CDCl ₃ ); 7.64-7.60 (m, 4H), 7.57, 7.43 (AA'BB', 4H), 7.31-7.25 (m, 2H), 6.89 (d, 1H, J = 8.00Hz), 4.11-4.04 (m, 2H), 3.04-2.99, 2.93-2.78, 2.53 -2.51, 1.90-1.86, 1.78-1.67 (m, 16H) 2.30 (s, 3H).

[Example 7] Synthesis of the compound represented by the formula (1-14-3)

4- (3-Methyl-3-butenyloxy) -3-methylphenylboronic acid and compound (1-13-) synthesized in the same manner as in 4- (3-butenyloxy) -2-methylphenylboronic acid of Example 4. Using 1-a), compound (1-14-3-a) was synthesized by the same method as in Example 4 above. The product was purified by column chromatography (silica gel, toluene) and recrystallization (heptane). Yield 6.5 g (yield 86%).

Using compound (1-14-2-a), compound (1-14-3) was synthesized in the same manner as in Example 1 above. The product was purified by column chromatography (silica gel, toluene: ethyl acetate = 10: 1) and recrystallization (ethanol). Yield 6.9 g (yield 85%).

Phase transition point (° C); C ・ 122.0 ・ N ・ 153.3 ・ I
^{1 1} H-NMR (ppm, CDCl ₃ ); 7.63-7.62 (m, 4H), 7.57, 7.29 (AA'BB', 4H), 7.45-7.42 (m, 4H). 2H), 6.90 (d, 1H, J = 9.00Hz), 3.00-2.77, 2.67-2.66, 2.51-2.50 (m, 7H), 2.29 (S, 3H), 2.17-1.83 (m, 4H), 1.55 (s, 3H).

[Example 8] Synthesis of the compound represented by the formula (1-14-4)

4- (4-Hexenyloxy) -3-methylphenylboronic acid and compound (1-13-1-a) synthesized in the same manner as in 4- (3-butenyloxy) -2-methylphenylboronic acid of Example 4. ) Was used to synthesize the compound (1-14-4-a) in the same manner as in Example 4 above. The product was purified by column chromatography (silica gel, heptane / toluene = 1/1) and recrystallization (toluene / ethanol). Yield 1.7 g (yield 88%).

Using compound (1-14-4-a), compound (1-14-4) was synthesized in the same manner as in Example 1 above. The product was purified by column chromatography (silica gel, toluene: ethyl acetate = 10: 1) and recrystallization (ethanol). Yield 0.96 g (yield 52%).

Phase transition point (° C.); C ・ 108.3 ・ N ・ 174.0 ・ I
^{1 1} H-NMR (ppm, CDCl ₃ ); 7.63-7.60 (m, 4H), 7.57, 7.29 (AA'BB', 4H), 7.44-7.40 (m, 2H), 6.89 (d, 1H, J = 8.00Hz), 4.04 (t, 2H, J = 6.00Hz), 3.05-3.00, 2.82-2.77, 2 .52-2.50 (m, 8H), 2.29 (s, 3H), 2.05-1.83, 1.80-1.60 (m, 8H).

[Example 9] Synthesis of the compound represented by the formula (1'-21)

Of compound (1'-21-a) 3.00 g (10.9 mmol), 4-bromo-2-methylbut-1-ene 3.56 g (23.9 mmol), and K2 CO _{3 3.6} g (26 mmol). The mixture was reacted in DMF (20 ml) in N2 atmosphere at 80 ° C. for 8 hours. After cooling the reaction solution, toluene (100 ml) was added, and the mixture was washed with pure water (100 ml). The organic layer was separated, dried in anhydrous י ₄ , and then filtered. After distilling off the solvent under reduced pressure, the residue was purified by column chromatography (silica gel, toluene) to obtain compound (1'-21-b). Yield 2.85 g (yield 64%).

Using compound (1'-21-b), compound (1'-21) was synthesized in the same manner as in Example 1 above. The product was purified by column chromatography (silica gel, toluene: ethyl acetate = 10: 1) and recrystallization (ethanol). Yield 0.95 g (yield 69%).

Phase transition point (° C); C ・ 151.8 ・ I
^{1 1} H-NMR (ppm, CDCl ₃ ); 7.63-7.59 (m, 4H), 7.56 (AA'XX', 2H), 7.43-7.41 (m, 2H), 6 .98 (AA'XX', 2H), 6.89 (d, 1H, J = 9.00Hz), 4.15-4.09, 2.80-2.76, 2.68-2.65, 2.23-2.13, 2.10-2.03 (m, 12H), 2.29, 1.44, 1.43 (s, 9H).

[Comparative Example 1]
As a result of measuring the phase transition point of the compound represented by the formula (ref. 1), the results were as follows.
Phase transition point (° C); C ・ 176.9 ・ I

From the comparison between the above Examples and Comparative Examples, it can be seen that the compound of the present invention tends to have liquid crystallinity. In particular, the compounds of Examples 3 to 8 have a wide liquid crystal phase in a temperature range from 80 ° C. to 180 ° C., which is a temperature range suitable for curing an epoxy.

[Synthesis Example 1] Synthesis of the compound represented by the formula (3-2-1)

CH 3-formyl-4,4'-dihydroxybiphenyl 2.00 g (9.34 mmol), 3,4-dihydro-2H-pyran 4.7 g (56 mmol), and PPTS 0.47 g (1.9 mmol) CH ₂ Cl ₂ In 20 ml, stirred overnight at room temperature. In the above reaction, 3-formyl-4,4'-dihydroxybiphenyl was added to Journal of Medicinal Chemistry, vol. 52, p. 858 (2009). Synthesized according to. 30 ml of saturated aqueous sodium hydrogen carbonate was added to the reaction solution, and the organic layer was separated. The organic layer is dried over anhydrous magnesium sulfate, filtered, the solvent is distilled off under reduced pressure, and the obtained product is purified by column chromatography (toluene / ethyl acetate = 10/1) to purify the compound (3-2). -1-a) was obtained. Yield 244 mg (yield 7.9%).

A solution of t-BuOK 294 mg (2.62 mmol) in THF (10 ml) was added to a solution of methyltriphenylphosphonium bromide in 868 mg (2.43 mmol) in THF (10 ml) at 0 ° C. or lower. After stirring at 0 ° C. for 30 minutes, the mixture was cooled to −20 ° C., and 1.00 g (1.87 mmol) of compound (3-2-1-a) was added. After stirring at room temperature for 2 hours, the mixture was poured into pure water (50 ml) and extracted with toluene (50 ml). The organic layer was washed with pure water (50 ml) and then dried over anhydrous magnesium sulfate. The organic layer was filtered, the solvent was distilled off under reduced pressure, and the obtained product was purified by column chromatography (heptane / toluene = 1/1 → toluene) to obtain compound (3-2-1-1b). .. Yield 766 mg, yield 77%.

To a mixed solution of 1.61 g (4.21 mmol) of compound (3-2-1-b) in THF (10 ml) -MeOH (10 ml), 425 mg (16.9 mmol) of pyridinium p-toluenesulfonate was added, and the mixture was added at room temperature. It was stirred in the evening. Brine and ethyl acetate (30 ml each) were added to the reaction solution, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained product was purified by column chromatography (toluene: ethyl acetate = 2: 1) to obtain compound (3-2-1). 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 = 11.000Hz), 4.99 (s, 1H), 4.76 (s, 1H).

１－ヨード－４―トランス（４－ｎ－ペンチル）シクロヘキシルベンゼン３．３０ｇ（９．２６ｍｍｏｌ）、４－エチニル－１，２－ジメトキシベンゼン１．５０ｇ（９．２５ｍｍｏｌ）、ジクロロビストリフェニルフォスフィンパラジウム（ＩＩ）１３０ｍｇ（０．１８５ｍｍｏｌ）、およびＣｕＩ ３５．２ｍｇ（０．１８５ｍｍｏｌ）の混合物を、Ｅｔ_３Ｎ（３０ｍｌ）中、Ｎ_２気流下４時間還流した。反応液を冷却後、トルエン（６０ｍｌ）および純水（５０ｍｌ）を反応液に加え、有機層を分離した。有機層は、ＭｇＳＯ_４で乾燥後、ろ過し、溶媒を減圧留去した。残渣をカラムクロマトグラフィー（シリカゲル、トルエン／酢酸エチル＝１０／１）および再結晶（ＥｔＯＨ）で精製することにより、化合物（ｐ－１－ａ）を得た。収量２．７２ｇ（収率７５％）。 [Synthesis Example 2] Synthesis of the compound represented by the formula (p-1)

1-iodo-4-trans (4-n-pentyl) cyclohexylbenzene 3.30 g (9.26 mmol), 4-ethynyl-1,2-dimethoxybenzene 1.50 g (9.25 mmol), dichlorobistriphenylphosphine palladium A mixture of (II) 130 mg (0.185 mmol) and CuI 35.2 mg (0.185 mmol) was refluxed in Et ₃ N (30 ml) for 4 hours under an N ₂ stream. After cooling the reaction solution, toluene (60 ml) and pure water (50 ml) were added to the reaction solution, and the organic layer was separated. The organic layer was dried with י ₄ , filtered, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, toluene / ethyl acetate = 10/1) and recrystallization (EtOH) to obtain compound (p-1-a). Yield 2.72 g (yield 75%).

The above-mentioned 1-iodo-4-trans (4-n-pentyl) cyclohexylbenzene and 4-ethynyl-1,2-dimethoxybenzene are described in J. Am. Chem. Soc. , 131,6763 (2009). And J. Org. Chem. , 73, 4241 (2008). Synthesized according to.

2.20 g (5.75 mmol) of compound (p-1-a) was hydrogenated in an autoclave in toluene / ethanol = 20/20 ml with Pd / C 320 m as a catalyst. At this time, the hydrogen pressure was 0.7 MPa. After the reaction, the catalyst was filtered off and the solvent was distilled off under reduced pressure. The residue was purified by recrystallization (EtOH) to obtain compound (p-1-b). Yield 1.70 g (yield 75%).

To 1.10 g (2.79 mmol) of compound (p-1-b) in CH ₂ Cl ₂ (10 ml), add 5.8 ml of BBr ₃ in CH ₂ Cl ₂ (1M) at -10 ° C. rice field. After stirring overnight at room temperature, the reaction solution was added to pure water (30 ml). AcOEt (40 ml) was added to this mixture and extracted. The organic layer was washed twice with pure water (15 ml) and then dried with ו ₄ . The solution was filtered and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, toluene / ethyl acetate = 1/1) and recrystallization (toluene) to obtain compound (p-1). Yield 870 mg (yield 85%).

Phase transition point (° C.); C. 147.4, N, 161.4, I.
^{1 1} H-NMR (ppm, CDCl ₃ ); 7.14-7.09 (AA'BB', 4H), 6.78 (d, 1H, J = 8.00Hz), 6.72 (d, 1H, J = 2.00Hz), 6.64 (dd, 1H, J = 8.00, 2.00Hz), 4.98, 4.86 (s, 1H), 2.84-2.79, 2.48 -2.39, 1.89-1.84, 1.49-0.88 (m, 25H).

[Example 10] Preparation of composition and confirmation of solubility 0.5000 g (1.300 mmol) of the compound represented by the formula (1-2-1) synthesized in Example 1 and 0.2786 g (1) of bisphenol E. .300 mmol) was placed in a sample bottle, cyclopentanone (2.80 ml) was added, and the solid content was dissolved to obtain a composition (composition 12) having a solid content concentration of about 20%. When this composition 10 was allowed to stand in a refrigerator set at 0 ° C. overnight, no precipitation occurred and the composition remained as it was.

[Example 11] to [Example 30]
A composition solution having a solid content concentration of 20% by weight shown below was prepared in the same manner as in Example 10 except that the epoxy compound and the curing agent were changed as shown in Table 1 below, and the solubility was confirmed. .. In Table 1, the column in which two types of epoxy compounds or curing agents are listed indicates that they are mixed, and the ratio thereof is shown by the molar ratio of each compound. Moreover, the molar ratio of the epoxy compound and the curing agent in each composition was made equal.

Table 1 Composition and its solubility (solvent cyclopentanone)

[Example 31]
0.5000 g (1.26 mmol) of the compound represented by the formula (1-14-3), 0.1794 g (0.8452 mmol) of the compound represented by the formula (3-2-1), and (p-1). ), 0.1330 g (0.3628 mmol) of the compound is placed in a sample bottle, cyclopentanone (3.14 ml) is added, the solid content is dissolved, and the composition having a solid content concentration of about 20% (composition 31). ) Was obtained. When this composition 31 was allowed to stand in a refrigerator set at 0 ° C. overnight, no precipitation occurred and the composition remained as it was.

[Comparative Example 2]
Using the compound represented by the formula (ref.1), the solubility was confirmed by the same method as in Example 10 above. As a result, it did not dissolve in cyclopentanone.

From the comparison between Examples 10 to 31 and Comparative Example 2, it can be seen that the compound of the present invention has high solubility in a solvent.

[Example 32] Preparation of composition, confirmation of liquid crystallinity, and confirmation of storage stability 1.000 g (2.601 mmol) of the compound represented by the formula (1-2-1) synthesized in Example 1, PDA 0. .1406 g (1.300 mmol) was placed in a sample bottle, tetrahydrofuran (10 ml) was added, and the solid content was dissolved (composition 32). When this composition was observed with a polarizing microscope on a hot plate, liquid crystallinity was confirmed.
Next, the solution was vacuum dried at room temperature for 2 hours to obtain a solvent-free composition (composition 32') as a viscous liquid.
When the above composition 34'was left in a refrigerator at 0 ° C. overnight, it kept a viscous liquid.

[Comparative Example 3]
1.000 g (2.574 mmol) of the compound represented by the formula (ref. 1) and 0.1392 g (1.287 mmol) of the PDA were placed in a sample bottle, and tetrahydrofuran (100 ml) was added to dissolve the solid content (composition). ref.3). When this composition was observed with a polarizing microscope, a region showing liquid crystallinity was confirmed in a part, but crystals were confirmed in other regions. Further, the solution was distilled off under reduced pressure with a solvent evaporator and then vacuum dried at room temperature for 2 hours to obtain a solvent-free composition (composition ref. 3'). This composition ref. Part of 3'was crystallized.

By comparing Example 32 and Comparative Example 3, it can be seen that the composition using the liquid crystal epoxy compound of the present invention is difficult to crystallize. Such compositions are very useful in preparing pasty samples.

[Example 33] to [Example 54] Confirmation of liquid crystallinity of the composition The liquid crystallinity of the compositions prepared in Examples 10 to 31 was confirmed. The results are shown in Table 2.
Table 2 Confirmation of liquid crystal properties of the composition

The compositions described in Examples 33 to 54 exhibited a uniform nematic phase in the liquid crystal temperature region, except for the composition described in Example 39. On the other hand, the composition of Comparative Example 3 ref. No. 3 did not have a uniform liquid crystal phase. This suggests that the composition using the liquid crystal epoxy compound of the present invention has high compatibility with the curing agent. The cured product obtained by curing such a composition is a material having no bias in the components and having excellent thermal conductivity and reliability.

[Example 55]
Measurement of thermal conductivity of cured product adjusted from composition 32 The above composition 32 was placed in an aluminum container having a diameter of 2.4 cm and held on a hot plate heated to a temperature of 150 ° C. for 120 minutes to increase the thickness. A 1.5 mm circular piece was taken out. The thermal conductivity of this cured product (cured product 32) was 0.95 W / m · K and 0.45 W / m · K, respectively, in the in-plane direction and the thickness direction of the sample.

[Example 56] to [Example 57]
The heat dissipation characteristics of the composition shown in Table 3 or the cured product prepared from the composition were confirmed by the same method as in Example 55. In the table, the molar% of each component compound in each component is shown in parentheses. Regarding the liquid crystal property, the case where there was a case was evaluated as ◯, and the case where there was no case was evaluated as x.

Table 3. Liquid crystallinity and thermal conductivity of the composition

[Example 58] Measurement of thermal conductivity of cured product 2
0.0400 g (0.588 mmol) of imidazole was added to and dissolved in the composition 10 prepared in Example 10 to obtain the composition 10C. The composition 10C was placed in an aluminum container having a diameter of 2.4 cm and held on a hot plate heated to a temperature of 150 ° C. for 120 minutes, and a circular piece having a thickness of about 1.0 mm was taken out. The thermal conductivity of this cured product (cured product 10C) was 0.90 W / m · K and 0.41 W / m · K, respectively, in the in-plane direction and the thickness direction of the sample.

[Example 59] to [Example 78]
Imidazole was added to the composition 31 (excluding the original composition and the composition 16) from the above composition 11 by the same method as in Example 58, and the composition 31C was prepared from the composition 11C. Further, the composition was heated to obtain a cured product. The results of measuring the thermal conductivity of these cured products are shown in Table 4.
Table 4. Thermal conductivity of the composition

[Example 79] Preparation of sample containing filler Weigh 1.0 g of the composition 32 and 0.90 g of boron nitride particles (PolyrTherm PTX-25 manufactured by Momentive Performance Materials Japan (Go)) and mix them well. After standing on a hot plate heated to a temperature of 80 ° C for 5 minutes, this sample was sandwiched between stainless steel plates and heated to a temperature of 150 ° C. IMC manufactured by Imoto Seisakusho Co., Ltd. A pressure of 20 MPa was applied at -19EC) and the mixture was held for 45 minutes, and a square piece having a thickness of 768 μm as a heat radiating member was taken out. The thermal conductivity of this sample (sample 32 containing filler) was 10.8 W / m · K.

[Example 80] and [Example 81]
Samples 33 and 34 containing a filler were prepared and the thermal conductivity was measured in the same manner as in Example 79 above, except that the compositions 33 and 34 were used instead of the composition 32. The results are shown in Table 5.

Table 5. Thermal conductivity of sample with filler 1

[Example 82] Preparation of sample containing filler 2
A sample (sample 22C containing a filler) was prepared in the same manner as in Example 79 except that 0.5 g of the composition 22C was used. The thermal conductivity of the filler-containing sample 22C was 12.0 W / m · K.

[Example 83] to [Example 90]
31C was prepared from the filler-containing sample 23C and the thermal conductivity was measured in the same manner as in Example 82 above, except that the composition 31C was used from the composition 23C instead of the composition 22C. The results are shown in Table 6.

Table 6. Thermal conductivity of sample with filler 2

[Example 91] and [Example 92]
0.5 g of the composition 24C or the composition 26C and 0.90 g of aluminum oxide particles (DAW-10 manufactured by Denka) are weighed and mixed well, and a sample containing a filler is used in the same manner as in Example 84 above. 24C _AO and 26C _AO were prepared and their thermal conductivity was measured. The results are shown in Table 7.

上記のように、本発明に開示された技術は、高い熱伝導率を与える事が分かる。 Table 7. Thermal conductivity of sample with filler 3

As mentioned above, it can be seen that the technique disclosed in the present invention provides high thermal conductivity.

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

Claims (16)

In a liquid crystal epoxy compound having two or more oxylanyls and two to five aromatic rings, the oxylanyl-bearing group was attached to the aromatic ring, and at least one oxylanyl was attached to the aromatic ring via carbon. Compound. The compound according to claim 1, wherein the liquid crystalline epoxy compound is a rod-shaped molecule. The compound according to claim 2, which is represented by the formula (1).

In formula (1), ^Rep is independently a group having 2 to 12 carbon atoms having an oxylanyl, at least one oxylanyl is bonded to an aromatic ring via carbon, and X is independently and single bonded. , -CH ₂ CH _2- , -CH ₂ O-, -CH = CH-, -C≡C-, or -COO-, R ¹ is independently hydrogen, alkyl with 1 to 8 carbon atoms, It is an alkoxy or ^Rep having 1 to 8 carbon atoms, and at least one of these alkyl and alkoxy -CH _2- may be replaced with -C (= O)-, and n is 0 to 2. The compound according to claim 3, wherein X is a single bond or —C≡C— in the liquid crystal epoxy compound represented by the formula (1). A composition comprising the compound according to any one of claims 1 to 4 and a curing agent. The composition according to claim 5, further comprising a curing accelerator. Claimed that the curing agent is an aromatic having two or more aromatic primary amines, an aliphatic primary amine, and a secondary amino in the molecular skeleton, or an aliphatic amine having two or more secondary aminos in the molecular skeleton. 5 or 6 according to the composition. The composition according to claim 7, wherein the curing agent is at least one compound represented by the formula (2-1) or (2-2).
EZ- (LZ) n-E (2-1)
L1 ^- Z-E (2-2)
In equations (2-1) and (2-2),
L is independently a single bond, cyclohexylene, phenylene, or naphthalene, and at least one hydrogen in these rings may be replaced by an alkyl having 1 to 10 carbon atoms.
L ¹ is hydrogen, cyclohexyl, phenyl, or naphthyl, and at least one hydrogen in these rings may be replaced with an alkyl having 1 to 10 carbon atoms.
Z is independently a single bond, -O-, -NH-, -S-, -SO _2- , -CO _2- , or an alkylene with 1-12 carbon atoms.
E is independently an amino, an alkylamino having 1 to 10 carbon atoms, a hydroxyl group, or a carboxy, and at least one of E is an amino or an alkylamino having 1 to 10 carbon atoms.
n is an integer from 0 to 7. The composition according to claim 5 or 6, wherein the curing agent is a phenol having two or more -OH in the molecular skeleton, or a compound in which at least one of -OH in the phenol is a short-chain ester.
The short-chain ester has a structure in which the group represented by (3-E) below is replaced with H of the OH group.

In the formula, R ¹³ represents a methyl, ethyl, propyl, butyl, pentyl, or hexyl group, and the propyl, butyl, pentyl, or hexyl group may be a branched chain. * Represents the bond position with O. The ninth aspect of the present invention, wherein the curing agent is at least one compound represented by the formulas (3-1) to (3-7), or a compound in which at least one of -OH in the compound is a short-chain ester. The composition described.

In equation (3-1),
Ring B is benzene, naphthalene, anthracene, fluorene, or 9,9-diphenylfluorene, in which at least one hydrogen is an alkyl having 1 to 3 carbon atoms or an alkoxy having 1 to 3 carbon atoms. May be replaced;
n31 is an integer of 2 or more and 4 or less.
In equation (3-2), n32 and n33 are independently integers of 1 to 3;
Z ³⁰ is 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 -and
At least one hydrogen on the benzene ring may be replaced with an alkyl having 1-3 carbon atoms or an alkenyl having 2-3 carbon atoms;
In equations (3-3) and (3-4),
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 iteration.
R ¹⁰ and R ¹¹ are independently 1,4-phenylene, 4,4'-biphenylene, or 1,3-cyclopentadienylene.
In equation (3-5),
n34 is an integer of 1 or more and 5000 or less,
In equation (3-6),
Z ³¹ is an independently single bond, -CH (CH ₃ )-, or -C (CH ₃ ) _2- , and n34 is an integer of 1 or more and 5000 or less.
In equation (3-7),
n34 is an integer of 1 or more and 5000 or less, and ^R12 is independently hydrogen or methyl.
The short-chain ester has a structure in which the group represented by (3-E) below is replaced with H of the OH group.

In the formula, R ¹³ represents a methyl, ethyl, propyl, butyl, pentyl, or hexyl group, and the propyl, butyl, pentyl, or hexyl group may be a branched chain. * Represents the bond position with O.
Further, at least one hydrogen on the aromatic ring in these formulas (3-3) to (3-7) may be replaced with methyl. The composition according to claim 5 or 6, wherein the curing agent is a compound containing a cyanate ester. The composition according to claim 5 or 6, wherein the curing agent is a compound containing a carboxylic acid, a carboxylic acid ester, an acid anhydride, or a thiol. The composition according to any one of claims 5 to 12, further comprising an inorganic filler. 13. The composition of claim 13, wherein the inorganic filler is aluminum oxide, boron nitride, or aluminum nitride. A material for electronic components obtained by curing the composition according to any one of claims 5 to 14. A compound represented by the formula (1').

In formula (1'), R ^ep'is independently a group of 4 to 12 carbon atoms having oxylanyl, and R ¹ is independently hydrogen or methyl.