JP2021193176A - Polymerizable compound, electronic component composition, and electronic component material - Google Patents

Abstract

To provide: a compound with a terphenyl backbone which has a liquid crystalline property and a low melting point; and a resin material with high thermal conductivity based on the compound.SOLUTION: The compound is represented by the formula (1) in the figure. In the formula (1), each Rce is independently a C4-12 group including an oxiranyl or oxetanyl, and each R1 is independently hydrogen, a C1-8 alkyl, or -ORce.SELECTED DRAWING: 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 a liquid crystal display 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 effectively 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 oxylan 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 compound having a terphenyl skeleton, which has a liquid crystallinity and a low melting point. Another object of the present invention is to provide a resin material having a high thermal conductivity using the compound.

式（１）中、Ｒ^ｃｅは独立して、オキシラニルまたはオキセタニルを含む炭素数４から１２の基であり、Ｒ^１は独立して、水素、炭素数１から８のアルキル、または−ＯＲ^ｃｅである。 The present inventors have found that the compound represented by the following formula (1) solves the above-mentioned problems, and have completed the present invention.

In formula (1), R ^ce is independently a group having 4 to 12 carbon atoms containing oxylanyl or oxetanyl, and R ¹ is independently being hydrogen, an alkyl having 1 to 8 carbon atoms, or −OR ^ce . be.

A composition made from a compound represented by the formula (1) tends to exhibit liquid crystallinity when itself or when the composition is cured. Therefore, the cured product has high thermal conductivity. Further, the composition using the compound represented by the formula (1) as a raw material is easy to be made into a paste. Therefore, it can be suitably used as a heat radiating 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 following embodiments.

式（１）中、Ｒ^ｃｅは独立して、オキシラニルまたはオキセタニルを含む炭素数４から１２の基であり、Ｒ^１は独立して、水素、炭素数１から８のアルキル、または−ＯＲ^ｃｅである。 The present invention includes the following items.
[1] A compound represented by the formula (1).

In formula (1), R ^ce is independently a group having 4 to 12 carbon atoms containing oxylanyl or oxetanyl, and R ¹ is independently being hydrogen, an alkyl having 1 to 8 carbon atoms, or −OR ^ce . be.

[2] A composition containing a compound represented by the formula (1) and a curing agent.

[3] The composition according to item [2], further comprising a curing accelerator.

[4] 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. The composition according to item [2] or [3].

[5] The composition according to item [4], wherein the curing agent is at least one compound represented by the formula (2-1) or (2-2).
E ¹ -Z- (L-Z) n-E ¹ (2-1)
L ¹ -Z-E (2-2)
In equations (2-1) and (2-2),
Z is independently a single bond, -O-, -NH-, -S-, -SO _2- , -CO _2- , or an alkylene with 1-12 carbon atoms.
In equation (2-1),
L is independently a single bond, cyclohexylene, phenylene, or naphthalene, and at least one hydrogen in these rings may be replaced with an alkyl having 1 to 10 carbon atoms.
E ¹ is independently an amino, an alkylamino having 1 to 10 carbon atoms, a hydroxyl group, or a carboxy, and at least one E is an amino or an alkylamino having 1 to 10 carbon atoms.
n is an integer from 0 to 7.
In equation (2-2),
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.
E is an amino or an alkylamino having 1 to 10 carbon atoms.

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、分岐鎖であってもよい。＊は結合位置を表す。） [6] Item [2] or [3], 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. * Represents the bond position. )

式（３−１）中、
ｎ３１は２以上４以下の整数であり；
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い。
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−を表し、
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い。
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、このｎ３５およびｎ３６は繰り返し毎に異なってもよく、
式（３−４）中、
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を表し、
式（３−５）中、
ｎ３４は１以上５０００以下の整数であり、
式（３−６）中、
ｎ３４は１以上５０００以下の整数であり、
Ｚ^３１は独立して、単結合、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−を表し、ｎ３４は１から５０００以下の整数を表す。
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。
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。
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く、＊は結合位置を表す。 [7] The term, 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 according to [6].

In equation (3-1),
n31 is an integer greater than or equal to 2 and less than or equal to 4.
Ring B is benzene, naphthalene, anthracene, fluorene, or 9,9-diphenylfluorene, in which at least one hydrogen is an alkyl having 1-3 carbon atoms or an alkoxy having 1-3 carbon atoms. It may be replaced.
In equation (3-2),
n32 and n33 are independently integers 1-3;
Z ³⁰ is a single bond, alkylene with 1 to 10 carbon atoms, -CH (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O-, -S-, or. Represents −SO ₂ −
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, these n35 and n36 may be different for each iteration.
In equation (3-4),
R ¹⁰ and R ¹¹ independently represent 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),
n34 is an integer of 1 or more and 5000 or less,
Z ³¹ independently represents a single bond, −CH (CH ₃ ) −, −C (CH ₃ ) ₂ −, and n34 represents an integer from 1 to 5000 or less.
In equation (3-7),
n34 is an integer between 1 and 5000, ^{inclusive, R 12} is hydrogen or methyl.
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 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, the propyl, butyl, pentyl, or hexyl group may be a branched chain, and * represents a bond position.

[8] The composition according to Item [2] or [3], wherein the curing agent is a compound containing a cyanate ester.

[9] The composition according to Item [2] or [3], wherein the curing agent is a compound containing a carboxylic acid, a carboxylic acid ester, an acid anhydride, or a thiol.

[10] The composition according to any one of Items [2] to [9], further comprising an inorganic filler.

[11] The composition according to item [10], wherein the inorganic filler is aluminum oxide, boron nitride, or aluminum nitride.

[12] A material for electronic components obtained by curing the composition according to any one of items [2] to [11].

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 kind of the compound represented by the formula (1).

式（１）中、Ｒ^ｃｅは独立して、オキシラニルまたはオキセタニルを含む炭素数４から１２の基であり、Ｒ^１は独立して、水素、炭素数１から８のアルキル、またはＯＲ^ｃｅである。 The present inventors have found that the compound represented by the following formula (1) solves the above-mentioned problems, and have completed the present invention.

In formula (1), R ^ce is independently a group of 4 to 12 carbon atoms containing oxylanyl or oxetanyl, and R ¹ is independently hydrogen, an alkyl having 1 to 8 carbon atoms, or OR ^ce . ..

In formula (1), R ^ce is a group having 4 to 12 carbon atoms containing oxylanyl or oxetanyl. At this time, in order to improve the heat resistance of the present invention cured product, as R ^ce, it is preferable to select a group from 4 to 6 carbon atoms containing oxiranyl or oxetanyl. The improved liquid crystallinity of the composition of the present invention, in order to improve the thermal conductivity, as R ^ce, it is preferable to select a group having 7 to 12 carbons containing oxiranyl or oxetanyl.

R ¹ is hydrogen, alkyl or ^{-OR, ce} from 1 to 8 carbon atoms. In order to improve the heat resistance of the present invention cured product, as R ^1, it is preferable to select the number 4 to 12 of the group having a carbon containing oxiranyl or oxetanyl. At this time, to improve the liquid crystal of the present invention the composition, in order to improve the thermal conductivity, as ^a group R, it is preferable to select the number 4-6 groups carbons that includes oxiranyl or oxetanyl.

In order to greatly improve the liquid crystallinity and the thermal conductivity of the composition of the present invention, it is preferable to select an alkyl having 1 to 5 carbon atoms as the ^{R 1 group, and an alkyl having 1 to 3 carbon atoms is used.} It is more preferable to select. Further to improve the compatibility of the composition of the present invention, in order to prevent the precipitation of crystals during storage as ¹ group R, it is preferable to select an alkyl of from 3 to 8 carbon atoms.

R ¹ may be replaced at any position on the three benzene rings. At this time, in order to greatly improve the liquid crystal property of the composition and greatly improve the thermal conductivity, it is preferable to position the composition in a position other than the position adjacent to ^{−OR ce.}

As described above, the compound represented by the formula (1) of the present invention is liquid crystal and has a low melting point. When -OR ^{ce is selected as R ce} or R ^1, it is preferable to select oxylanyl as these groups because it can be cured at a relatively low temperature of 200 ° C. or lower.

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. Other known oxylanyl compounds can be used in combination as long as the liquid crystallinity of the composition is not lost. As such a compound, a liquid crystalline oxylanyl compound that can be represented by the following formulas (o-1) to (o-5) can be preferably used.

また上記他のオキシラニル化合物としては、以下の式（ｏ−７）から式（ｏ−２１）で表される非液晶性オキシラニル化合物が好ましく用いられる。

As the other oxylanyl compound, a non-liquid crystal oxylanyl compound represented by the following formulas (o-7) to (o-21) is preferably used.

式（ｏ−１２）において、Ｚ^１０は単結合、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−を表す。

In equation (o-12), Z ¹⁰ is a single bond, -CH _2- , -O-, -S-, -CH (CH ₃ )-, -C (CH ₃ ) _2- , -SO ₂ -,- Represents C (CF ₃ ) ₂ −.

式（ｏ−１３）および式（ｏ−１４）において、Ｚ^１１は＞ＣＨ−または＞Ｃ（ＣＨ_３）−を表す。

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

Further, as the above-mentioned other oxylanyl compound, a resin having a structure represented by the following formulas (o-23) to (o-25) is also preferably used.

In equation (o-23), Z ¹² and Z ¹³ _{are single bonds, -CH 2-} , -O-, -S-, -CH (CH ₃ )-, -C (CH ₃ ) _2- , -SO ₂ -, -C (CF ₃ ) _2- represents, n21 represents an integer from 1 to 5000 or less.
In equations (o-24) and (o-25), n21 represents an integer from 1 to 5000, n22 and n23 represent 0 or 1, and when n21 is 2 or greater, n22 and n23 represent every iteration. May be different,
In formula (o-25), R ¹⁰ and R ¹¹ represent 1,4-phenylene, 4,4'-biphenylene, or cyclopentadienylene.
Further, the hydrogen on the aromatic ring in these formulas (o-24) to (o-25) may be replaced with methyl.

In equations (o-26) and (o-27), n21 represents an integer from 1 to 5000 or less. In equation (o-27), Z ¹⁴ represents a single bond, −CH (CH ₃ ) −, −C (CH ₃ ) ₂ −.
Further, hydrogen on the aromatic ring in these formulas (o-26) and (o-27) may be replaced with methyl.

The content of such a known oxylanyl 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 80% by weight with respect to the total weight of the oxylanyl 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 60% by weight, and it is more preferable to use it between 0.1% by weight and 50% by weight.

[Curing agent]
In the composition of the present invention, as the curing agent, known compounds such as amine, phenol, cyanate ester, carboxylic acid, carboxylic acid ester, acid anhydride, and thiol 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.
E ¹ -Z- (L-Z) n-E ¹ (2-1)
L ¹ -Z-E (2-2)

In equations (2-1) and (2-2),
Z is independently a single bond, -O-, -NH-, -S-, -SO _2- , -CO _2- , or an alkylene with 1-12 carbon atoms.
In equation (2-1),
L is independently a single bond, cyclohexylene, phenylene, or naphthalene, and at least one hydrogen in these rings may be replaced with an alkyl having 1 to 10 carbon atoms.
E ¹ is independently an amino, an alkylamino having 1 to 10 carbon atoms, a hydroxyl group, or a carboxy, and at least one E is an amino or an alkylamino having 1 to 10 carbon atoms.
n is an integer from 0 to 7.
In equation (2-2),
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.
E is an amino or an alkylamino having 1 to 10 carbon atoms.

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- 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),
n31 is an integer greater than or equal to 2 and less than or equal to 4.
Ring B is benzene, naphthalene, anthracene, fluorene, or 9,9-diphenylfluorene, in which at least one hydrogen is an alkyl having 1-3 carbon atoms or an alkoxy having 1-3 carbon atoms. It may be replaced.
In equation (3-2),
n32 and n33 are independently integers 1-3;
Z ³⁰ is a single bond, alkylene with 1 to 10 carbon atoms, -CH (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O-, -S-, or. Represents −SO ₂ −
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, these n35 and n36 may be different for each iteration.
In equation (3-4),
R ¹⁰ and R ¹¹ independently represent 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),
n34 is an integer of 1 or more and 5000 or less,
Z ³¹ represents a single bond, −CH (CH ₃ ) −, −C (CH ₃ ) ₂ −, and n34 represents an integer from 1 to 5000 or less.
In equation (3-7),
n34 is an integer between 1 and 5000, ^{inclusive, R 12} 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、分岐鎖であってもよい。また、＊は結合位置を表す。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. In addition, * represents the bond position. Among these R ^13, if you select the methyl, the crystallinity of the compound is increased, which may impair the liquid crystalline 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 oxylanyl: amine, it is 2: 1 and in the case of oxylanyl: phenol, it is 1: 1.

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

[Hardening 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. Such curing accelerators include 2-ethyl-4-methyl-1H-imidazole, 2-phenyl-4-methyl-1H-imidazole, 1,2-dimethylimidazole, 2-undecylimidazole, 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 is fast.

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, Berilia, Magnesium Oxide, Aluminum Oxide, Zinc Oxide, Silicon Oxide, Copper Oxide, Titanium Oxide, Cerium Oxide, Ittrium Oxide, Tin Oxide, Forminium Oxide, Bismus 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 (trade name) 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 oxylanyl. 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. For example, a polymerizable compound other than the formula (1), a non-polymerizable compound, a polymerization initiator, a solvent and the like can be mentioned.

As the polymerizable compound having a polymerizable group other than oxylanyl, there is no particular limitation as long as the characteristics of the electronic material of the present invention are not deteriorated, and known polymerizable compounds 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, and 3,5-di-t-butyl-4-hydroxytoluene (BHT) 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, or supermolecules, etc. May be added.

[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, the material for electronic parts of the present invention can be used as a heat radiating member.
The material for electronic parts consists of 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 room temperature to 350 ° C., preferably room temperature 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 manufacturing method when the inorganic filler is subjected to the coupling treatment will be described below. A known method can be used for 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]
A method for producing a film as a material for electronic components using a solvent-free composition for electronic components will be described below.
The solvent-free composition for electronic components is sandwiched in a heating plate using a compression molding machine and compression molded. 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.
The ease of handling of the composition for electronic components can be further improved by setting a partially cured state (semi-cured state). For example, it is possible to form a semi-cured composition into a sheet shape, cut it into a desired shape, place it between suitable members, and bond them 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 dissipation member may be any of a heat dissipation plate, a heat dissipation sheet, a heat dissipation film, a heat dissipation adhesive, a heat dissipation 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, uninterruptible power supplies, 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. Has been described. 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 following examples. When the temperature was not described, the measurement was performed at 23 ° C.

[Measurement of phase transition point of compound of formula (1) and identification of liquid crystal phase]
This was performed using a polarizing microscope (manufactured by Nikon) equipped with a hot stage (manufactured by METTLER TOLEDO) and a differential scanning calorimeter (manufactured by Perkin Elmer, Diamond DSC). Polarization microscopy measurements were observed under cross Nicol. Both heating rates were measured at 3 ° C./min. C is a crystal, N is a nematic phase, I is an isotropic liquid, and () is a monotropic liquid crystal phase.

[Confirmation of liquid crystallinity of composition]
The composition was sandwiched between glass plates, the composition was once melted, then rapidly cooled, and evenly adhered between the glasses. The obtained 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 a cross Nicol using the above-mentioned polarizing microscope. The magnification of the eyepiece and the objective lens was 10x10 times, respectively. When light leakage due to the scattering phenomenon is visually observed in about half or more of the observation area, it is judged to be liquid crystal.

[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]
^{-Sample consisting only of resin; 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 thickness direction and the in-plane 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]
As the epoxy compound represented by the formula (1), the following formulas (1-1) to (1-4) were used in Examples. Further, as a comparative compound, a compound represented by the formula (ref. 1) was also synthesized. These compounds were synthesized as described below. Further, the compound of the above formula (o-1) was also used. (O-1) was synthesized in accordance with Japanese Patent No. 5862479.

[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.

市販の２，４−ジブロモアニソール５．００ｇ（１８．８ｍｍｏｌ）、４−メトキシフェニルボロン酸６．２９ｇ（４１．４ｍｍｏｌ）、テトラキストリフェニルフォスフィンパラジウム（０）２．１７ｇ（１．８８ｍｍｏｌ）、およびＮａ_２ＣＯ_３８．３７ｇ（７９．０ｍｍｏｌ）の混合物を、ジメトキシエタン（４０ｍｌ）中、窒素気流下、３時間還流した。反応液を冷却後、純水及びトルエン各１００ｍｌを加えた。有機層を分離後、同量の純水で２回洗浄し、ＭｇＳＯ_４で乾燥した。ろ過及び溶媒を減圧留去後、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／酢酸エチル＝１０／１）で精製することにより、化合物（１−１−ａ）を得た。収量２．０５ｇ（収率３４％）。 [Example 1] Synthesis of the compound represented by the formula (1-1)

Commercially available 2,4-dibromoanisole 5.00 g (18.8 mmol), 4-methoxyphenylboronic acid 6.29 g (41.4 mmol), tetrakistriphenylphosphine palladium (0) 2.17 g (1.88 mmol), _{A mixture of 8.37 g (79.0 mmol) of Na 2} CO and Na _{2 CO 3 was} refluxed in dimethoxyethane (40 ml) under a nitrogen stream for 3 hours. After cooling the reaction solution, 100 ml each of pure water and toluene was added. After separating the organic layer, it was washed twice with the same amount of pure water and dried with _ו4. 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) to obtain compound (1-1-a). Yield 2.05 g (yield 34%).

4.98 g (15.5 mmol) of compound (1-1-a) was added to 48.5 ml (48.5 mmol) of CH ₂ Cl ₂ solution (1 mol / L) of _{BBr 3 cooled on an ice bath at 10 ° C. or lower.} Was added, and the mixture was stirred at room temperature overnight. Then, on an ice bath, the reaction solution was added to pure water (50 ml), and the resulting precipitate was filtered to obtain compound (1-1-1b). This compound was used as it was in the next reaction without purification.

Compound (1-1-b) 2.00g (7.19mmol ), 4- bromo-1,2-butylene oxide 16.3 g (108 _mmol), a mixture of _{K 2 CO 3 4.46g (32.3mmol)} , The mixture was refluxed in 2-butanone (30 ml) under a nitrogen stream for 20 hours. At this time, 4-bromo-1,2-butylene oxide was added to Bioorganic and Medicinal Chemistry Letters, 24 , 5399 (2014). Synthesized according to. After cooling the reaction solution, 100 ml each of pure water and toluene was added. After separating the organic layer, it was washed twice with the same amount of pure water and dried with _ו4. After filtration and distillation of the solvent under reduced pressure, the obtained product was purified by column chromatography (silica gel, toluene / ethyl acetate = 5/1) and recrystallized (ethanol) to obtain compound (1-1). rice field. Yield 1.90 g (yield 54%).

Phase transition point (° C.); C. (65.3.N.) 90.5.I
^{1 1} H NMR (ppm, CDCl ₃ ); 7.57-7.50 (m, 4H), 7.30 (d, 1H, J = 7.50Hz), 7.24 (dd, 1H, J = 7. 50, 1.50Hz), 7.14 (d, 1H, 1.50Hz), 7.01-6.90 (m, 4H), 4.20-4.15 (m, 6H), 2.16- 1.97 (m, 6H).

[Example 2] Synthesis of the compound represented by the formula (1-2) Same as in Example 1 except that 4-bromo-1,2-butylene oxide was replaced with 1-chloro-2,3-butylene oxide. The compound (1-2) was obtained by the above-mentioned method. At this time, 1-chloro-2,3-butylene oxide was synthesized according to US Pat. No. 4,461,020. Yield 48%.

Phase transition point (° C); C ・ (90.5 ・ N ・) 93.4 ・ I
^{1 1} H NMR (ppm, CDCl ₃ ); 7.57-7.51 (m, 4H), 7.37-7.15 (m, 3H), 7.01-6.90 (m, 4H), 4 .23-4.04 (m, 6H), 3.40-2.99 (m, 6H), 1.56-1.30 (m, 9H).

[Example 3] Synthesis of the compound represented by the formula (1-3) Same as in Example 1 except that 4-bromo-1,2-butylene oxide was replaced with 5-bromo-1,2-epoxypentane. The compound (1-3) was obtained by the above-mentioned method. At this time, 5-bromo-1,2-epoxypentane was used in Journal of the American Chemical Society, 133 , 7853 (2011). Synthesized according to. Yield 53%.

Phase transition point (° C.); C. (69.1, N.) 77.4, I
^{1 1} H NMR (ppm, CDCl ₃ ); 7.56-7.50 (m, 4H), 7.37-7.15 (m, 3H), 7.00-6.94 (m, 4H), 4 .11-4.06 (m, 6H), 3.07-2.42 (m, 9H), 2.11-1.57 (m, 12H).

[Example 4] Synthesis of the compound represented by the formula (1-4) Other than the use of 2-methyl-1,4-bis (4-hydroxyphenyl) benzene instead of the compound (1-1-b). Was synthesized according to the same method as in Example 2. At this time, 2-methyl-1,4-bis (4-hydroxyphenyl) benzene was used in Journal of Materials Chemistry, 15 , 1025 (2005). Was synthesized according to the method described in. Yield 62%.

Phase transition point (° C); C ・ 98.2 ・ N ・ 139.9 ・ I
^{1 1} H NMR (ppm, CDCl ₃ ); 7.57-7.51 (m, 2H), 7.45-7.40 (m, 2H), 7.29-7.26 (m, 3H), 7 0.01-6.95 (m, 4H), 4.43-4.04 (m, 4H), 3.32-2.74 (m, 4H), 2.34-2.33 (m, 3H) , 1.46-1.40 (m, 6H).

[Comparative Example 1] Synthesis of the compound represented by the formula (ref.1) The compound was synthesized by the same method as in Example 1 except that 4-bromo-1,2-butylene oxide was replaced with epibromohydrin. Compound (ref. 1) was obtained. This compound did not show liquid crystallinity.

Phase transition point (° C); C ・ 140.4 ・ I
^{1 1} H NMR (ppm, CDCl ₃ ); 7.56-7.50 (m, 4H), 7.36 (d, 1H, J = 8.00Hz), 7.24 (dd, 1H, J = 7. 50, 1.50Hz), 7.14 (d, 1H, 1.50Hz), 7.02-6.97 (m, 4H), 4.23-2.70 (m, 15H).

[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 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).

[Example 5] Preparation of composition and confirmation of liquid crystal property 1.000 g (2.047 mmol) of the compound represented by the formula (1-1) synthesized in Example 1 and 0.1660 g (1.535 mmol) of PDA were added. It was placed in a sample bottle and tetrahydrofuran (10 mmol) was added to dissolve the solid content. The solution of the present invention was obtained by vacuum drying this solution at room temperature for 2 hours. When this composition was observed with a polarizing microscope on a hot plate, light loss due to scattering was observed in almost the entire observation area.

-Measurement of thermal conductivity of cured product adjusted from composition 5 The above composition 5 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 obtain a thickness. Removed a 1.5 mm circular piece. The thermal conductivity of this cured product (cured product 5) was 0.92 W / m · K and 0.43 W / m · K, respectively, in the in-plane direction and the thickness direction of the sample.

[Example 6] to [Example 10]
The characteristics of the compositions shown in Table 1 below or the cured product prepared from the compositions were confirmed by the same method as in Example 5 above. 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. Further, Example 5 is reprinted.

Table 1. Liquid crystallinity and thermal conductivity of the composition

[Example 11]
・ Preparation of composition and confirmation of liquid crystal property 2
1.000 g (2.047 mmol) of the compound represented by the formula (1-1) synthesized in Example 1 and 0.6578 g (3.070 mmol) of bisphenol E are placed in a sample bottle, tetrahydrofuran (10 mmol) is added, and a solid is added. The minute was dissolved. The solution of the present invention was obtained by vacuum drying this solution at room temperature for 2 hours. When this composition was observed with a polarizing microscope on a hot plate, light loss due to scattering was observed in almost the entire observation area.

-Measurement of Thermal Conductivity of Cured Product Prepared from Composition 11 0.0139 g (0.2050 mmol) of imidazole was added to the above composition 11, and this mixture was placed in a φ2.4 cm aluminum container at 150 ° C. It was held on a hot plate heated to a temperature for 120 minutes, and a circular piece having a thickness of 1.3 mm was taken out. The thermal conductivity of this cured product (cured product 11) was 0.85 W / m · K and 0.38 W / m · K, respectively, in the in-plane direction and the thickness direction of the sample.

[Example 12] to [Example 14]
By the same method as in Example 11 above, the characteristics of the compositions shown in Table 2 below or the cured product prepared from the compositions were confirmed. 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. Further, Example 11 is reprinted.

Table 2 Liquid crystallinity and thermal conductivity of the composition 2

[Example 15] Preparation of sample containing filler Weigh 0.10 g of the composition obtained in Example 5 and 0.90 g of boron nitride particles (PolarTerm PTX-25 manufactured by Momentive Performance Materials Japan (Joint)). Mix well, sandwich it in a stainless steel plate, apply a pressure of 20 MPa with a compression molding machine (IMC-19EC manufactured by Imoto Seisakusho Co., Ltd.) heated to a temperature of 150 ° C, and hold it for 45 minutes as a heat dissipation member. A square piece having a thickness of 768 μm was taken out. The thermal conductivity of this sample (sample 5 containing filler) was 9.2 W / m · K.

[Example 16] to [Example 24]
Samples 6 to 10 containing a filler were prepared and the thermal conductivity was measured in the same manner as in Example 15 above, except that the compositions 6 to 10 were used instead of the composition 5. The results are shown in Table 3. In addition, Example 15 is reprinted.

［実施例２５］ フィラー入りサンプルの作製２
実施例１１で得た組成物１１ ０．１０ｇおよび酸化アルミニウム粒子（デンカ製ＤＡＷ−１０）０．９０ｇをそれぞれ量りとってよく混ぜ、上記実施例１５と同様な方法で、フィラー入りサンプル（フィラー入りサンプル１１_ＡＯ）を得た。このサンプルの熱伝導率は、７．２Ｗ／ｍ・Ｋであった。 Table 3. Thermal conductivity of sample with filler

[Example 25] Preparation of sample containing filler 2
0.10 g of the composition 11 obtained in Example 11 and 0.90 g of aluminum oxide particles (DAW-10 manufactured by Denka) are weighed and mixed well, and a sample containing a filler (containing a filler) is mixed in the same manner as in Example 15 above. Sample 11 _AO ) was obtained. The thermal conductivity of this sample was 7.2 W / m · K.

[Example 26] to [Example 28]
Samples 12 to 14 containing a filler were prepared and the thermal conductivity was measured in the same manner as in Example 25 above, except that the compositions 12 to 14 were used instead of the composition 11. The results are shown in Table 4. In addition, Example 25 is reprinted.

Table 4. Thermal conductivity of sample with filler 2

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 oxylanyl resins such as adhesives.

Claims (12)

A compound represented by the formula (1).

In formula (1), R ^ce is independently a group having 4 to 12 carbon atoms containing oxylanyl or oxetanyl, and R ¹ is independently being hydrogen, an alkyl having 1 to 8 carbon atoms, or −OR ^ce . be. A composition containing a compound represented by the formula (1) and a curing agent. The composition according to claim 2, further comprising a curing accelerator. Claim 2 that 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. Or the composition according to 3. The composition according to claim 4, wherein the curing agent is at least one compound represented by the formula (2-1) or (2-2).
E ¹ -Z- (L-Z) n-E ¹ (2-1)
L ¹ -Z-E (2-2)
In equations (2-1) and (2-2),
Z is independently a single bond, -O-, -NH-, -S-, -SO _2- , -CO _2- , or an alkylene with 1-12 carbon atoms.
In equation (2-1),
L is independently a single bond, cyclohexylene, phenylene, or naphthalene, and at least one hydrogen in these rings may be replaced with an alkyl having 1 to 10 carbon atoms.
E ¹ is independently an amino, an alkylamino having 1 to 10 carbon atoms, a hydroxyl group, or a carboxy, and at least one E is an amino or an alkylamino having 1 to 10 carbon atoms.
n is an integer from 0 to 7.
In equation (2-2),
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.
E is an amino or an alkylamino having 1 to 10 carbon atoms. The composition according to claim 2 or 3, 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 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. * Represents the bond position. ) The sixth 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),
n31 is an integer greater than or equal to 2 and less than or equal to 4.
Ring B is benzene, naphthalene, anthracene, fluorene, or 9,9-diphenylfluorene, in which at least one hydrogen is an alkyl having 1-3 carbon atoms or an alkoxy having 1-3 carbon atoms. May be replaced;
In equation (3-2),
n32 and n33 are independently integers 1-3;
Z ³⁰ is a single bond, alkylene with 1 to 10 carbon atoms, -CH (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -O-, -S-, or. Represents −SO ₂ −
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.
In equation (3-4),
R ¹⁰ and R ¹¹ independently represent 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),
n34 is an integer of 1 or more and 5000 or less,
Z ³¹ independently represents a single bond, −CH (CH ₃ ) −, −C (CH ₃ ) ₂ −, and n34 represents an integer from 1 to 5000 or less.
In equation (3-7),
n34 is an integer between 1 and 5000, ^{inclusive, R 12} is independently hydrogen or methyl.
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 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, the propyl, butyl, pentyl, or hexyl group may be a branched chain, and * represents a bond position. The composition according to claim 2 or 3, wherein the curing agent is a compound containing a cyanate ester. The composition according to claim 2 or 3, 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 2 to 9, further comprising an inorganic filler. The composition according to claim 10, 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 2 to 11.