Polymerizable compounds, compositions for electronic components, materials for electronic components

Abstract

To provide a liquid crystalline epoxy compound having liquid crystallinity and low melting point and to provide an epoxy resin material having a high thermal conductivity using the epoxy compound.SOLUTION: There is provided a liquid crystalline epoxy compound having two or more oxiranyls and two to five aromatic rings in which the oxiranyl groups are bonded to the aromatic rings and at least one of oxiranyl groups are bonded to an aromatic ring via a carbon atom, which is used as an epoxy resin material having a high thermal conductivity.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a composition for a heat dissipation member that efficiently conducts heat generated inside an electronic device, and a polymerizable compound having liquid crystallinity used therefor.

Background Art

[0002] In recent years, in semiconductor elements for power control such as hybrid vehicles and electric vehicles, and CPUs for high-speed computers, etc., it has been desired to increase the thermal conductivity of package materials so that the temperature of the internal semiconductor does not become too high. That is, the ability to efficiently release the heat generated from the semiconductor chip to the outside has become important.

[0003] As a method for solving such heat dissipation problems, there is a method of bringing a high thermal conductivity material (heat dissipation member) into contact with the heat generating part to conduct heat to the outside and dissipate heat. Examples of materials with high thermal conductivity include inorganic materials such as metals and metal oxides. However, such inorganic materials have problems in processability and insulation, etc., and it is very difficult to use them alone as a filler for semiconductor packages. Therefore, development of heat dissipation members in which these inorganic materials and resins are compounded to increase thermal conductivity has been carried out.

[0004] Generally, the increase in thermal conductivity of composite materials has been achieved by adding a large amount of inorganic fillers such as metal fillers to general-purpose resins such as polyethylene resin, polyamide resin, polystyrene resin, acrylic resin, and epoxy resin. However, the thermal conductivity of inorganic fillers is a value inherent to the substance and has an upper limit. Therefore, attempts have been widely made to improve the thermal conductivity of the composite material by improving the thermal conductivity of the resin. As a means to actually do this, for example, a method using an epoxy compound having liquid crystallinity is known.

[0005] Patent Document 1 discloses a terphenyl compound having two glycidyloxy groups. Patent Document 2 discloses a terphenyl compound having three glycidyloxy groups. However, the compounds disclosed in these patent documents have no liquid crystal temperature and have a high melting point of 117°C or higher.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] The problems of the present invention are to provide a liquid crystalline epoxy compound having liquid crystallinity and a low melting point, and an epoxy resin material having high thermal conductivity using the epoxy compound. Another problem of the present invention is to provide a liquid crystalline epoxy compound having high solubility in a solvent.

Means for Solving the Problems

[0008] The present inventors have found that, in a liquid crystalline epoxy compound having two or more oxiranyl groups and two to five aromatic rings, the group having the oxiranyl group is bonded to the aromatic ring, and at least one oxiranyl group is bonded to the aromatic ring through a methylene group, and the compound solves the above problems, and thus completed the present invention.

Effects of the Invention

[0009] A composition using the above compound as a raw material is likely to exhibit liquid crystallinity when the composition 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 this as a raw material is easily made into a paste. Therefore, it can be suitably used as a heat dissipation material for power semiconductors and the like. [Modes for carrying out the invention]

[0010] The embodiments of the present invention will be described in detail below. Furthermore, the present invention is not limited to these embodiments.

[0011] The present invention includes the following items, among others.

[0012] [1] A liquid crystalline epoxy compound having two or more oxiranils and two to five aromatic rings, wherein the oxiranil-containing group is bonded to the aromatic ring, and at least one oxiranil is bonded to the aromatic ring via carbon.

[0013] [2] The compound described in item [1], wherein the liquid crystalline epoxy compound is a rod-shaped molecule.

[0014] [3] The compound described in item [2], represented by formula (1). TIFF0007852759000001.tif32132In formula (1), R ep Independently, is a group having 2 to 12 carbon atoms with an oxyranyl group, where at least one oxyranyl is bonded to the aromatic ring via a carbon atom, and X is independently a single bond, -CH2CH2-, -CH2O-, -CH=CH-, -C≡C-, or -COO-, and R 1 These are independently hydrogen, C1-C8 alkyl groups, C1-C8 alkoxy groups, or R ep The alkyl and alkoxy groups are such that at least one -CH2- can be replaced with -C(=O)-, and n is between 0 and 2.

[0015] [4] The crystalline epoxy compound represented by formula (1), wherein X is a single bond or -C≡C-, as described in item [3].

[0016] [5] A composition comprising the compound and curing agent described in any one of items [1] to [4].

[0017] [6] The composition according to item [5], further comprising a curing accelerator.

[0018] [7] The composition according to item [5] or [6], wherein the curing agent is an aromatic primary amine, an aliphatic primary amine, an aromatic having two or more secondary aminos in its molecular skeleton, or an aliphatic amine having two or more secondary aminos in its molecular skeleton.

[0019] [8] The composition according to item [7], wherein the curing agent is at least one compound represented by formula (2-1) or (2-2). EZ-(LZ)nE (2-1) L 1 -ZE (2-2) In equations (2-1) and (2-2), L is independently a single bond, cyclohexylene, phenylene, or naphthalene, and at least one hydrogen of these rings may be replaced by an alkyl group having 1 to 10 carbon atoms. L 1 is hydrogen, cyclohexyl, phenyl, or naphthyl, and at least one hydrogen of these rings may be replaced by an alkyl group having 1 to 10 carbon atoms. Z is independently a single bond, -O-, -NH-, -S-, -SO2-, -CO2-, or an alkylene with 1 to 12 carbon atoms. E is independently an amino, a C1-C10 alkylamino, a hydroxyl group, or a carboxyl group, and at least one of E is an amino or a C1-C10 alkylamino. n is an integer between 0 and 7.

[0020] [9] The composition according to item [5] or [6], wherein the curing agent is a phenol having two or more -OH groups in its molecular skeleton, or a compound in which at least one of the -OH groups in the phenol is a short-chain ester. (A short-chain ester is a structure in which the group represented by (3-E) below is substituted for the H of the OH group.) TIFF0007852759000002.tif1447 R in the formula 13represents a methyl, ethyl, propyl, butyl, pentyl, or hexyl group, and the propyl, butyl, pentyl, or hexyl group may be a branched chain.)

[0021]

[10] The composition according to item [9], wherein the curing agent is at least one compound represented by formulas (3-1) to (3-7), or a short-chain ester thereof. TIFF0007852759000003.tif42115 TIFF0007852759000004.tif56148 TIFF0007852759000005.tif10297 TIFF0007852759000006.tif3552 In formula (3-1), ring B is benzene, naphthalene, anthracene, fluorene, or 9,9-diphenylfluorene, and in these ring Bs, at least one hydrogen may be replaced by an alkyl having 1 to 3 carbon atoms or an alkoxy having 1 to 3 carbon atoms; n31 is an integer of 2 or more and 4 or less. In formula (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(CH3)-, -C(CH3)2-, -C(CF3)2-, -O-, -S-, or -SO2-, at least one hydrogen on the benzene ring may be replaced by an alkyl having 1 to 3 carbon atoms or an alkenyl having 2 to 3 carbon atoms; In formulas (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, they may be different for each repetition, R 10 and R 11 are independently 1,4-phenylene, 4,4'-biphenylene, or cyclopentadienylene, In formula (3-5), n34 is an integer of 1 or more and 5000 or less, In formula (3-6), Z 31 The elements are independently single-joint, -CH(CH3)-, or -C(CH3)2-, and n34 is an integer between 1 and 5000. In formula (3-7), n34 is an integer between 1 and 5000, and R 12 It is hydrogen or methyl. A short-chain ester is a structure in which the group represented by (3-E) below is substituted for the H of the OH group. TIFF0007852759000007.tif1447 R in the formula 13 represents a methyl, ethyl, propyl, butyl, pentyl, or hexyl group, and the propyl, butyl, pentyl, or hexyl group may be a branched chain. Furthermore, at least one hydrogen atom on the aromatic ring in formulas (3-3) through (3-7) may be replaced with a methyl atom.

[0022]

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

[0023]

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

[0024]

[13] The composition according to any one of the items [5] to

[12] , further comprising an inorganic filler.

[0025]

[14] The composition according to item

[13] , wherein the inorganic filler is aluminum oxide or boron nitride.

[0026]

[15] A material for electronic components obtained by curing any one of the compositions described in sub-sub

[0027]

[16] A compound represented by formula (1'). TIFF0007852759000008.tif2198 In formula (1'), Rep’ R is independently a carbon-4 to carbon-12 group having oxyranil, 1 These are independently hydrogen or methyl.

[0028] The phrase "at least one hydrogen of the ring may be replaced by an alkyl group having 1 to 10 carbon atoms" refers to a configuration in which, for example, at least one of the hydrogens at positions 2, 3, 5, or 6 of 1,4-phenylene is replaced by a substituent such as fluorine or methyl. "Compound (1)" means the compound represented by formula (1), and may also mean at least one compound represented by formula (1).

[0029] [Liquid crystal epoxy compounds] As described above, the problem of this invention can be solved by using a liquid crystalline epoxy compound having two or more oxiranils and two to five aromatic rings, wherein the group having the oxiranil is bonded to the aromatic ring, and at least one oxiranil is bonded to the aromatic ring via carbon. In this case, "via carbon" refers to a methylene group in which the atom directly connected to the aromatic ring may be substituted, or a carbon atom constituting the oxiranil.

[0030] The liquid crystalline epoxy compound is preferably in the form of a rod, as this reduces crystallinity and makes it easier to form into a paste. For such rod-shaped liquid crystalline compounds, it is preferable that the liquid crystal core has 3 to 5 aromatic rings in order to expand the liquid crystal temperature range.

[0031] The core of the liquid crystal described above refers to a structure in which aromatic rings and alicyclic rings are linked by relatively conformally defined bonding groups. Examples of such bonding groups include single bonds, ethylene, oxymethylene, double bonds, triple bonds, or esters.

[0032] The rod-shaped liquid crystalline compound described above has a structure in which aromatic rings or alicyclic rings are arranged linearly as the liquid crystal core, with flexible substituents such as alkyl groups bonded to both ends of the core. In this case, the linear structure does not need to be strictly straight and may be bent at an angle of about 45 degrees.

[0033] In such rod-shaped liquid crystalline compounds, it is preferable that the molecular structure does not contain esters in order to prevent decomposition at temperatures above 200°C.

[0034] As for the rod-shaped liquid crystal compound mentioned above, it is more preferable to select the compound represented by formula (1) because it exhibits a wide temperature range in which it is liquid crystal, is easy to manufacture, and has high heat resistance when cured.

[0035] TIFF0007852759000009.tif32132 In formula (1), R ep Independently, are groups with 2 to 12 carbon atoms containing oxyranyl, and each independently is a single bond, -CH2CH2-, -CH2O-, -CH=CH-, -C≡C-, or -COO-, and R 1 These are independently hydrogen, C1-C8 alkyl groups, C1-C8 alkoxy groups, or R ep The alkyl and alkoxy groups are such that at least one -CH2- can be replaced with -C(=O)-, and n is between 0 and 2.

[0036] In the compound of formula (1), R ep These are, independently, groups containing oxyranyl with 2 to 12 carbon atoms. In this case, R ep The structure other than oxyranil is not particularly limited, but in order to give high heat resistance when cured, it is preferable that the group contains oxyranil with 2 to 10 carbon atoms, and is particularly preferable that it contains oxyranil with 2 to 8 carbon atoms. Furthermore, the -CH2- of these oxyranil-containing groups may be substituted with -O-. Compounds with a structure in which -O- is directly bonded to the aromatic ring are particularly easy to synthesize. However, in order to suppress the crystallinity of the compound and improve its liquid crystalline properties, at least one R ep It needs to be bonded to the aromatic ring via carbon. On the other hand, both R ep When bonded to the aromatic ring via carbon, the liquid crystalline properties tend to decrease. Therefore, at least one R epIt is preferable that the atom is bonded to the aromatic ring via an O-cell.

[0037] In the compound of formula (1), the linking group X is independently a single bond, -CH2CH2-, -CH2O-, -CH=CH-, -C≡C-, or -COO-. The direction of the bond in these linking groups is arbitrary. In this case, in order to improve the heat resistance of the cured product, it is preferable to select a single bond, -CH2CH2-, -CH2O-, or -C≡C- as X, and in order to give the compound a wide liquid crystal temperature range, it is particularly preferable to select a single bond or -C≡C-. Furthermore, in terms of ease of synthesis, it is most preferable to select a single bond.

[0038] In the compound of formula (1), R 1 Each of these is independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or R ep Furthermore, one of these alkyl and alkoxy groups -CH2- may be substituted with -CO-. In this case, the liquid crystal temperature range of the compound can be expanded, thus these R 1 It is preferable to select alkyl or alkoxy as R, and it is particularly preferable to select alkyl. ep If X is not the same group, hydrogen is also preferable for similar reasons. To expand the liquid crystal temperature range of the compound, R 1 It is most preferable to select methyl as the compound. Furthermore, in order to improve the heat resistance of the cured product, R 1 as R ep It is preferable to select this option.

[0039] In the compound of formula (1), n ​​is between 0 and 2. In this case, n is preferably 1 or 2, as this expands the liquid crystal temperature range of the compound.

[0040] A suitable example of a liquid crystalline epoxy compound represented by formula (1) is formula (1-1) Equations (1-3), (1-8) to (1-24), (1-27), (1-30) to (1-37), and (1-39) ~Formula(1-4 7 Examples of compounds include those listed above.

[0041] TIFF0007852759000010.tif236127 TIFF0007852759000011.tif223128 TIFF0007852759000012.tif217128 TIFF0007852759000013.tif252141 TIFF0007852759000014.tif254142

[0042] In equations (1-1) to (1-48), R ep1 and R ep2 Aside from oxyranyl, each of these independently represents a group with 2 to 12 carbon atoms, consisting of a single carbon-carbon bond and a hydrogen atom bonded to a carbon atom.

[0043] In order to solve the problems of the present invention, it is most preferable to select one of the compounds represented by formulas (1-1) to (1-48) from formulas (1-11) to (1-18) and formulas (1-20) to (1-23) among the compounds represented by formulas (1-1) to (1-48) above. These compounds have a wide liquid crystal temperature range, and it is in a temperature range suitable for curing.

[0044] The compounds represented by formula (1') of the present invention have high solubility in solvents. Therefore, when compositions containing these compounds are used for printing, crystal formation can be suppressed, resulting in excellent printability.

[0045] TIFF0007852759000015.tif23108 In formula (1'), R ep’ R is independently a carbon-4 to carbon-12 group having oxyranil, 1 These are independently hydrogen or methyl.

[0046] In equation (1'), R ep’ R is independently a group having 4 to 12 carbon atoms that contains oxyranyl. Since oxyranyl consists of 2 C and 1 O, ep’It has 2 to 10 hydrocarbons in addition to oxiranil. In this case, to increase solubility in the solvent, it is preferable to have 3 to 10 hydrocarbons in addition to oxiranil. For a similar purpose, R ep’ It is preferable that the compound has branched chains. On the other hand, if the number of hydrocarbon groups and branched chains increases, the liquid crystalline properties decrease, and the heat resistance of the cured product decreases. To prevent this, it is preferable to have 3 to 5 hydrocarbons in addition to oxyranil.

[0047] Two R's ep’ The compounds described in formula (1'), including those in which both R groups are bonded to the aromatic ring via an -O- group, are highly soluble in solvents. However, at least one R group ep’ Compounds in which the aromatic ring is bonded via carbon atoms are preferable because they exhibit higher solubility and liquid crystalline properties.

[0048] In equation (1'), R 1 R is independently hydrogen or methyl. In this case, in order to improve liquid crystalline properties, 1 It is preferable to either not select CH3 or select one CH3, and to select one CH3 in order to improve solubility in the solvent.

[0049] A preferred example of a compound represented by formula (1') is a compound represented by formulas (1-1) to (1-48) above, where R ep1 and R ep2 Examples include compounds in which the group has oxyranil and consists of 4 to 12 carbon atoms. Among these compounds, in order to further solve the problems of the present invention, it is most preferable to select one of the compounds represented by formulas (1-11) to (1-18) and formulas (1-20) to (1-23). ​​These compounds have a wide liquid crystal temperature range, and that temperature range is suitable for curing.

[0050] Another preferred example of the compound represented by formula (1') is the compound represented by formulas (1'-1) through (1'-24) below.

[0051] TIFF0007852759000016.tif191134

[0052] TIFF0007852759000017.tif191137

[0053] TIFF0007852759000018.tif191137

[0054] These compounds have high solubility in solvents and can be manufactured inexpensively. Among these compounds, those represented by formulas (1'-1) to (1'-16) are more preferable due to their wide liquid crystal temperature range.

[0055] The composition of the present invention is characterized by comprising 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 crystalline properties. Furthermore, by curing while maintaining this state, the entanglement of molecular skeletons in the cured product is relaxed. As a result, a material that efficiently conducts heat is provided.

[0056] The composition of the present invention is characterized by containing a compound represented by formula (1) above. One or more compounds of formula (1) may be used. In addition, other known epoxy compounds may be used in combination, as long as they do not cause the composition to lose its liquid crystalline properties. As such compounds, liquid crystalline epoxy compounds represented by formulas (o-1) to (o-6) can be preferably used.

[0057] TIFF0007852759000019.tif115115

[0058] In addition, non-crystalline epoxy compounds represented by formulas (o-7) to (o-21) are also preferably used as other epoxy compounds.

[0059] TIFF0007852759000020.tif170107

[0060] In equation (o-12), Z 10-CH2-, -O-, -S-, -CH(CH3)-, -C(CH3)2-, -SO2-, or -C(CF3)2-.

[0061] TIFF0007852759000021.tif203109

[0062] In equations (o-13) and (o-14), Z 11 represents CH or CCH3.

[0063] TIFF0007852759000022.tif135100

[0064] In addition, resins having structures represented by formulas (o-23) to (o-27) are also preferably used as other epoxy compounds.

[0065] TIFF0007852759000023.tif80167

[0066] In formula (o-23), Z 12 and Z 13 The bonds are independently single bonds, -CH2-, -O-, -S-, -CH(CH3)-, -C(CH3)2-, -SO2-, or -C(CF3)2-, and n21 is an integer between 1 and 5000. In equations (o-24) and (o-25), n21 is an integer between 1 and 5000, n22 and n23 are independently 0 or 1, and if n21 is 2 or greater, they may be different in each iteration. R 10 and R 11 These are independently 1,4-phenylene, 4,4'-biphenylene, or cyclopentadienylene. Furthermore, the hydrogen atoms on the aromatic rings in formulas (o-24) through (o-25) may be replaced with methyl atoms.

[0067] TIFF0007852759000024.tif104109

[0068] In equations (o-26) and (o-27), Z 14 The elements are independently single-bonded, -CH(CH3)-, or -C(CH3)2-, and n21 represents an integer between 1 and 5000. Furthermore, the hydrogen atoms on the aromatic rings in formulas (o-26) and (o-27) may be substituted with methyl atoms.

[0069] The content of such known epoxy compounds in the compound of formula (1) is not particularly limited, as long as the composition or its cured product exhibits the desired properties. That is, it can be used in amounts between 0.1% and 99.9% by weight relative to the total weight of the epoxy compound. In this case, to exhibit the effects of the present invention, it is preferable to use an amount between 0.1% and 90% by weight, and more preferably between 0.1% and 80% by weight.

[0070] [Hardening agent] As curing agents that can be used in combination with the compositions of the present invention, all known compounds such as amines, phenols, cyanate esters, carboxylic acids, carboxylic acid esters, acid anhydrides, or thiols can be used.

[0071] As an amine-based curing agent, it is preferable that it be at least one compound represented by the following formula (2-1) or (2-2) because it does not significantly impair the liquid crystalline properties of the composition and is readily available. EZ-(LZ)nE (2-1) L 1 -ZE (2-2) In equations (2-1) and (2-2), L is independently a single bond, cyclohexylene, phenylene, or naphthalene, and at least one hydrogen of these rings may be replaced by an alkyl group having 1 to 10 carbon atoms. L 1 is hydrogen, cyclohexyl, phenyl, or naphthyl, and at least one hydrogen of these rings may be replaced by an alkyl group having 1 to 10 carbon atoms. Z is independently a single bond, -O-, -NH-, -S-, -SO2-, -CO2-, or an alkylene with 1 to 12 carbon atoms. E is independently an amino, a C1-C10 alkylamino, a hydroxyl group, or a carboxyl group, and at least one of E is an amino or a C1-C10 alkylamino. n is an integer between 0 and 7.

[0072] Compounds represented by formula (2-1) include aliphatic polyhydric amines with 2 to 12 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, p-xylenediamine, and m-xylenediamine, as well as p-phenylenediamine, N-methyl-p-phenylenediamine, N-ethyl-p-phenylenediamine, N-propyl-p-phenylenediamine, N-butyl-p-phenylenediamine, 2,5-diaminotoluene, m-phenylenediamine, N-methyl-m-phenylenediamine, N-ethyl-m-phenylenediamine, N-propyl-m-phenylenediamine, and N-butyl-m-phenylenediamine. Examples include aromatic polyhydric amines such as diamine, 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'-diaminodiphenylsulfone, bis(4-aminophenyl)phenylmethane, m-tolidine, o-tolidine, and other aromatic polyhydric amines, as well as alicyclic polyhydric amines such as 1,4-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,2-cyclohexyldiamine, and 1,3-bis(aminomethyl)cyclohexane.

[0073] Among these, p-phenylenediamine, N-methyl-p-phenylenediamine, N-ethyl-p-phenylenediamine, N-propyl-p-phenylenediamine, N-butyl-p-phenylenediamine, 2,5-diaminotoluene, m-phenylenediamine, N-methyl-m-phenylenediamine, N-ethyl-m-phenylenediamine, N-propyl-m-phenylenediamine, N-butyl-m-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfone are particularly preferred due to their good compatibility when incorporated into a composition and excellent storage stability.

[0074] Compounds represented by formula (2-2) include aliphatic amines with 2 to 12 carbon atoms such as n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, and n-dodecylamine; aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,6-dimethylaniline, 2,4,6-trimethylaniline, 2-ethylaniline, 1-naphthylamine, and 1-amino-2-methylnaphthalene; and alicyclic amines such as cyclohexylamine and 2-methylcyclohexylamine. Among these, aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,6-dimethylaniline, 2,4,6-trimethylaniline, and 2-ethylaniline are particularly preferred due to their good compatibility when incorporated into a composition and excellent storage stability.

[0075] As a phenolic curing agent, it is preferable that it be at least one phenol compound represented by the following formulas (3-1) to (3-7), or a short-chain ester thereof, because it does not significantly impair the liquid crystalline properties of the composition and is readily available.

[0076] TIFF0007852759000025.tif42115 TIFF0007852759000026.tif56148 TIFF0007852759000027.tif10297 TIFF0007852759000028.tif3552

[0077] In formula (3-1), Ring B is benzene, naphthalene, anthracene, fluorene, or 9,9-diphenylfluorene, where at least one hydrogen in ring B may be replaced by a C1-C3 alkyl or C1-C3 alkoxy; n31 is an integer between 2 and 4 (inclusive).

[0078] In equation (3-2), n32 and n33 are independent integers between 1 and 3; Z 30 These are single bonds, alkylenes with 1 to 10 carbon atoms, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -O-, -S-, or -SO2-. At least one hydrogen atom on the benzene ring may be replaced by an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms;

[0079] In equations (3-3) and (3-4), n34 is an integer between 1 and 5000, n35 and n36 are independently 0 or 1, and if n34 is 2 or greater, they may be different in each iteration. R 10 and R 11 These are independently 1,4-phenylene, 4,4'-biphenylene, or cyclopentadienylene. In formula (3-5), n34 is an integer between 1 and 5000, In formula (3-6), Z 31 The elements are independently single-joint, -CH(CH3)-, or -C(CH3)2-, and n34 is an integer between 1 and 5000. In formula (3-7), n34 is an integer between 1 and 5000, and R 12 It is hydrogen or methyl. Furthermore, at least one hydrogen atom on the aromatic ring in formulas (3-3) through (3-7) may be replaced with a methyl atom.

[0080] The short-chain esters of phenol compounds represented by the above formulas (3-1) to (3-7) are structures in which the group represented by (3-E) below is substituted for the H of the OH group.

[0081] TIFF0007852759000029.tif1447 R in the formula 13 R represents a methyl, ethyl, propyl, butyl, pentyl, or hexyl group, and the propyl, butyl, pentyl, or hexyl group may be a branched chain. 13 If methyl is selected, the crystallinity of the compound increases, which may impair the liquid crystalline properties of the composition. In such cases, it is preferable to select (3-E) which has a longer-chain alkyl group. On the other hand, if a long-chain alkyl group is used, the heat resistance of the cured product may decrease. In such cases, it is preferable to select (3-E) which has a shorter-chain alkyl group.

[0082] Preferred carboxy-containing curing agents include phthalic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and benzophenone-4,4'-dicarboxylic acid.

[0083] The curing agents that can be used in the compositions of the present invention are not limited to the known compounds such as amines, phenols, cyanate esters, carboxylic acids, carboxylic acid esters, acid anhydrides, or thiols mentioned above. For example, to cure the composition at a higher temperature in order to create a semi-cured sheet, it is also preferable to add dicyandiamide or the like.

[0084] In the composition of the present invention, there are no particular restrictions on the ratio of the compound of formula (1) to the curing agent. In order to improve heat resistance and to efficiently advance the reaction, it is preferable to have the reactive groups of the compound of formula (1) and the curing agent be equivalent in weight. For example, in the case of epoxy:amine, the ratio is 2:1, and in the case of epoxy:phenol, it is 1:1.

[0085] The above-mentioned hardening agent may be used in the form of one type or multiple types.

[0086] [Curing accelerator] In the compositions of the present invention, particularly when using phenolic curing agents, it is preferable to add curing accelerators to the composition to efficiently advance the reaction in order to improve heat resistance. Examples of such curing accelerators include imidazole-based curing accelerators such as 2-ethyl-4-methyl-1H-imidazole, 2-phenyl-4-methyl-1H-imidazole, 1,2-dimethylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphorus-based curing accelerators such as triphenylphosphine; and amine-based curing accelerators such as 2,4,6-tris(dimethylaminomethyl)phenol, triethylenediamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, and 1,8-diazabicyclo[5.4.0]undeca-7-ene. Among such curing accelerators, it is preferable to use imidazole-based curing accelerators because they have a curing temperature of 200°C or lower and exhibit high curing properties.

[0087] In the composition of the present invention, the concentration of the curing accelerator is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more, relative to the weight of the polymerizable compound of the present invention, in order to improve heat resistance and efficiently advance the reaction. Furthermore, in order to avoid deterioration of reliability due to sublimation of the curing accelerator, etc., the concentration is preferably 5% by weight or less, and more preferably 3% by weight or less, relative to the weight of the polymerizable compound of the present invention.

[0088] [Inorganic filler] The electronic component composition of the present invention may contain an inorganic filler. Inorganic fillers contained in electronic component compositions include nitrides such as aluminum nitride, boron nitride, and silicon nitride, which are highly thermally conductive fillers. Other inorganic or metallic fillers may include diamond, graphite, silicon carbide, silicon, beryllia, magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, copper oxide, titanium oxide, cerium oxide, yttrium oxide, tin oxide, holmium oxide, bismuth oxide, cobalt oxide, calcium oxide, aluminum nitride, boron nitride, silicon nitride, magnesium hydroxide, aluminum hydroxide, gold, silver, copper, platinum, iron, tin, lead, nickel, aluminum, magnesium, tungsten, molybdenum, and stainless steel. Preferably, boron nitride, aluminum nitride, and aluminum oxide are used. Boron nitride and aluminum nitride are preferred because they have very high thermal conductivity in the planar direction, low dielectric constant, and high insulating properties. Hexagonal boron nitride (h-BN) and aluminum nitride are particularly preferred.

[0089] Examples of inorganic filler shapes include spherical, amorphous, fibrous, rod-shaped, cylindrical, plate-shaped, and tetrapod-shaped. The type, shape, size, and amount of inorganic filler can be appropriately selected according to the purpose. For example, if a cured product (electronic component material) formed from an electronic component composition requires insulation, a conductive inorganic filler may be used as long as the desired insulation is maintained.

[0090] The average particle size of the inorganic filler is preferably, for example, 0.1 to 200 μm. More preferably, it is 1 to 100 μm. A particle size of 0.1 μm or more provides good thermal conductivity, while a particle size of 200 μm or less allows for increased packing density. In this specification, the average particle size is based on particle size distribution measurement by laser diffraction and scattering. Specifically, using analysis based on Fraunhofer diffraction theory and Mie scattering theory, the median diameter is defined as the diameter at which the larger and smaller sides are equal in volume (by volume) when the powder is divided into two parts from a certain particle size using a wet method.

[0091] The amount of inorganic filler added is preferably 20 to 95% by weight, for example, when used in a heat dissipation member. More preferably, it is 50 to 95% by weight. An amount of 20% by weight or more is preferable because it increases the thermal conductivity. An amount of 95% by weight or less is preferable because it prevents the heat dissipation member from becoming brittle.

[0092] Inorganic fillers may be used in their unmodified state, or their surface may be treated with a coupling agent. For example, boron nitride (h-BN) may be treated with a silane coupling agent. In the case of boron nitride, since there are no reactive groups on the plane of the particles, the silane coupling agent will bond only around them. Boron nitride treated with a coupling agent can form bonds with polymerizable compounds in the electronic component composition, and these bonds are thought to contribute to heat conduction. Therefore, the coupling agent is preferably one that reacts with groups of oxyranil, oxetanil, or a curing agent. For example, amine-based agents, or those containing oxyranil or oxetanil, are preferred. Specifically, examples from JNC Corporation include Sylace S310, S320, S330, S360, S510, and S530.

[0093] Inorganic fillers may be those that have been treated with a coupling agent and then surface-modified with a 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 the boron nitride surface-modified with the polymerizable compound can form bonds with the polymerizable compound and curing agent in the electronic component composition, these bonds are thought to contribute to heat conduction. For example, the polymerizable compound may be the polymerizable compound of the present invention shown in formula (1), or it may be any other polymerizable compound.

[0094] [Other components] The compositions of the present invention are not limited to any other components that may be included. Examples include polymerizable compounds having polymerizable groups other than epoxy, non-polymerizable compounds, polymerization initiators, and solvents.

[0095] As for polymerizable compounds having polymerizable groups other than epoxy, there are no particular restrictions as long as they do not degrade the properties of the electronic material of the present invention, and known polymerizable compounds can be used. Among these, radical polymerizing compounds such as acrylic compounds and styrene-based compounds can be preferably used, and these compounds that have liquid crystalline properties can be used more preferably. Examples of polymerization initiators include thermal polymerization initiators, photocationic polymerization initiators, and photoanionic polymerization initiators. Examples of thermal cationic polymerization initiators include sulfonium salts, boron trifluoride-amine complexes, dicyanazides, organic acid hydrazides, and toluenesulfonic acid esters. Known photocationic initiators include sulfonium salts, iodonium salts, and nonionic types. Known photoanionic initiators include oxime types, carbamate types, guanidium carboxylate types, and nifedipine types.

[0096] If the composition of the present invention contains compounds that undergo radical polymerization, such as acrylic compounds or styrene compounds, a radical polymerization initiator may be used.

[0097] The compositions 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, and diethylene glycol diethyl ether. Examples include methyl ether, dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, diethyl carbonate, ethyl methyl carbonate, γ-butyrolactone, methyl lactate, ethyl lactate, butyl lactate, 2-ethylhexanol, 1-propanol, isobutyl alcohol, n-butanol, 2-pentanone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, and ethylene glycol. The solvent may be used alone or in mixtures of two or more.

[0098] Since the compositions of the present invention have high polymerizability, stabilizers may be added to facilitate handling. Known stabilizers can be used without limitation. Examples include hydroquinone, 4-ethoxyphenol, and 3,5-di-t-butyl-4-hydroxytoluene (BHT).

[0099] Furthermore, additives (such as oxides) may be added to adjust the viscosity and color of the electronic component composition. For example, titanium dioxide can be used to make it white, carbon black to make it black, and fine silica powder can be used to adjust the viscosity. In addition, to further increase the mechanical strength, inorganic fibers such as glass and carbon fiber, or cloths thereof, or synthetic fibers such as polyvinyl formal, polyvinyl butyral, polyester, polyamide, and polyimide, or supramolecules may be added.

[0100] It is known that the thermal conductivity of a material can be further improved by controlling the orientation of the liquid crystals. For this purpose, it is also preferable to add a so-called orientation control agent to the composition of the present invention to control the orientation of the liquid crystals. An example of a vertical orientation agent that orients a liquid crystalline composition perpendicular to the substrate plane is a compound having a hydrocarbon structure with 10 to 50 carbon atoms and having a hydroxyl group, amino group, or carboxyl group at one end of the structure.

[0101] [Materials for electronic components] The electronic component material of the present invention is obtained by curing the electronic component composition according to the second embodiment described above and then molding the cured product according to the application. For example, the electronic component material can be used as a heat dissipation member.

[0102] The material for electronic components is a polymer obtained by polymerizing (curing) the composition of the present invention. This polymer has high thermal conductivity and excellent chemical stability, heat resistance, hardness, and mechanical strength. The mechanical strength refers to Young's modulus, tensile strength, tear strength, flexural strength, flexural modulus, impact strength, etc.

[0103] The composition of the present invention is a thermosetting resin. Thermosetting resins harden by heating the raw material composition, which polymerizes the monomers contained in the composition and further causes three-dimensional crosslinking. Preferably, the heating temperature is within the temperature range in which the composition of the present invention exhibits a liquid crystal phase. In addition, as the hardening of the composition of the present invention progresses to a certain extent, the liquid crystal temperature range may rise. In such cases, hardening may be carried out within the elevated liquid crystal temperature range.

[0104] The curing temperature may be constant, or it 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 properties of the material. Furthermore, heating at a temperature higher than the initial curing temperature is preferable to improve heat resistance.

[0105] 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 polymerization, slow cooling is preferable to suppress stress and strain. Alternatively, reheating may be performed to alleviate strain.

[0106] A crosslinking agent may be added to further enhance crosslinking. This results in a polymer (cured product) with extremely excellent chemical resistance and heat resistance. Any known crosslinking agent can be used without limitation, but examples include trimethylolpropanetris (3-mercaptopropionate).

[0107] The electronic component material of the present invention can be used in the form of sheets, films, thin films, fibers, molded articles, etc. Preferred forms are films and thin films. Films and thin films are obtained by polymerizing the electronic component composition applied to a substrate or sandwiched between substrates. They can also be obtained by applying an electronic component composition containing a solvent to a substrate and then removing the solvent. Furthermore, films can also be obtained by press molding the polymer. In this specification, the film thickness of a sheet is 1 mm or more, the film thickness is 5 μm or more, preferably 10 to 900 μm, more preferably 20 to 800 μm, and the film thickness is less than 5 μm. The film thickness may be appropriately changed depending on the application.

[0108] The electronic component material of the present invention possesses excellent properties such as high thermal conductivity, chemical stability, heat resistance, hardness, and mechanical strength. Therefore, it is useful for heat sinks, heat sink sheets, heat sink films, heat sink coatings, heat sink adhesives, heat sink molded products, and the like.

[0109] Although the materials for electronic components formed from the polymerizable compounds of the present invention have been described above as being used as heat dissipation materials, the applications of these materials for electronic components are not limited to heat dissipation. For example, they may be used as encapsulants or adhesives.

[0110] [Method for manufacturing compositions for electronic components] The electronic component composition refers to the heat dissipation material of the present invention, which may contain inorganic fillers to enhance thermal conductivity, and whether or not coupling treatment is performed on the inorganic fillers is not required. As an example of manufacturing the electronic component composition, a manufacturing method in which coupling treatment is applied to the inorganic fillers is described below. Known methods can be used for the coupling treatment.

[0111] As an example, first, inorganic filler particles and a coupling agent are added to a solvent. After stirring with a stirrer or the like, the mixture is left to stand. After the solvent dries, the mixture is heat-treated under vacuum conditions using a vacuum dryer or the like. The solvent is added to these inorganic filler particles, and they are pulverized by ultrasonic treatment. The solution is separated and purified using a centrifuge. After discarding the supernatant, the solvent is added and the same procedure is repeated several times. The purified inorganic filler particles are dried using an oven.

[0112] Next, the coupled inorganic filler particles and polymerizable compounds are mixed using an agate mortar and pestle, and then kneaded using a twin-screw roller. After that, the mixture is separated and purified by sonication and centrifugation.

[0113] Furthermore, an amine-based curing agent is added and mixed using an agate mortar or the like, and then kneaded using a twin-screw roller or the like. This yields a solvent-free composition for electronic components.

[0114] [Method for manufacturing materials for electronic components] As an example, a method for producing a film as an electronic component material using a solvent-free composition for electronic components is described below.

[0115] A solvent-free composition for electronic components is placed between heating plates in a compression molding machine and molded by compression molding. The polymerizable compound polymerizes at a predetermined temperature and time to form a polymer. Post-curing may be performed at an appropriate time and temperature. The pressure during compression molding is 50 to 500 kgf / cm². 2 Preferably, and more preferably, 70-250 kgf / cm² 2 Therefore, a higher pressure is generally preferable during curing. However, it is preferable to adjust the pressure appropriately depending on the fluidity of the mold and the desired physical properties (such as which direction of thermal conductivity is emphasized) and apply an appropriate pressure.

[0116] Furthermore, electronic component compositions become easier to handle if they are partially hardened (in a semi-hardened state). For example, a semi-hardened composition can be formed into a sheet, cut into the desired shape, and then placed and bonded between suitable components.

[0117] A method for producing a film as an electronic component material using an electronic component composition containing a solvent is described below.

[0118] An electronic component composition is applied to a substrate, and the solvent is dried and removed to form a coating layer of uniform thickness. Examples of application methods include spin coating, roll coating, caten coating, flow coating, print coating, microgravure coating, gravure coating, wire bar coating, dip coating, spray coating, and meniscus coating.

[0119] 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, or by blowing warm or hot air onto it. The conditions for solvent removal are not particularly limited; it is sufficient to dry the coating layer until the solvent is mostly removed and the fluidity of the coating layer is lost.

[0120] [Electronic components] Examples of electronic components include electronic devices having a heat-generating section. When using the electronic component material of the present invention as a heat dissipation member, the heat dissipation member is placed on the electronic device so as to be in contact with the heat-generating section. The shape of the heat dissipation member may be any of the following: a heat sink, a heat sink sheet, a heat sink film, a heat sink adhesive, a heat sink molded product, etc. In this way, the heat dissipation member dissipates the heat generated in the electronic device, preventing failures due to heat, and thereby extending the lifespan of electronic equipment equipped with the electronic device.

[0121] Semiconductor elements can be cited as an example of electronic devices. Heat dissipation materials possess high thermal conductivity, as well as high heat resistance and high insulation properties. Therefore, they are particularly effective for insulated gate bipolar transistors (IGBTs), which require a more efficient heat dissipation mechanism due to their high power consumption. An IGBT is a type of semiconductor element, a bipolar transistor with a MOSFET incorporated into its gate, and is used in power control applications. Examples of electronic devices equipped with IGBTs include the main conversion element of 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 induction cooktops.

[0122] [Method for synthesizing the compound represented by formula (1)] The compound of formula (1) can be synthesized by combining known methods in organic synthesis chemistry. Methods for introducing the desired polymerizable group and ring structure to the starting material are described, for example, in textbooks such as Houben-Weyl (Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart), Organic Syntheses (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press), and New Experimental Chemistry Course (Maruzen). Alternatively, one may refer to Japanese Patent Publication No. 2006-265527. [Examples]

[0123] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to what is described in the examples. Unless otherwise specified, measurements were taken at 23°C.

[0124] [Measuring the phase transition point of compounds and identifying the liquid crystal phase] Measurements were performed using a polarizing microscope and a differential scanning calorimeter. The polarizing microscope consisted of a Nikon VHX5000 digital microscope (KEYENCE) with a polarizing plate attached. A hot stage system HS1 (Mettler Toledo) was used to control the temperature. Polarizing microscope measurements were performed under crossed nicols. The magnification of the eyepiece and objective lenses was 10x20x, respectively. A Perkin Elmer Diamond DSC differential scanning calorimeter was used. During measurements, the heating and cooling rates were both 3°C / min. In the examples, C represents crystal, S represents smectic phase, N represents nematic phase, I represents isotropic liquid, and () represents monotropic liquid crystal phase.

[0125] [Confirmation of liquid crystalline properties of the composition] A few drops of the composition were placed on a glass slide and maintained at 80°C for 10 minutes to evaporate the solvent. A coverslip was placed on the sample and sandwiched between glass plates. The composition was melted at a temperature above that of an isotropic liquid, then rapidly cooled to ensure even contact between the glass plates. The sample was observed under crossed nicols using the polarizing microscope described above. Liquid crystalline properties were determined if the presence or absence of orientation defects characteristic of the liquid crystal phase, the phase transition temperature range, the fluidity of the sample, and light loss due to scattering phenomena were visible in more than half of the observation area. Alternatively, if the composition was vertically oriented, the dark-field region occupied most of the area, but the region where orientation defects characteristic of the liquid crystal state existed was observed, and if such defects were present, liquid crystalline properties were determined.

[0126] [NMR measurement] NMR was measured using the VARIAN NMR SYSTEM from VARIAN Corporation. 1 The magnetic field strength for the 1H NMR measurement was 500 MHz. The sample was dissolved in a deuterated solvent such as CDCl3, and the measurement was performed at room temperature. The number of integration steps was 8. The internal standard was tetramethylsilane. In the NMR symbols, s means singlet, d means doublet, t means triplet, m means multiplet, and br means broad.

[0127] [Measurement of thermal conductivity] • Sample consisting solely of resin; using LFA467 HyperFlash manufactured by NETZSCH GmbH, the thermal diffusivity (α, m) of the sample was measured. 2 The thermal diffusivity ( / s) was determined. The thermal diffusivity was measured in both the in-plane and thickness directions of the sample. The specific heat (c, J / (Kg)) and density (ρ, g / m³) of the sample were determined. 3 The thermal conductivity (W / (Km)) was calculated from the following formula. κ = α x c x ρ At this time, specific heat was measured using a Rigaku Thermo Plus EVO2 DSC-8231 high-sensitivity differential scanning calorimeter. Specific gravity was measured using a Shinko Denshi DME-220 specific gravity scale. • Filler-filled sample: The thermal diffusivity in the thickness direction of the sample was measured using an ai-Phase Mobile 1u thermal diffusivity measuring device manufactured by i-Phase Co., Ltd. The specific heat and density of the sample were also measured in the same manner as above. From these values, the thermal conductivity was determined in the same manner as above.

[0128] [Epoxy compounds] As polymerizable compounds represented by formula (1), the compounds represented by formulas (1-2-1), (1-10-1), (1-11-1), (1-13-1), (1-14-1) through (1-14-4), and (1'-21) were used in the examples. These compounds were synthesized as described in the following examples. As a comparative compound, the compound represented by formula (ref. 1) described in International Patent Publication No. 2005 / 061473 was used. Furthermore, the compound represented by the above formula (o-1) was also used. Compound (o-1) was synthesized in accordance with Japanese Patent Publication No. 5862479. The phase transition point of compound (o-1) was C·51.1·N·64.6·I (°C). TIFF0007852759000030.tif18116 TIFF0007852759000031.tif16125 TIFF0007852759000032.tif22121 TIFF0007852759000033.tif23125 TIFF0007852759000034.tif23125 TIFF0007852759000035.tif67110 TIFF0007852759000036.tif17110 TIFF0007852759000037.tif18116

[0129] [Hardening agent] 1,3-Phenylenediamine (PDA) and 3,5-Dimethylaniline (DMA) were used as is, without purification, from Tokyo Chemical Industries, Ltd. Bisphenol E and the compound represented by the following formula (3-2-1) were used as phenolic curing agents. Bisphenol E was used as is, without purification, from Tokyo Chemical Industries, Ltd. TIFF0007852759000038.tif1287 TIFF0007852759000039.tif1470

[0130] [Vertical alignment agent] The following formula (p-1) was used. This compound was synthesized as described in the examples below. TIFF0007852759000040.tif2094

[0131] [Example 1] Synthesis of the compound represented by formula (1-2-1) TIFF0007852759000041.tif24165

[0132] A mixture of 1.29 g (5.16 mmol) of commercially available 2,5-dibromotoluene, 2.00 g (11.3 mmol) of 4-(3-butenyl)phenylboronic acid, 0.238 g (0.206 mmol) of tetrakistriphenylphosphinepalladium (0), and 1.44 g (13.6 mmol) of Na2CO3 was refluxed in 20 ml of dimethoxyethane under a nitrogen stream for 3 hours. 4-(3-butenyl)phenylboronic acid was synthesized according to Japanese Patent Publication No. 2014-31322. After the reaction was complete, the reaction mixture was cooled and 100 ml each of pure water and toluene were added. After separating the organic layer, it was washed twice with the same amount of pure water and dried over MgSO4. After filtration and removal of the solvent under reduced pressure, the resulting product was purified by column chromatography (silica gel, heptane / toluene = 1 / 1) to obtain compound (1-2-1-a). Yield: 946 mg (52% yield).

[0133] To a solution of 1.00 g (2.83 mmol) of compound (1-2-1-a) in CH2Cl2 (10 ml), 1.50 g (mCPBA, 65%, 5.65 mmol) of 3-chloroperbenzoic acid was added at a temperature below 10°C, and the mixture was stirred overnight at room temperature. After cooling the reaction mixture in an ice bath, 5 ml of 10% aqueous solution of sodium thiosulfate pentahydrate and 5 ml of 10% aqueous solution of sodium bicarbonate were added, and the mixture was stirred at room temperature for 30 minutes. The organic layer was separated from this reaction mixture and washed with 5 ml of 10% aqueous solution of sodium bicarbonate and 5 ml of pure water. After separation of the organic layer, it was dried over MgSO4. After filtration and removal of the solvent under reduced pressure, the resulting product was purified by column chromatography (silica gel, toluene / ethyl acetate = 10 / 1) and recrystallization (ethanol) to obtain compound (1-2-1). Yield: 680 mg (62% yield).

[0134] Phase transition temperature (°C): C·67.3·N·76.4·I 1 H-NMR(ppm,CDCl3);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).

[0135] [Example 2] Synthesis of the compound represented by formula (1-10-1) TIFF0007852759000042.tif20165 Using 2.00 g (6.60 mmol) of 4-bromo-4'-(3-butenyloxy)biphenyl, synthesized by the same method as in Synlett, No. 14, p. 2295 (2007), a coupling reaction with 4-(3-butenyl)phenylboronic acid was carried out in the same manner as in Example 1. The resulting product was purified by column chromatography (silica gel, toluene) and recrystallization (toluene) to obtain compound (1-10-1-a). Yield was 2.02 g (86% yield).

[0136] The compound represented by formula (1-10-1-a) was oxidized with mCPBA in the same manner as in Example 1. The resulting 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 (25% yield).

[0137] Phase transition temperature (°C): C·250.2·S 1 H-NMR(ppm,CDCl3);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).

[0138] [Example 3] Synthesis of the compound represented by formula (1-11-1) TIFF0007852759000043.tif52164

[0139] A mixture of 1.00 g (5.35 mmol) of commercially available 4-bromo-3-methylphenol, 1.27 g (7.21 mmol) of 4-(3-butenyl)phenylboronic acid, 0.127 g (0.110 mmol) of tetrakistriphenylphosphine palladium (0), and 1.33 g (12.5 mmol) of Na2CO3 was refluxed for 6 hours under a nitrogen stream in 12 ml of dimethoxyethane and 4 ml of water. After the reaction was complete, the reaction mixture was cooled and 100 ml each of pure water and toluene were added. The organic layer was separated, washed twice with the same amount of pure water, and dried over MgSO4. After filtration and removal of the solvent under reduced pressure, the resulting product was purified by column chromatography (silica gel, toluene) to obtain compound (1-11-1-a). Yield: 1.01 g (79.3% yield).

[0140] 1.01 g (4.24 mmol) of compound (1-11-1-a) and 1.5 ml of pyridine were dissolved in 10 ml of methylene chloride. 0.8 ml (4.89 mmol) of anhydrous trifluoromethanesulfonic acid was added at room temperature or below. The reaction mixture was stirred overnight, then transferred to 50 ml of distilled water and extracted with 50 ml of toluene. The organic layer was washed with dilute hydrochloric acid, distilled water, and sodium bicarbonate solution (50 ml each), and then dried over anhydrous magnesium sulfate. The organic layer was filtered, the solvent was removed under reduced pressure, and the resulting product was purified by column chromatography (heptane) to obtain compound (1-11-1-b). Yield: 1.39 g (87% yield).

[0141] A mixture of 940 mg (4.90 mmol) of 4-(3-butenyloxy)-phenylboronic acid, 1.39 g (3.75 mmol) of compound (1-9-1-b), 66 mg (0.094 mmol) of dichlorobistriphenylphosphine palladium(II), and 1.05 g (9.91 mmol) of Na2CO3 was refluxed under a nitrogen stream for 2 hours in a THF / pure water = 10 / 5 ml mixed solvent. After cooling the reaction mixture, pure water (50 ml) and toluene (50 ml) were added, and liquid-liquid extraction was performed. The organic layer was dried over anhydrous MgSO4, filtered, and the solvent was removed under reduced pressure. Compound (1-11-1-c) was obtained by purification of the residue by column chromatography (silica gel, toluene) and recrystallization (ethanol). Yield: 1.12 g (81% yield).

[0142] The compound represented by formula (1-11-1-c) was oxidized with mCPBA in the same manner as in Example 1. Compound (1-11-1) was obtained by purification of the resulting product by column chromatography (silica gel, toluene / ethyl acetate = 50 / 1) and recrystallization (ethanol). Yield: 585 mg (48%).

[0143] Phase transition temperature (°C): C·67.3·N·100.1·I 1 H-NMR(ppm,CDCl3);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).

[0144] [Example 4] Synthesis of the compound represented by formula (1-13-1) TIFF0007852759000044.tif44163 A mixture of 2.50 g (13.4 mmol) of commercially available 4-bromo-3-methylphenol, 2.34 g (17.3 mmol) of 4-bromo-1-butene, and 2.77 g (20.0 mmol) of K2CO3 was refluxed in 20 ml of methyl ethyl ketone for 20 hours. After cooling the reaction mixture, 50 ml of pure water and 50 ml of toluene were added, and liquid-liquid extraction was performed. The organic layer was dried over anhydrous MgSO4, filtered, and the solvent was removed under reduced pressure. The residue was purified by column chromatography (silica gel, toluene) to obtain 4-(3-butenyloxy)-2-methylbromobenzene. Yield: 2.51 g (78% yield).

[0145] Following the method described on page 101 of "Experimental Chemistry Course, 5th Edition, 18: Synthesis of Organic Compounds VI," Maruzen Co., Ltd., 4-(3-butenyloxy)-2-methylphenylboronic acid was synthesized using the above-mentioned 4-(3-butenyloxy)-2-methylbromobenzene. Yield: 2.51 g (78% yield). This compound was used directly in the next reaction without purification. Yield: 1.97 g (92% yield).

[0146] A mixture of 930 mg (4.51 mmol) of 4-(3-butenyloxy)-2-methylphenylboronic acid, 1.00 g (3.48 mmol) of compound (1-13-1-a), 61 mg of dichlorobistriphenylphosphine palladium(II), and 960 mg (9.06 mmol) of Na2CO3 was refluxed under a nitrogen stream for 4 hours in a THF / pure water = 20 / 20 ml mixed solvent. After cooling the reaction mixture, pure water (50 ml) and toluene (50 ml) were added, and liquid-liquid extraction was performed. The organic layer was dried over anhydrous MgSO4, filtered, and the solvent was removed under reduced pressure. Compound (1-13-1-b) was obtained by purification of the residue by column chromatography (silica gel, heptane / toluene = 10 / 1 → 5 / 1) and recrystallization (heptane). Yield 0.87 g (68% yield). The above compound (1-13-1-a) was synthesized using the same method as EP1013649A.

[0147] The compound represented by formula (1-13-1-b) was oxidized with mCPBA in the same manner as in Example 1. Compound (1-13-1) was obtained by purification of the resulting product by column chromatography (silica gel, toluene / ethyl acetate = 20 / 1) and recrystallization (ethanol). Yield: 0.41 g (90% yield).

[0148] Phase transition temperature (°C): C·65.8·N·105.8·I 1 H-NMR(ppm,CDCl3);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=8.00,2.5 0Hz),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).

[0149] [Example 5] Synthesis of the compound represented by formula (1-14-1) TIFF0007852759000045.tif21164

[0150] Compound (1-14-1-b) was synthesized using 4-(3-butenyloxy)-3-methylphenylboronic acid and compound (1-13-1-a), which were synthesized in the same manner as in Example 4. The product was purified by column chromatography (silica gel, heptane:toluene = 1:1) and recrystallization (heptane). Yield was 0.82 g (64% yield).

[0151] Compound (1-14-1-b) was used to synthesize compound (1-14-1) in the same manner as in Example 1. The product was purified by column chromatography (silica gel, toluene → toluene / ethyl acetate = 10 / 1) and recrystallization (ethanol). Yield was 0.55 g (62% yield).

[0152] Phase transition temperature (°C): C·144.1·N·183.4·I 1 H-NMR(ppm,CDCl3);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).

[0153] [Example 6] Synthesis of the compound represented by formula (1-14-2) TIFF0007852759000046.tif20164

[0154] Using 4-(4-pentenyloxy)-3-methylphenylboronic acid and compound (1-13-1-a), which were synthesized in the same manner as 4-(3-butenyloxy)-2-methylphenylboronic acid in Example 4, compound (1-14-2-a) was synthesized in the same manner as in Example 4. The product was purified by column chromatography (silica gel, toluene) and recrystallization (heptane). Yield was 9.5 g (82% yield).

[0155] Compound (1-14-2-a) was used to synthesize compound (1-14-2) in the same manner as in Example 1. The product was purified by column chromatography (silica gel, toluene / ethyl acetate = 10 / 1) and recrystallization (ethanol). Yield was 6.4 g (62% yield).

[0156] Phase transition temperature (°C): C·126.6·N·184.0·I 1 H-NMR(ppm,CDCl3);7.64-7.60(m,4H),7.57,7.43(AA'BB',4H),7.31-7.25(m,2H),6.89(d,1H,J=8.00 Hz),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).

[0157] [Example 7] Synthesis of the compound represented by formula (1-14-3) TIFF0007852759000047.tif20164

[0158] Compound (1-14-3-a) was synthesized using 4-(3-methyl-3-butenyloxy)-3-methylphenylboronic acid, synthesized in the same manner as in Example 4, and compound (1-13-1-a), in the same manner as in Example 4. The product was purified by column chromatography (silica gel, toluene) and recrystallization (heptane). Yield was 6.5 g (86% yield).

[0159] Compound (1-14-3) was synthesized using compound (1-14-2-a) in the same manner as in Example 1. The product was purified by column chromatography (silica gel, toluene:ethyl acetate = 10:1) and recrystallization (ethanol). Yield was 6.9 g (85% yield).

[0160] Phase transition temperature (°C): C·122.0·N·153.3·I 1 H-NMR(ppm,CDCl3);7.63-7.62(m,4H),7.57,7.29(AA'BB',4H),7.45-7.42(m,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).

[0161] [Example 8] Synthesis of the compound represented by formula (1-14-4) TIFF0007852759000048.tif18164

[0162] Using 4-(4-hexenyloxy)-3-methylphenylboronic acid and compound (1-13-1-a), which were synthesized in the same manner as 4-(3-butenyloxy)-2-methylphenylboronic acid in Example 4, compound (1-14-4-a) was synthesized in the same manner as in Example 4. The product was purified by column chromatography (silica gel, heptane / toluene = 1 / 1) and recrystallization (toluene / ethanol). Yield was 1.7 g (88% yield).

[0163] Compound (1-14-4-a) was used to synthesize compound (1-14-4) in the same manner as in Example 1. The product was purified by column chromatography (silica gel, toluene:ethyl acetate = 10:1) and recrystallization (ethanol). Yield: 0.96 g (52% yield).

[0164] Phase transition temperature (°C): C·108.3·N·174.0·I 1 H-NMR(ppm,CDCl3);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).

[0165] [Example 9] Synthesis of the compound represented by formula (1'-21) TIFF0007852759000049.tif25169

[0166] A mixture of compound (1'-21-a) 3.00 g (10.9 mmol), 4-bromo-2-methylbuto-1-ene 3.56 g (23.9 mmol), and K2CO3 3.6 g (26 mmol) was reacted in DMF (20 ml) under an N2 atmosphere at 80°C for 8 hours. After cooling the reaction mixture, toluene (100 ml) was added and the mixture was washed with pure water (100 ml). After separating the organic layer, it was dried over anhydrous MgSO4 and filtered. After removing 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 (64% yield).

[0167] Compound (1'-21-b) was used to synthesize compound (1'-21) in the same manner as in Example 1. The product was purified by column chromatography (silica gel, toluene:ethyl acetate = 10:1) and recrystallization (ethanol). Yield: 0.95 g (69% yield).

[0168] Phase transition temperature (°C): C·151.8·I 1 H-NMR(ppm,CDCl3);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,1 H,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).

[0169] [Comparative Example 1] The phase transition point of the compound represented by formula (ref. 1) was measured and the results were as follows: Phase transition temperature (°C): C·176.9·I

[0170] From a comparison of the above examples with comparative examples, it can be seen that the compounds of the present invention tend to exhibit liquid crystalline properties. In particular, the compounds of Examples 3 to 8 have a wide liquid crystalline phase in the temperature range of 80°C to 180°C, which is a temperature range suitable for epoxy curing.

[0171] [Synthesis Example 1] Synthesis of the compound represented by formula (3-2-1) TIFF0007852759000050.tif63163

[0172] A mixture of 2.00 g (9.34 mmol) of 3-formyl-4,4'-dihydroxybiphenyl, 4.7 g (56 mmol) of 3,4-dihydro-2H-pyran, and 0.47 g (1.9 mmol) of PPTS was stirred overnight at room temperature in 20 ml of CH2Cl2. In the above reaction, 3-formyl-4,4'-dihydroxybiphenyl was synthesized according to the Journal of Medicinal Chemistry, vol. 52, p. 858 (2009). 30 ml of saturated sodium bicarbonate solution was added to the reaction mixture, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and filtered. After removing the solvent under reduced pressure, the resulting product was purified by column chromatography (toluene / ethyl acetate = 10 / 1) to obtain compound (3-2-1-a). Yield: 244 mg (7.9% yield).

[0173] To a solution of 868 mg (2.43 mmol) of methyltriphenylphosphonium bromide in 10 ml of THF, a solution of 294 mg (2.62 mmol) of t-BuOK in 10 ml of THF was added at or below 0°C. After stirring at 0°C for 30 minutes, the mixture was cooled to -20°C, and 1.00 g (1.87 mmol) of compound (3-2-1-a) was added. After stirring at room temperature for 2 hours, the mixture was poured into 50 ml of pure water and extracted with 50 ml of toluene. The organic layer was washed with 50 ml of pure water and dried over anhydrous magnesium sulfate. The organic layer was filtered, the solvent was removed by reduced pressure, and the resulting product was purified by column chromatography (heptane / toluene = 1 / 1 → toluene) to obtain compound (3-2-1-b). Yield: 766 mg, yield: 77%.

[0174] To a THF (10 ml)-MeOH (10 ml) mixed solution of compound (3-2-1-b) 1.61 g (4.21 mmol) of pyridinium p-toluenesulfonate was added and the mixture was stirred overnight at room temperature. Brine and ethyl acetate (30 ml each) were added to the reaction mixture, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by vacuum distillation. The resulting product was purified by column chromatography (toluene:ethyl acetate = 2:1) to obtain compound (3-2-1). Yield 100%.

[0175] Melting point (°C): 138.0–145.7. 1 H-NMR(ppm,CDCl3);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=17.50,10.50 Hz),6.91-6.87(AA'BB',2H),6.85(d,1H,J=8.50Hz),5.80(d,1H,J=18.00Hz),5.41(d,1H,J=11.00Hz),4.99(s,1H),4.76(s,1H).

[0176] [Synthesis Example 2] Synthesis of the compound represented by formula (p-1) TIFF0007852759000051.tif57164 A mixture of 3.30 g (9.26 mmol) of 1-iodo-4-trans(4-n-pentyl)cyclohexylbenzene, 1.50 g (9.25 mmol) of 4-ethynyl-1,2-dimethoxybenzene, 130 mg (0.185 mmol) of dichlorobistriphenylphosphine palladium(II), and 35.2 mg (0.185 mmol) of CuI was refluxed in 30 ml of Et3N under a N2 stream for 4 hours. After cooling the reaction mixture, 60 ml of toluene and 50 ml of pure water were added to the reaction mixture, and the organic layer was separated. The organic layer was dried over MgSO4, filtered, and the solvent was removed under reduced pressure. Compound (p-1-a) was obtained by purification of the residue by column chromatography (silica gel, toluene / ethyl acetate = 10 / 1) and recrystallization (EtOH). Yield 2.72 g (75% yield).

[0177] The above-mentioned 1-iodo-4-trans(4-n-pentyl)cyclohexylbenzene and 4-ethynyl-1,2-dimethoxybenzene were synthesized according to J.Am.Chem.Soc.,131,6763(2009) and J.Org.Chem.,73,4241(2008), respectively.

[0178] 2.20 g (5.75 mmol) of compound (p-1-a) was hydrogenated in an autoclave using Pd / C 320m as a catalyst in toluene / ethanol = 20 / 20 ml. The hydrogen pressure at this time was 0.7 MPa. After the reaction, the catalyst was filtered off and the solvent was removed by reduced pressure distillation. Compound (p-1-b) was obtained by recrystallization (EtOH) of the residue. The yield was 1.70 g (75% yield).

[0179] To a 10 ml solution of 1.10 g (2.79 mmol) of compound (p-1-b) in CH2Cl2, 5.8 ml of a 1 M solution of BBr3 in CH2Cl2 was added at -10°C. After stirring overnight at room temperature, the reaction mixture was added to 30 ml of pure water. AcOEt (40 ml) was added to this mixture and extracted. The organic layer was washed twice with 15 ml of pure water and dried over MgSO4. The solution was filtered, and the solvent was removed by vacuum distillation. Compound (p-1) was obtained by purification of the residue by column chromatography (silica gel, toluene / ethyl acetate = 1 / 1) and recrystallization (toluene). Yield 870 mg (85% yield).

[0180] Phase transition temperature (°C): C·147.4·N·161.4·I. 1 H-NMR(ppm,CDCl3);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).

[0181] [Example 10] Preparation of composition and confirmation of solubility 0.5000 g (1,300 mmol) of the compound represented by formula (1-2-1) synthesized in Example 1, and 0.2786 g (1,300 mmol) of bisphenol E were placed in a sample bottle, 2.80 ml of cyclopentanone was added, and the solids were dissolved to obtain a composition (composition 12) with a solid content of approximately 20%. When this composition 10 was left standing overnight in a refrigerator set to 0°C, no precipitate formed and it remained in its original state.

[0182] [Examples 11] to [Examples 30] Except for changing the epoxy compound and curing agent as shown in Table 1 below, a 20% by weight solids composition solution was prepared in the same manner as in Example 10, and its solubility was confirmed. In Table 1, columns listing two types of epoxy compound or curing agent indicate that they are mixed, and the proportion is shown afterward as the molar ratio of each compound. The molar ratio of epoxy compound to curing agent in each composition was kept equal.

[0183] Table 1 Composition and its solubility (solvent: cyclopentanone) TIFF0007852759000052.tif166151

[0184] [Example 31] 0.5000 g (1.206 mmol) of the compound represented by formula (1-14-3), 0.1794 g (0.8452 mmol) of the compound represented by formula (3-2-1), and 0.1330 g (0.3628 mmol) of the compound represented by formula (p-1) were placed in a sample bottle, 3.14 ml of cyclopentanone was added, and the solids were dissolved to obtain a composition (composition 31) with a solid content of approximately 20%. When composition 31 was left standing overnight in a refrigerator set to 0°C, no precipitate formed and it remained in its original state.

[0185] [Comparative Example 2] The solubility of the compound represented by formula (ref. 1) was confirmed using the same method as in Example 10 above. As a result, it did not dissolve in cyclopentanone.

[0186] From a comparison of Examples 10 to 31 and Comparative Example 2, it can be seen that the compounds of the present invention have high solubility in solvents.

[0187] [Example 32] Preparation of composition, confirmation of liquid crystalline properties, and confirmation of storage stability 1.000 g (2.601 mmol) of the compound represented by formula (1-2-1) synthesized in Example 1 and 0.1406 g (1.300 mmol) of PDA were placed in a sample bottle, and tetrahydrofuran (10 ml) was added to dissolve the solids (Composition 32). When this composition was observed under a polarizing microscope on a hot plate, its liquid crystalline properties were confirmed. Next, this 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 overnight in a refrigerator at 0°C, it remained a viscous liquid.

[0188] [Comparative Example 3] 1.000 g (2.574 mmol) of the compound represented by formula (ref. 1) and 0.1392 g (1.287 mmol) of PDA were placed in a sample bottle, and 100 ml of tetrahydrofuran was added to dissolve the solids (composition ref. 3). When this composition was observed under a polarizing microscope, some areas exhibiting liquid crystalline properties were confirmed, but crystals were observed in other areas. Furthermore, the solvent was removed from this solution under reduced pressure using 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. 3' was partially crystallized.

[0189] A comparison of Example 32 and Comparative Example 3 shows that the composition using the liquid crystalline epoxy compound of the present invention is less prone to crystallization. Such compositions are extremely useful when preparing paste-like samples.

[0190] [Examples 33 to 54] Confirmation of liquid crystalline properties of compositions The liquid crystalline properties of the compositions prepared in Examples 10 to 31 were confirmed. The results are shown in Table 2. Table 2 Confirmation of liquid crystalline properties of the composition TIFF0007852759000053.tif130142

[0191] The compositions described in Examples 33 to 54, with the exception of the composition described in Example 39, exhibited a uniform nematic phase in their liquid crystal temperature range. On the other hand, composition ref. 3 of Comparative Example 3 did not form a uniform liquid crystal phase. This suggests that the compositions using the liquid crystalline epoxy compound of the present invention have high compatibility with the curing agent. Cured products obtained by curing such compositions have no component imbalance and are materials with excellent thermal conductivity and reliability.

[0192] [Example 55] Measurement of the thermal conductivity of the cured product prepared from composition 32 The above composition 32 was placed in a φ2.4 cm aluminum container and held on a hot plate heated to 150°C for 120 minutes, and a circular piece with a thickness of 1.5 mm was removed. The thermal conductivity of this cured product (cured product 32) was 0.95 W / m·K and 0.45 W / m·K in the in-plane direction and the thickness direction of the sample, respectively.

[0193] [Examples 56] to [Examples 57] The heat dissipation characteristics of the compositions listed in Table 3, or cured products prepared from these compositions, were confirmed using the same method as in Example 55 described above. In the table, the molar percentages of each component compound in each constituent are shown in parentheses. Regarding liquid crystalline properties, ○ indicates that they are present, and × indicates that they are not.

[0194] Table 3. Liquid crystallinity and thermal conductivity of the composition TIFF0007852759000054.tif52170

[0195] [Example 58] Measurement of the thermal conductivity of the cured product 2 Composition 10 prepared in Example 10 was dissolved with 0.0400 g (0.588 mmol) of imidazole to obtain composition 10C. Composition 10C was placed in a φ2.4 cm aluminum container and held on a hot plate heated to 150°C for 120 minutes, and a circular piece with a thickness of approximately 1.0 mm was removed. The thermal conductivity of this cured product (cured product 10C) was 0.90 W / m·K and 0.41 W / m·K in the in-plane direction and the thickness direction of the sample, respectively.

[0196] [Examples 59] to [Examples 78] In the same manner as in Example 58, imidazole was added to compositions 11 through 31 (excluding the original composition and composition 16) to prepare compositions 11C through 31C. The compositions were then heated to obtain cured products. The results of measuring the thermal conductivity of these cured products are shown in Table 4. Table 4. Thermal conductivity of the composition TIFF0007852759000055.tif125151

[0197] [Example 79] Preparation of filler-containing samples 1.0 g of composition 32 and 0.90 g of boron nitride particles (PolarTherm PTX-25, manufactured by Momentive Performance Materials Japan LLC) were weighed out and thoroughly mixed. After standing on a hot plate heated to 80°C for 5 minutes, the sample was sandwiched between stainless steel plates and held at a pressure of 20 MPa for 45 minutes in a compression molding machine (IMC-19EC, manufactured by Imoto Seisakusho Co., Ltd.) heated to 150°C. A square piece with a thickness of 768 μm was extracted to serve as a heat dissipation material. The thermal conductivity of this sample (filler-containing sample 32) was 10.8 W / m·K.

[0198] [Example 80] and [Example 81] Filler-filled samples 33 and 34 were prepared in the same manner as described in Example 79, except that compositions 33 and 34 were used instead of composition 32, and their thermal conductivity was measured. The results are shown in Table 5.

[0199] Table 5. Thermal conductivity of filler-containing samples 1 TIFF0007852759000056.tif26140

[0200] [Example 82] Preparation of filler-containing sample 2 A sample (filler-containing sample 22C) was prepared in the same manner as in Example 79, except that 0.5 g of composition 22C was used. The thermal conductivity of this filler-containing sample 22C was 12.0 W / m·K.

[0201] [Examples 83] to [Examples 90] Except for using composition 23C to 31C instead of composition 22C, 31C was prepared from filler-containing sample 23C in the same manner as described in Example 82 above, and its thermal conductivity was measured. The results are shown in Table 6.

[0202] Table 6. Thermal conductivity of filler-containing samples. TIFF0007852759000057.tif57142

[0203] [Example 91] and [Example 92] Weigh out 0.5 g of composition 24C or composition 26C and 0.90 g of aluminum oxide particles (Denka DAW-10), mix them well, and prepare filler-filled sample 24C in the same manner as described in Example 84 above. AO and 26C AO A solution was prepared, and its thermal conductivity was measured. The results are shown in Table 7.

[0204] Table 7. Thermal conductivity of filler-containing samples 3 TIFF0007852759000058.tif26140 As described above, the technology disclosed in this invention provides high thermal conductivity. [Industrial applicability]

[0205] The technology of the present invention can be suitably used as a packaging material for semiconductor devices. It can also be used as a substitute for other epoxy resins, such as adhesives.

Claims

1. A compound represented by formula (1), wherein the compound is represented by any one of formulas (1-1), (1-3), (1-8) to (1-24), (1-27), (1-30) to (1-37), and (1-39) to (1-47). In formula (1), R ｅｐ is independently a 2- to 12 carbon group having an oxyranil, with at least one oxyranil bonded to the aromatic ring via carbon, where Rep are distinct from each other, where X is independently a single bond or -C≡C-, and R １ These are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, or R ｅｐ And n is either 1 or 2. In equations (1-1), (1-3), (1-8) to (1-24), (1-27), (1-30) to (1-37), and (1-39) to (1-47), R ｅｐ１ and R ｅｐ２ This represents a group with 2 to 12 carbon atoms, having one oxyranyl group, and all other atoms independently consisting of a carbon-carbon single bond and a hydrogen atom bonded to a carbon atom.

2. A composition comprising the compound and curing agent described in claim 1.

3. The composition according to claim 2, further comprising a curing accelerator.

4. The composition according to claim 2 or 3, wherein the curing agent is an aromatic primary amine, an aliphatic primary amine, an aromatic having two or more secondary aminos in its molecular skeleton, or an aliphatic amine having two or more secondary aminos in its molecular skeleton.

5. The composition according to claim 4, wherein the curing agent is at least one compound represented by formula (2-1) or (2-2). E-Z-(L-Z)n-E (2-1) L １ -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 of these rings may be replaced by an alkyl group having 1 to 10 carbon atoms. L １ is hydrogen, cyclohexyl, phenyl, or naphthyl, and at least one hydrogen of these rings may be replaced by an alkyl group having 1 to 10 carbon atoms. Z is independently a single bond, -O-, -NH-, -S-, -SO ２ -, -CO ２ -, or an alkylene having 1 to 12 carbon atoms, E is independently an amino, a C1-C10 alkylamino, a hydroxyl group, or a carboxyl group, and at least one of E is an amino or a C1-C10 alkylamino. n is an integer between 0 and 7.

6. The composition according to claim 2 or 3, wherein the curing agent is a phenol having two or more -OH groups in its molecular skeleton, or a compound in which at least one of the -OH groups in the phenol is a short-chain ester. A short-chain ester is a structure in which the group represented by (3-E) below is substituted for the hydrogen in 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 to O.

7. The composition according to claim 6, wherein the curing agent is at least one compound represented by formulas (3-1) to (3-7), or a compound in which at least one of the -OH groups in that compound is a short-chain ester. In formula (3-1), Ring B is benzene, naphthalene, anthracene, fluorene, or 9,9-diphenylfluorene, where at least one hydrogen in ring B may be replaced by a C1-C3 alkyl or C1-C3 alkoxy; n31 is an integer between 2 and 4 (inclusive). In equation (3-2), n32 and n33 are independent integers between 1 and 3; Z ３０ These are single bonds, alkylenes with 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 atom on the benzene ring may be replaced by an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms; In equations (3-3) and (3-4), n34 is an integer between 1 and 5000, n35 and n36 are independently 0 or 1, the sum of n35 and n36 is 1 or greater, and if n34 is 2 or greater, it may be different in each iteration. R １０ and R １１ These are independently 1,4-phenylene, 4,4'-biphenylene, or 1,3-cyclopentadienylene, In formula (3-5), n34 is an integer between 1 and 5000, In formula (3-6), Z ３１ These are independent single bonds, -CH(CH ３ )-, or-C(CH ３ ) ２ - and n34 is an integer between 1 and 5000. In formula (3-7), n34 is an integer between 1 and 5000, and R １２ These are independently hydrogen or methyl. A short-chain ester is a structure in which the group represented by (3-E) below is substituted for the hydrogen in 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 to O. Furthermore, at least one hydrogen atom on the aromatic ring in formulas (3-3) through (3-7) may be replaced with a methyl atom.

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

9. The composition according to claim 2 or 3, wherein the curing agent is a compound comprising a carboxylic acid, a carboxylic acid ester, an acid anhydride, or a thiol.

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

11. The composition according to claim 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 claims 2 to 11.

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