阅读说明：本技术 环氧树脂、树脂组合物、树脂片材、树脂固化物、树脂基板及层叠基板 (Epoxy resin, resin composition, resin sheet, cured resin, resin substrate, and laminated substrate ) 是由 稻垣尭 佐藤彩乃 于 2020-03-24 设计创作，主要内容包括：一种环氧树脂,其在分别配置于两末端的具有环氧基的末端基团之间具有第一结构及第二结构的一者或两者,所述第一结构是依次键合有芳香族环基、醚氧、亚甲基、芳香族环基、亚甲基、醚氧、芳香族环基而成的,所述第二结构是依次键合有芳香族环基、亚甲基、醚氧、芳香族环基、醚氧、亚甲基、芳香族环基而成的。(An epoxy resin having one or both of a first structure and a second structure between terminal groups having epoxy groups respectively disposed at both ends, the first structure being formed by bonding an aromatic ring group, an ether oxygen, a methylene group, an aromatic ring group, a methylene group, an ether oxygen, and an aromatic ring group in this order, and the second structure being formed by bonding an aromatic ring group, a methylene group, an ether oxygen, an aromatic ring group, an ether oxygen, a methylene group, and an aromatic ring group in this order.)

1. An epoxy resin composition, wherein,

one or both of the first structure and the second structure are provided between the terminal groups having epoxy groups respectively provided at both ends,

the first structure is formed by bonding an aromatic ring group, ether oxygen, methylene, an aromatic ring group, methylene, ether oxygen and an aromatic ring group in sequence,

the second structure is formed by bonding an aromatic ring group, a methylene group, an ether oxygen group, an aromatic ring group, an ether oxygen group, a methylene group and an aromatic ring group in sequence.

2. The epoxy resin according to claim 1,

comprising a first aromatic ring unit, a second aromatic ring unit and a third aromatic ring unit, and a skeleton in which the first aromatic ring unit and the second aromatic ring unit are alternately arranged,

the first aromatic ring unit is composed of a first aromatic ring group and two ether oxygens bonded to the first aromatic ring group,

the second aromatic ring unit is composed of a second aromatic ring group and two methylene groups bonded to the second aromatic ring group,

the third aromatic ring unit is composed of a third aromatic ring group and an end group having an epoxy group bonded to the third aromatic ring group,

the first aromatic ring unit is disposed at both ends of the skeleton and is bonded to the third aromatic ring group via a methylene group, or

The second aromatic ring unit is disposed at both ends of the skeleton and is bonded to the third aromatic ring group via an ether oxygen.

3. The epoxy resin according to claim 1,

represented by the following general formula (1) or the following general formula (2),

in the formula (1), Ar₁Each independently is a first aromatic ring group with or without substituents, Ar₂Each independently represents a second aromatic ring group having or not having a substituent，Ar₃Each independently represents a third aromatic ring group having a substituent or not, each Z independently represents a terminal group having an epoxy group, n is an integer of 0 or more,

in the formula (2), Ar₁Each independently is a first aromatic ring group with or without substituents, Ar₂Each independently represents a second aromatic ring group having or not having a substituent, Ar₃Each independently represents a third aromatic ring group having a substituent or not, each Z independently represents a terminal group having an epoxy group, and n is an integer of 0 or more.

4. The epoxy resin according to claim 2 or 3,

any one or more of the first aromatic ring group, the second aromatic ring group, and the third aromatic ring group is a p-phenylene group which may have a substituent.

5. The epoxy resin according to any one of claims 2 to 4,

the first aromatic ring group and the third aromatic ring group are the same,

the second aromatic ring group is p-phenylene.

6. The epoxy resin according to any one of claims 1 to 5, wherein,

represented by the following general formula (9),

in the formula (9), R1-R4, R9-R12, and R17-R20 are each independently any one selected from hydrogen, a methyl group, a trifluoromethyl group, a halogen group, and a nitro group, Z is each independently a terminal group having an epoxy group, and n is an integer of 0 or more.

7. The epoxy resin according to claim 6,

any one of the R1 to the R4 is methyl and the other is hydrogen, any one of the R9 to the R12 is methyl and the other is hydrogen, and any one of the R17 to the R20 is methyl and the other is hydrogen.

8. The epoxy resin according to claim 3 or 6,

and n is an integer of 0-10.

9. The epoxy resin according to any one of claims 1 to 8, wherein,

the terminal group having an epoxy group is a group in which an epoxy group is bonded to a linking group having at least one of a methylene group, an ether bond, an ester bond, a ketone group, and an amide bond.

10. The epoxy resin according to any one of claims 1 to 9, wherein,

the terminal group having an epoxy group is any one of the following formulas (3) to (8),

11. a resin composition characterized by containing, as a main component,

comprising the epoxy resin according to any one of claims 1 to 10.

12. A resin sheet, wherein,

the resin composition according to claim 11.

13. A cured resin material, wherein,

a cured product comprising the resin composition according to claim 11.

14. A resin substrate, wherein,

a cured product comprising the resin composition according to claim 11.

15. A laminated substrate, wherein,

a resin composition according to claim 11, wherein a plurality of resin substrates are laminated, and at least one of the plurality of resin substrates contains a cured product of the resin composition.

Technical Field

The present disclosure relates to an epoxy resin, a resin composition, a resin sheet, a resin cured product, a resin substrate, and a laminated substrate.

The present application claims priority based on japanese patent application No. 2019-068680, filed in japan on 29/3/2019, the contents of which are incorporated herein by reference.

Background

In recent years, along with the demand for miniaturization of electronic devices, high-performance and high-density mounting of parts has been carried out. Therefore, the processing of heat generated from electronic components and the like becomes important.

Heat generated from electronic components and the like is mainly radiated to the outside through the substrate without providing a special cooling mechanism. A laminate substrate for a power supply, on which resin substrates are laminated, is required to have particularly high heat dissipation properties. Therefore, the thermal conductivity of the resin substrate is improved by adding inorganic particles such as alumina, boron nitride, and magnesium oxide to the resin. For example, patent document 1 describes an epoxy resin composition containing an epoxy resin, a curing agent, and an inorganic filler.

However, if the content of inorganic particles in the resin is increased in order to increase the thermal conductivity, a problem arises in the process applicability in the molding of the substrate. Therefore, development of a resin capable of obtaining a cured product having high thermal conductivity has been carried out in order to obtain a substrate having high heat dissipation properties even if the process applicability is ensured by suppressing the content of inorganic particles in the resin.

As a resin having high thermal conductivity, there is an epoxy resin into which a mesomorphic skeleton is introduced (for example, see non-patent document 1).

In addition, patent document 2 discloses a mixture of an epoxy resin obtained by reacting at least a 2-functional epoxy resin with a bisphenol compound.

Patent document 3 discloses a resin composition containing a filler and a thermosetting resin having mesogens in the molecule.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 6074447

Patent document 2: japanese patent laid-open No. 2012 and 131992

Patent document 3: international publication No. 2013/065159

Non-patent document

Non-patent document 1: zhuze Shuang from Gao, high molecular 65 Vol 2 Yue No., p65-67, 2016

Disclosure of Invention

Technical problem to be solved by the invention

However, conventional epoxy resins have not obtained cured products having sufficiently high thermal conductivity, and it is required to improve the thermal conductivity of the cured products.

The present disclosure has been made in view of the above-mentioned problems, and an object thereof is to provide an epoxy resin that can provide a cured product having high thermal conductivity.

Another object of the present disclosure is to provide a resin composition containing the epoxy resin of the present disclosure, a resin sheet, a resin cured product, a resin substrate, and a laminated substrate.

Technical solution for solving technical problem

The present inventors have made extensive studies with a view to solving the above problems, focusing on the skeleton and terminal groups of the epoxy resin.

As a result, they found that: the epoxy resin may have a structure in which an aromatic ring group which may have a substituent, an ether oxygen and a methylene group are bonded in a specific order, and terminal groups having an epoxy group are bonded to both ends of the epoxy resin.

That is, the present disclosure relates to the following inventions.

[1] An epoxy resin having one or both of a first structure and a second structure between terminal groups having epoxy groups respectively disposed at both ends,

the first structure is formed by bonding an aromatic ring group, ether oxygen, methylene, an aromatic ring group, methylene, ether oxygen and an aromatic ring group in sequence,

the second structure is formed by bonding an aromatic ring group, a methylene group, an ether oxygen group, an aromatic ring group, an ether oxygen group, a methylene group and an aromatic ring group in sequence.

[2] The epoxy resin according to [1], which comprises a first aromatic ring unit, a second aromatic ring unit and a third aromatic ring unit, and which comprises a skeleton in which the first aromatic ring unit and the second aromatic ring unit are alternately arranged,

the first aromatic ring unit is composed of a first aromatic ring group and two ether oxygens bonded to the first aromatic ring group,

the second aromatic ring unit is composed of a second aromatic ring group and two methylene groups bonded to the second aromatic ring group,

the third aromatic ring unit is composed of a third aromatic ring group and an end group having an epoxy group bonded to the third aromatic ring group,

the first aromatic ring unit is disposed at both ends of the skeleton and is bonded to the third aromatic ring group via a methylene group, or

The second aromatic ring unit is disposed at both ends of the skeleton and is bonded to the third aromatic ring group via an ether oxygen.

[3] The epoxy resin according to [1], which is represented by the following general formula (1) or the following general formula (2).

(in the formula (1), Ar₁Each independently is a first aromatic ring group with or without substituents, Ar₂Each independently represents a second aromatic ring group having or not having a substituent, Ar₃Each independently is a third aromatic ring group with or without a substituent; each Z is independently a terminal group having an epoxy group; n is an integer of 0 or more. )

(in the formula (2), Ar₁Each independently is a first aromatic ring group with or without substituents, Ar₂Each independently represents a second aromatic ring group having or not having a substituent, Ar₃Each independently is a third aromatic ring group with or without a substituent; each Z is independently a terminal group having an epoxy group; n is an integer of 0 or more. )

[4] The epoxy resin according to [2] or [3], wherein at least one of the first aromatic ring group, the second aromatic ring group, and the third aromatic ring group is a p-phenylene group which may have a substituent.

[5] The epoxy resin according to any one of [2] to [4], wherein the first aromatic ring group and the third aromatic ring group are the same,

the second aromatic ring group is p-phenylene.

[6] The epoxy resin according to any one of [1] to [5], which is represented by the following general formula (9).

(in the formula (9), R1-R4, R9-R12, and R17-R20 are each independently any one selected from the group consisting of hydrogen, methyl, trifluoromethyl, a halogen group, and a nitro group; Z is each independently a terminal group having an epoxy group; and n is an integer of 0 or more.)

[7] The epoxy resin according to [6], wherein any one of R1 to R4 is methyl and the others are hydrogen, any one of R9 to R12 is methyl and the others are hydrogen, and any one of R17 to R20 is methyl and the others are hydrogen.

[8] The epoxy resin according to [3] or [6], wherein n is an integer of 0 to 10.

[9] The epoxy resin according to any one of [1] to [8], wherein the terminal group having an epoxy group is a group in which an epoxy group is bonded to a linking group having at least one of a methylene group, an ether bond, an ester bond, a ketone group, and an amide bond.

[10] The epoxy resin according to any one of [1] to [9], wherein the terminal group having an epoxy group is any one of the following formulas (3) to (8).

[11] A resin composition comprising the epoxy resin according to any one of [1] to [10 ].

[12] A resin sheet obtained by molding the resin composition according to [11 ].

[13] A cured resin product comprising the cured resin composition according to [11 ].

[14] A resin substrate comprising a cured product of the resin composition according to [11 ].

[15] A laminated substrate, wherein a plurality of resin substrates are laminated, and at least one of the plurality of resin substrates contains a cured product of the resin composition according to [11 ].

ADVANTAGEOUS EFFECTS OF INVENTION

The epoxy resin of the present disclosure has one or both of a first structure and/or a second structure between terminal groups having epoxy groups respectively disposed at both ends, the first structure being formed by bonding an aromatic ring group, an ether oxygen, a methylene group, an aromatic ring group, a methylene group, an ether oxygen, and an aromatic ring group in this order, and the second structure being formed by bonding an aromatic ring group, a methylene group, an ether oxygen, an aromatic ring group, an ether oxygen, a methylene group, and an aromatic ring group in this order. The first structure and the second structure are mesogens exhibiting liquid crystallinity, and have structures in which an aromatic ring group imparting rigidity, a methylene group imparting mobility, and an ether oxygen are arranged in a specific order. Thus, the epoxy resin of the present disclosure can stabilize a smectic liquid crystal phase by appropriate mobility of mesogens themselves even without having a long side chain as seen in a general liquid crystal molecule. Accordingly, the epoxy resin of the present disclosure has high orientation, and curing the epoxy resin of the present disclosure can provide a cured product having a smectic liquid crystal structure and high thermal conductivity with suppressed phonon scattering.

Drawings

Fig. 1 is a schematic perspective view showing an example of a resin sheet and a resin substrate.

Fig. 2 is a schematic sectional view of the resin sheet and the resin substrate of fig. 1 taken along line ii-ii.

Fig. 3 is a schematic perspective view of the laminated substrate.

Fig. 4 is a schematic sectional view of the laminated substrate of fig. 3 taken along line iv-iv.

Detailed Description

Preferred examples of the present disclosure will be described below in detail with reference to the accompanying drawings as appropriate. The drawings used in the following description are sometimes enlarged and shown in order to facilitate understanding of the features of the present disclosure. Therefore, the dimensional ratios of the components shown in the drawings may be different from the actual dimensional ratios. The materials, dimensions, and the like exemplified in the following description are examples, and the present disclosure is not limited to these examples, and can be implemented by appropriately changing the materials, dimensions, and the like within a range in which the gist thereof is not changed.

Epoxy resin "

The epoxy resin of the present embodiment has a first structure and/or a second structure between terminal groups having epoxy groups respectively disposed at both ends.

The first structure is a structure in which an aromatic ring group, an ether oxygen group, a methylene group, an aromatic ring group, a methylene group, an ether oxygen group, and an aromatic ring group are bonded in this order.

The second structure is a structure in which an aromatic ring group, a methylene group, an ether oxygen group, an aromatic ring group, an ether oxygen group, a methylene group, and an aromatic ring group are bonded in this order.

The epoxy resin of the present embodiment preferably includes a first aromatic ring unit, a second aromatic ring unit, and a third aromatic ring unit, which are described below.

The first aromatic ring unit is composed of a first aromatic ring group and 2 ether oxygens bonded to the first aromatic ring group.

The second aromatic ring unit is composed of a second aromatic ring group and 2 methylene groups bonded to the second aromatic ring group.

The third aromatic ring unit is composed of a third aromatic ring group and an end group having an epoxy group bonded to the third aromatic ring group.

The epoxy resin of the present embodiment preferably includes a skeleton in which the first aromatic ring unit and the second aromatic ring unit are alternately arranged 1 or more times.

The first aromatic ring unit may be disposed at both ends of the skeleton, or the second aromatic ring unit may be disposed at both ends of the skeleton. Preferably, the first aromatic ring unit or the second aromatic ring unit is disposed at both ends of the skeleton, thereby producing a skeleton having a symmetrical structure.

In the epoxy resin of the present embodiment, when the first aromatic ring unit is disposed at both ends of the skeleton, the first aromatic ring unit is bonded to the third aromatic ring group via a methylene group. In the epoxy resin of the present embodiment, when the second aromatic ring unit is disposed at both ends of the skeleton, the second aromatic ring unit is bonded to the third aromatic ring group through an ether oxygen.

The first aromatic ring group, the second aromatic ring group, and the third aromatic ring group in the epoxy resin of the present embodiment may all be aromatic ring groups, and may have a substituent. The term "may have a substituent" may mean having or not having a substituent. The first aromatic ring group, the second aromatic ring group and the third aromatic ring group may be different from each other, or may be partially or entirely the same, and may be determined as appropriate depending on the use of the epoxy resin, and the like.

When the epoxy resin of the present embodiment has a plurality of first aromatic ring groups, the plurality of first aromatic ring groups may be different from each other, or may be partially or entirely the same. An epoxy resin in which all of the plurality of first aromatic ring groups are the same can be easily produced, and is therefore preferable.

When the epoxy resin of the present embodiment has a plurality of second aromatic ring groups, the plurality of second aromatic ring groups may be different from each other, or may be partially or entirely the same. An epoxy resin in which all of the plurality of second aromatic ring groups are the same can be easily produced, and is therefore preferable.

The third aromatic ring groups disposed at both ends of the skeleton of the epoxy resin of the present embodiment may be different from each other or the same. Epoxy resins having the same third aromatic ring group disposed at both ends of the skeleton can be easily produced, and are therefore preferred.

In the epoxy resin of the present embodiment, any one or more of the first aromatic ring group, the second aromatic ring group, and the third aromatic ring group is preferably a phenylene group which may have a substituent, in order to obtain an epoxy resin which can give a cured product having higher thermal conductivity. The phenylene group as the phenylene group which may have a substituent may be any of an o-phenylene group, an m-phenylene group and a p-phenylene group. The phenylene group is particularly preferably a p-phenylene group in order to be an epoxy resin having a skeleton exhibiting high orientation.

In the epoxy resin of the present embodiment, either one of the first aromatic ring group and the second aromatic ring group is more preferably a p-phenylene group. Such an epoxy resin is preferable because a cured product having a higher thermal conductivity can be obtained.

In the epoxy resin of the present embodiment, it is particularly preferable that the second aromatic ring group is a p-phenylene group. Such an epoxy resin can provide a cured product having a further higher thermal conductivity.

In the epoxy resin of the present embodiment, the substituent of the first aromatic ring group, the second aromatic ring group, and the third aromatic ring group is preferably any one selected from a methyl group, a trifluoromethyl group, a halogen group, and a nitro group, and may be appropriately determined depending on the use of the epoxy resin, and the like, and is not particularly limited. Among these substituents, methyl, trifluoromethyl and halogen groups are preferable, and methyl is particularly preferable, from the viewpoints of chemical stability and reduction of environmental load.

In the epoxy resin of the present embodiment, the terminal group having an epoxy group bonded to the third aromatic ring group is preferably a group in which an epoxy group is bonded to a linking group having one or more of a methylene group, an ether bond, an ester bond, a ketone group, and an amide bond, and can be appropriately determined depending on the use of the epoxy resin and the like. When the terminal group having an epoxy group bonded to the third aromatic ring group is a group in which an epoxy group is bonded to any of the above-mentioned linking groups, the bond between the terminal group having an epoxy group and the skeleton is not too rigid, and the balance between orientation and molecular mobility is good. As a result, the epoxy resin has sufficient solubility in a solvent and can provide a cured product having good thermal conductivity.

The terminal group having an epoxy group in the epoxy resin of the present embodiment is a group that can be easily introduced into the skeleton of the epoxy resin, and specifically, any of the following formulas (3) to (8) is preferable in order to obtain an epoxy resin having more excellent thermal conductivity. The terminal group may be appropriately determined depending on the use of the epoxy resin and the like. In order to produce an epoxy resin having higher thermal conductivity, the terminal group having an epoxy group is particularly preferably a terminal group represented by formula (3) or formula (7). In order to facilitate the synthesis of the epoxy resin, the terminal group having an epoxy group is preferably a terminal group represented by formula (3).

Examples of the epoxy resin of the present embodiment include epoxy resins represented by the following general formula (1) or the following general formula (2).

(in the formula (1), Ar₁Each independently represents a first aromatic ring group which may have a substituent, Ar₂Each independently represents a second aromatic ring group which may have a substituent, Ar₃Each independently a third aromatic ring group which may have a substituent; each Z is independently a terminal group having an epoxy group; n is an integer of 0 or more. )

(in the formula (2), Ar₁Each independently represents a first aromatic ring group which may have a substituent, Ar₂Each independently represents a second aromatic ring group which may have a substituent, Ar₃Each independently a third aromatic ring group which may have a substituent; each Z is independently a terminal group having an epoxy group; n is an integer of 0 or more. )

The epoxy resin represented by the general formula (1) and the general formula (2) includes: a first aromatic ring unit represented by the formula (1) or (2) — O-Ar₁-O-represents), a second aromatic ring unit (represented by-CH in formula (1)₂-Ar₁-CH₂-represents (a), and a third aromatic ring unit (represented by-Ar in formula (1) and formula (2))₃-Z represents).

In the epoxy resin represented by general formula (1) and formula (2), the first aromatic ring unit has a first aromatic ring group (Ar in formula (1) and formula (2))₁Represents) and 2 ether oxygens bonded to the first aromatic ring group.

The second aromatic ring unit has a second aromatic ring group (Ar in formula (1) and formula (2))₂Represents) and 2 methylene groups bonded to the second aromatic ring group.

The third aromatic ring unit is represented by Ar of formulae (1) and (2)₃A third aromatic cyclic group and an end group having an epoxy group (represented by Z in formulae (1) and (2)) bonded to the third aromatic cyclic group.

The first aromatic ring group, the second aromatic ring group, and the third aromatic ring group contained in the epoxy resin represented by general formula (1) and general formula (2) may each have a substituent.

The epoxy resin represented by general formula (1) includes a skeleton in which first aromatic ring units and second aromatic ring units are alternately arranged in a chain shape, and has a skeleton in which both ends are terminated with the second aromatic ring units. In the epoxy resin represented by the general formula (1), methylene groups of the second aromatic ring unit are arranged at both ends of the skeleton, and the second aromatic ring unit is bonded to Ar of the general formula (1) through an ether oxygen₃The third aromatic ring group shown is bonded.

In addition, the general formula (2) The epoxy resin includes a skeleton in which first aromatic ring units and second aromatic ring units are alternately arranged in a chain, and has a skeleton in which both ends are terminated with the first aromatic ring units. In the epoxy resin represented by the general formula (2), ether oxygens of the first aromatic ring unit are arranged at both ends of the skeleton, and the first aromatic ring unit is bonded to Ar of the general formula (2) through a methylene group₃The third aromatic ring group shown is bonded.

Accordingly, both ends of the epoxy resin represented by the general formulae (1) and (2) are terminal groups having an epoxy group represented by Z in the formulae (1) and (2) bonded to the third aromatic ring group.

In the epoxy resin of the present embodiment, examples of the epoxy resin in which all of the first aromatic ring group, the second aromatic ring group and the third aromatic ring group are p-phenylene groups which may have a substituent include epoxy resins represented by the following general formula (10) or the following general formula (11).

(in the formula (10), R1-R20 are each independently any one selected from the group consisting of hydrogen, methyl, trifluoromethyl, a halogen group and a nitro group, Z is an epoxy-containing terminal group, and n is an integer of 0 or more.)

(in the formula (11), R1-R20 are each independently any one selected from the group consisting of hydrogen, methyl, trifluoromethyl, a halogen group and a nitro group, Z is an epoxy-containing terminal group, and n is an integer of 0 or more.)

The epoxy resin represented by general formula (10) or general formula (11) has a first aromatic ring unit composed of a p-phenylene group which may have a substituent as a first aromatic ring group and 2 ether oxygens arranged at the para-position with respect to the first aromatic ring group. The aromatic ring unit has a second aromatic ring unit composed of a p-phenylene group which may have a substituent as a second aromatic ring group and 2 methylene groups arranged at the para-position with respect to the first aromatic ring group. Further, the aromatic ring has a third aromatic ring unit composed of a p-phenylene group which may have a substituent as a third aromatic ring group and an epoxy group-containing terminal group (represented by Z in formulae (10) and (11)).

The epoxy resin represented by general formula (10) has a skeleton in which first aromatic ring units and second aromatic ring units are alternately arranged and both ends of the skeleton are terminated with the second aromatic ring units. Further, the terminal group containing an epoxy group and the ether oxygen bonded to the skeleton are disposed para to the p-phenylene group which may have a substituent as the third aromatic ring group, and the third aromatic ring unit is disposed symmetrically with respect to the skeleton. Thus, the skeleton of the epoxy resin represented by the general formula (10) exhibits liquid crystallinity and high orientation. Therefore, the epoxy resin represented by the general formula (10) can give a cured product having a further excellent thermal conductivity.

The epoxy resin represented by general formula (11) has a skeleton in which first aromatic ring units and second aromatic ring units are alternately arranged and both ends of the skeleton are terminated with the first aromatic ring units. Further, the terminal group containing an epoxy group and the methylene group bonded to the skeleton are disposed para to the p-phenylene group which may have a substituent as the third aromatic ring group, and the third aromatic ring unit is disposed symmetrically with respect to the skeleton. Thus, the skeleton of the epoxy resin represented by the general formula (11) exhibits liquid crystallinity and high orientation. Therefore, the epoxy resin represented by the general formula (11) can give a cured product having a further excellent thermal conductivity.

In the epoxy resin of the present embodiment, examples of the epoxy resin in which the first aromatic ring group and the third aromatic ring group are p-phenylene groups which may have a substituent, and the second aromatic ring group is p-phenylene group include epoxy resins represented by the following general formula (9).

(in the formula (9), R1-R4, R9-R12, R17-R20 are each independently any one selected from hydrogen, methyl, trifluoromethyl, a halogen group, and a nitro group; Z is each independently a terminal group having an epoxy group; n is an integer of 0 or more.)

In the epoxy resin represented by general formula (9), the first aromatic ring group and the third aromatic ring group are p-phenylene groups which may have a substituent, and the second aromatic ring group is p-phenylene group. Therefore, the epoxy resin represented by the general formula (9) has a skeleton in which methylene groups are bonded to both sides of a p-phenylene group, and exhibits a higher orientation. Therefore, according to the epoxy resin represented by the general formula (9), a cured product having a further excellent thermal conductivity can be obtained. In the epoxy resin represented by the general formula (9), the second aromatic ring group is an unsubstituted p-phenylene group, and therefore, the raw material can be easily obtained.

In the epoxy resin represented by the general formula (9), the terminal group containing an epoxy group and the ether oxygen bonded to the skeleton are disposed para to the p-phenylene group which may have a substituent as the third aromatic ring group. Therefore, in the epoxy resin represented by the general formula (9), for example, the bonding portion between the terminal group containing an epoxy group and the skeleton is not too rigid and the balance between orientation and molecular mobility is good, compared with the case where the terminal group containing an epoxy group and the methylene group bonded to the skeleton are disposed at a para position with respect to the p-phenylene group which may have a substituent as the third aromatic ring group. As a result, the epoxy resin represented by the general formula (9) has sufficient solubility in a solvent, and a cured product having good thermal conductivity can be obtained.

In the epoxy resin represented by the general formula (1), the formula (2), the formula (9) to the formula (11), Z is preferably a group having an epoxy group as a terminal group and bonded to a connecting group having at least one of a methylene group, an ether bond, an ester bond, a ketone group, and an amide bond, and more preferably any of the formulas (3) to (8). In the epoxy resins represented by the general formulae (1), (2), (9) to (11), when Z is any of the formulae (3) to (8), the epoxy resin having a further excellent thermal conductivity is obtained. In addition, since the groups represented by the formulae (3) to (8) can be easily introduced into the skeleton of the epoxy resin, when Z is any of the formulae (3) to (8), the epoxy resin can be easily produced.

In particular, in the epoxy resin represented by the general formula (9), Z is preferably a terminal group represented by the formula (3). In such an epoxy resin, a third aromatic ring group which is a p-phenylene group which may have a substituent and an end group having an epoxy group represented by formula (3) bonded to the third aromatic ring group are bonded to both ends of the skeleton. Therefore, the third aromatic ring group and the terminal group having an epoxy group do not inhibit the formation of a smectic liquid crystal phase in the epoxy resin, and a cured product having good thermal conductivity can be obtained.

In the epoxy resin represented by the general formula (1), the formula (2), the formula (9) to the formula (11), n represents the number of repeating units shown in parentheses. In the epoxy resin represented by the general formula (1), the formula (2), the formula (9) to the formula (11), n is an integer of 0 or more. N in the formulae (1), (2), and (9) to (11) is 0 or more in order to obtain the effect of improving the thermal conductivity of the cured product by having the above skeleton, and n is preferably 1 or more, and more preferably 2 or more in order to obtain the effect of improving the thermal conductivity of the cured product by having the above skeleton, which is more remarkable. The upper limit of n in the formulae (1), (2), (9) to (11) is not particularly limited, but is preferably 10 or less in order to ensure solubility of the epoxy resin in a solvent, and more preferably 6 or less in order to obtain an epoxy resin having better solubility in a solvent.

n may be selected as desired. For example, n may be any one of integers shown as 0, 1,2, 3, 4,5, 6, 7, 8, 9, and 10. For example, the lower limit of n may be any of integers in the range of 0 to 10, and the upper limit of n may be any of integers in the range of 0 to 10. Specifically, n may be an integer in the range of 0 to 10, an integer in the range of 0 to 9, an integer in the range of 0 to 8, an integer in the range of 0 to 6, an integer in the range of 0 to 5, an integer in the range of 0 to 4, an integer in the range of 0 to 3, or an integer in the range of 0 to 2. n may be an integer in the range of 1 to 9, an integer in the range of 1 to 8, an integer in the range of 1 to 6, an integer in the range of 1 to 5, an integer in the range of 1 to 4, an integer in the range of 1 to 3, or an integer in the range of 1 to 2. n may be 1. n may be an integer in the range of 2 to 9, an integer in the range of 2 to 8, an integer in the range of 2 to 6, an integer in the range of 2 to 5, an integer in the range of 2 to 4, or an integer in the range of 2 to 3.

The skeleton of the epoxy resin of the present embodiment has a repeating unit composed of 1 first aromatic ring unit and 1 second aromatic ring unit. The epoxy resin of the present embodiment may be a mixture containing a plurality of epoxy resins having different numbers of repeating units, or may be a single epoxy resin having the same number of repeating units.

When the epoxy resin of the present embodiment is a mixture containing a plurality of epoxy resins having different numbers of repeating units, the average polymerization degree as the average value of the number of repeating units of the epoxy resin contained in the mixture is preferably 1.0 to 6.0, and more preferably 2.0 to 5.0. When the average polymerization degree is 1.0 or more, the epoxy resin has a cured product with a further higher thermal conductivity. When the average polymerization degree is 6.0 or less, the epoxy resin has better solubility in a solvent.

In the epoxy resin of the present embodiment, even if n in the epoxy resin represented by general formula (1), formula (2), formula (9) to formula (11) is 0, the epoxy resin has the first structure or the second structure between the terminal groups having an epoxy group disposed at both ends. The first structure is a structure in which an aromatic ring group, an ether oxygen group, a methylene group, an aromatic ring group, a methylene group, an ether oxygen group, and an aromatic ring group are bonded in this order. The second structure is a structure in which an aromatic ring group, a methylene group, an ether oxygen group, an aromatic ring group, an ether oxygen group, a methylene group, and an aromatic ring group are bonded in this order. The first structure and the second structure are mesogens exhibiting liquid crystallinity, and have a structure in which an aromatic ring group imparting rigidity, a methylene group imparting mobility, and an ether oxygen are arranged in a specific order. Thus, according to the epoxy resin of the present embodiment, a cured product having high thermal conductivity can be obtained.

In the epoxy resins represented by the general formulae (9) to (11), it is preferable that any one of R1 to R4 is methyl and the others are hydrogen, any one of R9 to R12 is methyl and the others are hydrogen, and any one of R17 to R20 is methyl and the others are hydrogen. In other words, the first aromatic ring group and the third aromatic ring group in the epoxy resin represented by general formulae (9) to (11) are preferably p-phenylene groups having 1 methyl group. In this case, for example, as compared with the case where all of the first aromatic ring group, the second aromatic ring group, and the third aromatic ring group are p-phenylene groups having no substituent, the crystallinity of the skeleton is reduced, and the smectic liquid crystal phase is stabilized. As a result, an epoxy resin capable of providing a cured product having excellent thermal conductivity is obtained.

In the epoxy resin of the present embodiment, the first aromatic ring group and the third aromatic ring group are preferably the same. When the first aromatic ring group and the third aromatic ring group are the same, the epoxy resin can be easily produced and has excellent productivity, as compared with the case where the first aromatic ring group and the third aromatic ring group are different.

In particular, when the first aromatic ring group and the third aromatic ring group are the same and the second aromatic ring group is a p-phenylene group, an epoxy resin which can be easily produced and has excellent productivity is obtained.

In the epoxy resin of the present embodiment, the first aromatic ring group and the second aromatic ring group may be the same or different. That is, the first aromatic ring group and the second aromatic ring group may both be a p-phenylene group having no substituent. In this case, the raw material is preferably easily available. When the first aromatic ring group and the second aromatic ring group are different from each other, the symmetry of the skeleton structure is lower than when the first aromatic ring group and the second aromatic ring group are the same. Therefore, the crystallinity of the epoxy resin is reduced, and the smectic liquid crystal phase is stabilized. As a result, an epoxy resin capable of providing a cured product having excellent thermal conductivity is obtained.

Specific examples of the preferred epoxy resin of the present embodiment include epoxy resins represented by general formula (a) and general formula (B).

The epoxy resin represented by the general formula (a) is an epoxy resin in which the first aromatic ring group and the third aromatic ring group are p-phenylene groups having a methyl group, the second aromatic ring group is p-phenylene groups, the terminal group having an epoxy group is a terminal group represented by the formula (3), and the terminal group having an epoxy group and the ether oxygen bonded to the skeleton are arranged para to the p-phenylene group which may have a substituent as the third aromatic ring group.

The epoxy resin represented by the general formula (B) is an epoxy resin in which the first aromatic ring group and the third aromatic ring group are p-phenylene groups having a methyl group, the second aromatic ring group is p-phenylene groups, the terminal group having an epoxy group is a terminal group represented by the formula (7), and the terminal group having an epoxy group and the ether oxygen bonded to the skeleton are arranged para to the p-phenylene group which may have a substituent as the third aromatic ring group.

(in the formula (A), n is an integer of 0 or more.)

(in the formula (B), n is an integer of 0 or more.)

Process for producing epoxy resin "

The epoxy resin of the present embodiment can be produced, for example, by the following method.

A1 st raw material which is an aromatic compound having 2 phenolic hydroxyl groups and a 2 nd raw material which is an aromatic compound having a monohalomethyl group are prepared.

Then, the 1 st and 2 nd starting materials are subjected to a two-molecule nucleophilic substitution reaction (S)_N2 reaction), a 1 st precursor compound having a structure to be a source of the skeleton of the epoxy resin of the present embodiment is synthesized. The conditions for reacting the 1 st material with the 2 nd material may be appropriately determined depending on the combination of the 1 st material and the 2 nd material, and are not particularly limited.

The 1 st raw material used in the method for producing an epoxy resin according to the present embodiment is an aromatic compound having 2 phenolic hydroxyl groups, and is appropriately selected depending on the structure of the epoxy resin to be produced. Examples of the 1 st raw material include: methyl hydroquinone, tetramethyl hydroquinone, trimethyl hydroquinone, 2- (trifluoromethyl) -1, 4-benzenediol, fluorohydroquinone, chlorohydroquinone, bromohydroquinone, 2, 5-dihydroxynitrobenzene, tetrafluorohydroquinone, tetrachlorohydroquinone, tetrabromohydroquinone, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 4'-dihydroxybiphenyl, 3',5,5'-tetramethyl biphenyl-4,4' -diol, and the like.

The 2 nd raw material used in the method for producing an epoxy resin according to the present embodiment is an aromatic compound having a monohalomethyl group, and is appropriately selected depending on the structure of the epoxy resin to be produced. Examples of the 2 nd raw material include: alpha, alpha '-dichloro-p-xylene, 1,4-bis (chloromethyl) -2-methylbenzene, 3,6-bis (chloromethyl) durene, 1,4-bis (bromomethyl) -2-fluorobenzene, 1,4-bis (bromomethyl) -2-chlorobenzene, 2-bromo-1,4-bis (bromomethyl) benzene, 1,4-bis (chloromethyl) -2-nitrobenzene, 1,4-bis (bromomethyl) -2,3,5,6-tetrafluorobenzene, alpha', 2,3,5,6-hexachloro-p-xylene, 1,2,4,5-tetrabromo-3,6-bis (bromomethyl) benzene, 1,2-dibromo-3,6-bis (chloromethyl) -4,5-dimethylbenzene, 1,4-bis (bromomethyl) -2,5-dimethylbenzene, 4' -bis (chloromethyl) biphenyl, 2,6-bis (bromomethyl) naphthalene, 1,5-bis (chloromethyl) naphthalene, and the like.

Subsequently, the 1 st precursor compound thus obtained and the 3 rd raw material are reacted with each other to synthesize a 2 nd precursor compound. The conditions for reacting the 1 st precursor compound with the 3 rd raw material may be appropriately determined depending on the combination of the 1 st precursor compound and the 3 rd raw material, and are not particularly limited.

The 3 rd raw material used in the method for producing an epoxy resin according to the present embodiment is appropriately selected depending on the structure of the terminal group having an epoxy group, the structure of the third aromatic ring group, and the like in the produced epoxy resin. In addition, as the 3 rd raw material, when the elements of the 1 st precursor compound synthesized in advance at both ends of the skeleton have the structure derived from the 1 st raw material and the structure derived from the 2 nd raw material, different materials are used.

When the 1 st precursor compound has a structure in which the elements disposed at both ends of the skeleton are derived from the 1 st raw material, an aromatic compound having a monohalomethyl group is used as the 3 rd raw material in the same manner as the 2 nd raw material. Specifically, examples thereof include: α, α '-dichloro-p-xylene, 1,4-bis (chloromethyl) -2-methylbenzene, 3,6-bis (chloromethyl) durene, 1,4-bis (bromomethyl) -2-fluorobenzene, 1,4-bis (bromomethyl) -2-chlorobenzene, 2-bromo-1,4-bis (bromomethyl) benzene, 1,4-bis (chloromethyl) -2-nitrobenzene, 1,4-bis (bromomethyl) -2,3,5,6-tetrafluorobenzene, α', 2,3,5,6-hexachloro-p-xylene, 1,2,4,5-tetrabromo-3,6-bis (bromomethyl) benzene, 1,2-dibromo-3,6-bis (chloromethyl) -4,5-dimethylbenzene, 1,4-bis (bromomethyl) -2,5-dimethylbenzene, 4' -bis (chloromethyl) biphenyl, 2,6-bis (bromomethyl) naphthalene, 1,5-bis (chloromethyl) naphthalene, and the like.

When the 1 st precursor compound has a structure in which the elements disposed at both ends of the skeleton are derived from the 2 nd raw material, an aromatic compound having 2 phenolic hydroxyl groups can be used as the 3 rd raw material, as in the 1 st raw material. Further, as the 3 rd raw material, an aromatic compound having 1 phenolic hydroxyl group and an amino group or a carboxyalkyl group may be used. Specifically, examples thereof include: methyl hydroquinone, tetramethylhydroquinone, trimethylhydroquinone, 2- (trifluoromethyl) -1, 4-benzenediol, fluorohydroquinone, chlorohydroquinone, bromohydroquinone, 2, 5-dihydroxynitrobenzene, tetrafluorohydroquinone, tetrachlorohydroquinone, tetrabromohydroquinone, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 4'-dihydroxybiphenyl, 3',5,5'-tetramethylbiphenyl-4,4' -diol, 4-aminophenol, 4-amino-m-cresol, methyl 4-hydroxybenzoate, and the like.

Next, the epoxy resin of the present embodiment can be obtained by reacting a 2 nd precursor compound with a compound containing a structure that is a source of an end group having an epoxy group, the 2 nd precursor compound being obtained by reacting a 1 st precursor compound with a 3 rd raw material.

The epoxy resin of the present embodiment can be produced, for example, by a method in which the 2 nd precursor compound is reacted with an olefin compound, a group derived from the olefin compound is bonded to the end of the 2 nd precursor compound, and then the end of the group derived from the olefin compound is converted to an epoxy group using an oxidizing agent such as m-chloroperbenzoic acid (mCPBA) or hydrogen peroxide.

In the case of producing an epoxy resin having the same structure as the first aromatic ring group and the third aromatic ring group or the same structure as the second aromatic ring group and the third aromatic ring group as the epoxy resin, the step of reacting the 1 st precursor compound with the 3 rd starting material may be omitted.

Specifically, an epoxy resin may be obtained by reacting the 1 st precursor compound with a compound having a structure that is a source of an end group having an epoxy group. In addition, an epoxy resin may be produced by a method in which a group derived from an olefin compound is bonded to the end of a 1 st precursor compound by reacting the 1 st precursor compound with an olefin compound, and then the end of the group derived from the olefin compound is converted to an epoxy group using an oxidizing agent such as m-chloroperbenzoic acid (mCPBA) or hydrogen peroxide.

The epoxy resin obtained by the production method of the present embodiment has, between the terminal groups having the reactive groups respectively disposed at both ends: a first structure in which an aromatic ring group, an ether oxygen group, a methylene group, an aromatic ring group, a methylene group, an ether oxygen group, and an aromatic ring group are bonded in this order; and/or a second structure in which an aromatic ring group, a methylene group, an ether oxygen group, an aromatic ring group, an ether oxygen group, a methylene group, and an aromatic ring group are bonded in this order.

In the method for producing an epoxy resin according to the present embodiment, it is preferable to simultaneously produce a mixture containing a plurality of epoxy resins having different numbers of repeating units. When a cured product is produced using the epoxy resin of the present embodiment, it is sometimes preferable to mix a plurality of epoxy resins of the present embodiment and use them as needed for use. When a mixture containing a plurality of epoxy resins having different numbers of repeating units is simultaneously produced, a process of mixing a plurality of epoxy resins of the present embodiment may not be performed when producing a cured product using the epoxy resin of the present embodiment, and a cured product can be efficiently produced.

In the method for producing an epoxy resin according to the present embodiment, after a mixture containing a plurality of epoxy resins having different numbers of repeating units is simultaneously produced, a single epoxy resin having a specific molecular weight may be separated from the mixture of the plurality of epoxy resins by a known method as needed.

The epoxy resin of the present embodiment preferably includes a skeleton having a symmetrical structure in which the first aromatic ring unit and the second aromatic ring unit are alternately arranged. The skeleton is a mesogen element exhibiting liquid crystallinity, and has a structure in which an aromatic ring group (a first aromatic ring group and a second aromatic ring group) for imparting rigidity, a methylene group for imparting mobility, and an ether oxygen are arranged in a specific order. Thus, the epoxy resin of the present embodiment can stabilize a smectic liquid crystal phase by appropriate mobility of mesogens themselves even without having a long side chain as seen in a normal liquid crystal molecule. Therefore, the epoxy resin of the present embodiment has high orientation, and curing the epoxy resin of the present embodiment can provide a cured product having a smectic liquid crystal structure and high thermal conductivity with suppressed phonon scattering.

"resin composition"

The resin composition of the present embodiment contains the above-described epoxy resin of the present embodiment as a resin component, and may contain only 1 kind of epoxy resin of the present embodiment, or may contain 2 or more kinds.

The resin composition of the present embodiment preferably contains the epoxy resin of the present embodiment described above as a resin component, and further contains a curing agent and a curing accelerator (catalyst).

Examples of the curing agent include: p-phenylenediamine, 1, 5-diaminonaphthalene, hydroquinone, 2,6-dihydroxynaphthalene, phloroglucinol, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-aminobenzoic acid, phenol resin, polyamidoamine, and the like. Among the above, 4-aminobenzoic acid is particularly preferably used as the curing agent in order to obtain a cured product having a higher thermal conductivity.

The amount of the curing agent can be arbitrarily selected, and for example, the total amount of functional groups that can be cured with epoxy groups is usually 0.5 to 1.5 equivalent times, preferably 0.9 to 1.1 equivalent times, based on the total amount of epoxy groups in the resin component.

As the curing accelerator, for example, a basic organic compound having a high boiling point can be used. Specifically, the compound has a boiling point of 200 ℃ or higher and is selected from tertiary amines, tertiary phosphines, 4-Dimethylaminopyridine (DMAP), imidazoles and the like. Among them, 2-ethyl-4-methylimidazole (2E4MZ) and 1- (2-cyanoethyl) -2-phenylimidazole, which are imidazole-based epoxy resin curing agents, are preferably used as the curing accelerator, particularly from the viewpoint of ease of handling.

The content of the curing accelerator in the resin composition may be arbitrarily selected, and is, for example, 0 to 5 parts by mass relative to 100 parts by mass of the total of the resin component and the curing agent. The amount of the surfactant may be 0.5 to 5 parts by mass, 1 to 3 parts by mass, 2 to 4 parts by mass or the like.

The resin composition of the present embodiment may contain a resin component other than the epoxy resin of the present embodiment as needed within a range in which the effects of the epoxy resin of the present embodiment can be obtained. The resin component other than the epoxy resin of the present embodiment may contain 1 or 2 or more kinds of compounds such as an epoxy compound such as 4,4' -bisphenol diglycidyl ether, a compound having an amino group such as p-phenylenediamine, and a compound having an amide group such as sulfonamide.

The resin composition of the present embodiment may contain inorganic particles as needed. As the inorganic particles, there can be mentioned: boron nitride particles, magnesium oxide particles, aluminum hydroxide particles, aluminum nitride particles, silica particles, and the like. As the inorganic particles, one of these particles may be used alone, or two or more of these particles may be used in combination.

The content of the inorganic particles may be arbitrarily selected, and is preferably 200 to 700 parts by mass, and more preferably 300 to 600 parts by mass, based on 100 parts by mass of the total of the resin composition components other than the inorganic particles. The amount of the organic solvent may be 200 to 500 parts by mass, 200 to 400 parts by mass, 200 to 300 parts by mass, or 400 to 500 parts by mass. When the content of the inorganic particles is 200 parts by mass or more, the effect of improving the thermal conductivity of the cured product of the resin composition becomes remarkable. When the content of the inorganic particles is 700 parts by mass or less, sufficient moldability can be obtained when a resin substrate is molded using a cured product of the resin composition.

The resin composition of the present embodiment may contain a solvent as needed. As the solvent, there may be mentioned: ketones such as acetone and Methyl Ethyl Ketone (MEK), alcohols such as methanol, ethanol and isopropanol, aromatic compounds such as toluene and xylene, ethers such as Tetrahydrofuran (THF) and 1, 3-dioxolane, esters such as ethyl acetate and γ -butyrolactone, and amides such as N, N-Dimethylformamide (DMF) and N-methylpyrrolidone. As the solvent, one of these solvents may be used alone, or two or more of them may be used in combination.

The content of the solvent in the resin composition may be selected as needed, and is, for example, 0 to 500 parts by mass with respect to 100 parts by mass of the total of the resin component and the curing agent. The amount of the surfactant may be 0 to 400 parts by mass, 5 to 300 parts by mass, 10 to 200 parts by mass, 100 to 200 parts by mass or the like.

The resin composition may contain any other components than the above components as required. As the optional components, there may be mentioned: coupling agents such as silane coupling agents and titanate coupling agents, flame retardants such as halogens, plasticizers, lubricants, and the like.

The resin composition of the present embodiment can be produced, for example, by a method of mixing the resin component containing the epoxy resin of the present embodiment described above, a curing agent, a curing accelerator, and other components contained as necessary.

Since the resin composition of the present embodiment contains the epoxy resin of the present embodiment described above, a cured product having high thermal conductivity can be obtained by curing the epoxy resin.

Resin sheet "

Fig. 1 is a schematic perspective view showing an example of a resin sheet and a resin substrate according to an embodiment. The resin sheet 12 shown in fig. 1 is a sheet obtained by molding a resin composition. The resin sheet 12 may contain the resin composition as it is, or may contain a part or all of the resin composition in a B-staged (semi-cured) state.

Fig. 2 is a sectional view taken along line ii-ii of fig. 1. Fig. 2 shows a cross section when the resin sheet 12 is cut in the thickness direction. The resin sheet 12 includes a core 30 and a resin component 22 that penetrates the core 30 and covers both surfaces of the core 30. The circle in fig. 2 indicates the glass fiber contained in the core material 30. The resin component 22 may be an uncured resin composition, or may be a partially or entirely semi-cured product of a resin composition.

Examples of the core material 30 include a woven fabric and a nonwoven fabric. Examples of the material of the woven fabric and the nonwoven fabric include: and at least one fiber selected from glass fibers, carbon fibers, metal fibers, natural fibers, and synthetic fibers such as polyester fibers and polyamide fibers.

The resin sheet 12 can be produced as follows.

The resin composition is impregnated into the core material 30 by a method such as coating or impregnation. When the resin composition contains a solvent, the resin composition is impregnated into the core material 30, and then heated and dried to remove the solvent. The heating condition for removing the solvent in the resin composition can be selected arbitrarily, and for example, it can be set to about 1 to 120 minutes at 60 to 150 ℃, and preferably about 3 to 90 minutes at 70 to 120 ℃.

In the case where a part or all of the resin component 22 is a semi-cured product of the resin composition, the resin sheet 12 is partially or completely cured and semi-cured by heating to remove the solvent in the resin composition and simultaneously curing the part or all of the resin composition infiltrated into the core material 30. After the heating for removing the solvent in the resin composition, a part or the whole of the resin composition infiltrated into the core material 30 may be cured to be in a semi-cured state under the same conditions as the heating for removing the solvent in the resin composition.

Through the above steps, the resin sheet 12 having the resin component 22 composed of the uncured or at least partially semi-cured resin composition can be obtained.

The resin sheet 12 shown in fig. 1 is a sheet obtained by molding the resin composition of the present embodiment, and therefore, by curing the resin composition by heat treatment, a resin cured product having high thermal conductivity can be obtained. Therefore, the resin sheet 12 shown in fig. 1 is suitable as a material of the resin substrate.

The resin sheet 12 of the present embodiment can be used as a precursor of a resin substrate (cured resin) containing a cured product of a resin composition.

In the present embodiment, the resin sheet 12 is described by taking as an example a resin sheet having a core material 30 as shown in fig. 2, but the resin sheet of the present disclosure may be a resin sheet formed of only a resin component without a core material.

Further, a metal foil such as a copper foil may be laminated on the surface of the resin sheet.

Cured resin and resin substrate "

The resin substrate 10 (cured resin product) of the present embodiment shown in fig. 1 and 2 is obtained by thermally curing a resin component 22 contained in a resin sheet 12, and contains a cured product 20 of the resin composition of the present embodiment.

The resin substrate 10 of the present embodiment can be manufactured by a method of heating the resin sheet 12 using the resin sheet 12 of the present embodiment described above as a precursor.

Specifically, the resin sheet 12 of the present embodiment is heated to thermally cure the resin component 22 in an uncured state or a semi-cured state, thereby producing the cured product 20. The heating conditions for curing the resin component 22 may be selected as needed, and are preferably about 1 to 300 minutes at 100 to 250 ℃. Heating for curing the resin component 22 may be performed under pressure or reduced pressure as necessary.

The resin substrate 10 of the present embodiment is a resin cured product containing a cured product of the resin composition of the present embodiment, and therefore has high thermal conductivity.

In the present embodiment, as the resin substrate 10 (cured resin), as shown in fig. 2, a resin substrate including the core material 30 and the cured product 20 covering the core material 30 is described as an example, but the cured resin and the resin substrate of the present disclosure may be constituted by only a cured product of the resin composition.

The resin cured product and the resin substrate of the present disclosure can be produced by heating an amorphous resin composition, for example, as in the case where the resin composition is used as an adhesive.

Laminated substrate "

Fig. 3 is a schematic perspective view of a laminated substrate according to an embodiment. FIG. 4 is a cross-sectional view taken along line IV-IV of FIG. 3. Fig. 4 shows a cross section when the laminated substrate is cut in the laminating direction. As shown in fig. 3 and 4, the laminate substrate 50 is formed by laminating and integrating a plurality of resin substrates 10 shown in fig. 2.

The laminated substrate 50 can be manufactured by, for example, heating a plurality of resin substrates 10 stacked on one another. The laminated substrate 50 may be manufactured by a method in which a plurality of resin sheets 12 are stacked and heated to thermally cure a resin component in an uncured state or a semi-cured state to obtain a cured product 20. The heating conditions for the plurality of resin substrates 10 and the plurality of resin sheets 12 may be, for example, about 1 to 300 minutes at 100 to 250 ℃.

When the plurality of resin substrates 10 or the plurality of resin sheets 12 are heated, pressurization may be applied as necessary. The pressurizing condition may be, for example, about 0.1 to 10 MPa. When the plurality of resin substrates 10 or the plurality of resin sheets 12 are heated, pressurization is not essential, and heating may be performed under reduced pressure or vacuum.

The laminated substrate 50 of the present embodiment has high thermal conductivity because the resin substrate 10 is laminated thereon.

In the present embodiment, the laminated substrate 50 is described by taking as an example the laminated substrate in which the plurality of resin substrates 10 shown in fig. 2 containing the cured product 20 of the resin composition are laminated, but the laminated substrate of the present disclosure may be any laminated substrate as long as at least one of the plurality of resin substrates is a resin substrate containing the cured product of the resin composition of the present disclosure.

The laminate substrate of the present disclosure may be, for example, a metal laminate having a metal layer on the upper surface and/or the lower surface. In this case, various known metal layers can be appropriately selected and used as the metal layer. Specifically, as the metal layer, for example, a metal plate or a metal foil made of a metal such as copper, nickel, or aluminum can be used. The thickness of the metal layer is not particularly limited, and may be, for example, about 3 to 150 μm. As the metal layer, a metal layer obtained by etching and/or drilling a metal plate or a metal foil may be used.

While the embodiments of the present disclosure have been described above with reference to the drawings, the configurations and combinations thereof in the embodiments are merely examples, and additions, omissions, substitutions, and other modifications of the configurations can be made without departing from the scope of the present disclosure.

Examples

< Synthesis of epoxy resin >

Synthesis examples 1 to 52 "

An epoxy resin represented by the general formula (1), namely Ar in the formula (1), was synthesized by the method shown below₁A first aromatic ring radical shown and Ar₃The third aromatic ring group shown is the same as that of the epoxy resin of synthesis examples 1 to 52, wherein Z in formula (1) is a terminal group shown in formula (3).

The 1 st material shown in tables 1 to 2 and the 2 nd material shown in tables 1 to 2 were weighed in a three-necked flask at the ratios shown in tables 1 to 2, respectively, and dissolved in 1L of Tetrahydrofuran (THF) to obtain a 1 st mixed solution. Thereafter, the 1 st mixed solution was refluxed (reflux) in a nitrogen stream to remove dissolved oxygen in the 1 st mixed solution. Subsequently, potassium carbonate in an amount (mole number) 2 times that of the 2 nd raw material was added to the 1 st mixed solution, and the mixture was reacted while maintaining a reflux state for 12 hours.

After completion of the reaction, the obtained suspension was poured into water, stirred for 30 minutes, and the resulting precipitate was collected by filtration. The recovered precipitate was vacuum-dried for 12 hours or more, dissolved in 1L of THF, and epichlorohydrin (300g) was added to prepare a 2 nd mixed solution. Thereafter, the 2 nd mixed solution was refluxed in a nitrogen gas flow, and dissolved oxygen in the 2 nd mixed solution was removed. Subsequently, a 50% aqueous solution (25g) of sodium hydroxide was added to the mixed solution 2, and the mixture was reacted while maintaining the reflux state for 12 hours.

After completion of the reaction, the obtained suspension was poured into water, stirred for 30 minutes, and the resulting precipitate was collected by filtration. The recovered precipitate was vacuum-dried for 12 hours or more to obtain epoxy resins of Synthesis examples 1 to 52.

Synthesis example 53 "

An epoxy resin represented by the general formula (1), namely Ar in the formula (1), was synthesized by the method shown below₁A first aromatic ring group and Ar₃The third aromatic ring group is p-phenylene having 1 methyl group, Ar₂The epoxy resin of synthesis example 53 in which the second aromatic ring group shown is an unsubstituted p-phenylene group and Z in formula (1) is a terminal group shown in formula (4).

The 1 st material shown in table 2 and the 2 nd material shown in table 2 were weighed in a three-necked flask at the ratios shown in table 2, respectively, and dissolved in 1L of Tetrahydrofuran (THF) to obtain a 1 st mixed solution. Thereafter, the 1 st mixed solution was refluxed in a nitrogen stream to remove dissolved oxygen in the 1 st mixed solution. Subsequently, potassium carbonate in an amount (mole number) 2 times that of the 2 nd raw material was added to the 1 st mixed solution, and the mixture was reacted while maintaining a reflux state for 12 hours.

After completion of the reaction, the obtained suspension was poured into water, stirred for 30 minutes, and the resulting precipitate was collected by filtration. The recovered precipitate was vacuum-dried for 12 hours or more, dissolved in 1L of THF, and added with 1-bromo-4-butene (40.5g, 0.30mol) to prepare a 2 nd mixed solution. Thereafter, the 2 nd mixed solution was refluxed in a nitrogen gas flow, and dissolved oxygen in the 2 nd mixed solution was removed. Subsequently, a 50% aqueous solution (25g) of sodium hydroxide was added to the mixed solution 2, and the mixture was reacted while maintaining the reflux state for 12 hours.

After completion of the reaction, the obtained suspension was poured into water, stirred for 30 minutes, and the resulting precipitate was collected by filtration. The collected precipitate was vacuum-dried for 12 hours or more, dissolved in chloroform, and m-chloroperbenzoic acid (mCPBA) (50g, 0.29mol) was added in several portions to prepare a 3 rd mixed solution. Thereafter, the 3 rd mixed solution was allowed to react at room temperature for 8 hours, and was concentrated under reduced pressure until the amount of the 3 rd mixed solution became about half the amount. The resulting suspension was poured into methanol (MeOH), stirred for 30 minutes, and the resulting precipitate was filtered and recovered. The recovered precipitate was vacuum-dried for 12 hours to obtain an epoxy resin of Synthesis example 53.

Synthesis example 54 "

An epoxy resin represented by the general formula (1), namely Ar in the formula (1), was synthesized by the method shown below₁The first aromatic ring group is p-phenylene having 1 methyl group, Ar₂A second aromatic ring group and Ar₃An epoxy resin of synthesis example 54 in which the third aromatic ring group shown is an unsubstituted p-phenylene group, and Z in formula (1) is a terminal group shown in formula (5).

The 1 st material shown in table 2 and the 2 nd material shown in table 2 were weighed in a three-necked flask at the ratios shown in table 2, respectively, and dissolved in 1L of Tetrahydrofuran (THF) to obtain a 1 st mixed solution. Thereafter, the 1 st mixed solution was refluxed in a nitrogen stream to remove dissolved oxygen in the 1 st mixed solution. Subsequently, potassium carbonate in an amount (mole number) 2 times that of the 1 st raw material was added to the 1 st mixed solution, and the mixture was kept under reflux for 12 hours to carry out a reaction.

Subsequently, methyl 4-hydroxybenzoate (22.8g, 0.15mol) and potassium carbonate (41.4g, 0.30mol) as a 3 rd raw material were added to the 1 st mixed solution to prepare a 2 nd mixed solution. The 2 nd mixed solution was maintained at reflux for 12 hours and allowed to react. Thereafter, water was added to the mixed solution 2, and the mixture was refluxed for 6 hours.

After the completion of the reaction, the obtained suspension was poured into water, neutralized with hydrochloric acid so that the pH became 6 or less, stirred for 30 minutes, and the resulting precipitate was collected by filtration. The recovered precipitate was vacuum-dried for 12 hours or more, dissolved in 1L of THF, and epichlorohydrin (300g) was added to prepare a 3 rd mixed solution. Thereafter, the 3 rd mixed solution was refluxed in a nitrogen stream to remove dissolved oxygen in the 3 rd mixed solution. Subsequently, potassium carbonate (41.5g, 0.3mol) was added to the 3 rd mixed solution, and the mixture was reacted while maintaining a reflux state for 12 hours.

After completion of the reaction, the obtained suspension was poured into water, stirred for 30 minutes, and the resulting precipitate was collected by filtration. The recovered precipitate was vacuum-dried for 12 hours or more to obtain an epoxy resin of Synthesis example 54.

Synthesis example 55 "

An epoxy resin represented by the general formula (1), namely Ar in the formula (1), was synthesized by the method shown below₁The first aromatic ring group is p-phenylene having 1 methyl group, Ar₂The second aromatic ring group is unsubstituted p-phenylene, Ar₃The epoxy resin of synthesis example 55 in which the third aromatic ring group shown is an unsubstituted p-phenylene group and Z in formula (1) is a terminal group represented by formula (6).

The precipitate used in the 3 rd mixed solution in Synthesis example 54 was dissolved in 1L of N, N-Dimethylformamide (DMF), and thionyl chloride (35.7g, 0.3mol) was added dropwise, and the mixture was reacted while maintaining at 90 ℃.

After completion of the reaction, thionyl chloride and the solvent were distilled off under reduced pressure, and DMF and triethylamine (30g) were added to the reaction vessel, followed by dropwise addition of 1-amino-3-propene (8.6g, 0.15mol) and stirring for 8 hours to effect a reaction. Thereafter, water was added to the obtained reaction mixture, and the mixture was stirred for 30 minutes, and the resulting precipitate was collected by filtration.

The recovered precipitate was dissolved in chloroform, and m-chloroperbenzoic acid (mCPBA) (50g, 0.29mol) was added in several portions and reacted at room temperature for 8 hours. The resulting suspension was concentrated under reduced pressure until the amount of the suspension became about half of the amount of the liquid, poured into methanol (MeOH), and stirred for 30 minutes, and the resulting precipitate was filtered and recovered. The recovered precipitate was vacuum-dried for 12 hours to obtain an epoxy resin of Synthesis example 55.

Synthesis example 56 "

An epoxy resin represented by the general formula (1), namely Ar in the formula (1), was synthesized by the method shown below₁A first aromatic ring group and Ar₃The third aromatic ring group is p-phenylene having 1 methyl group, Ar₂The second aromatic ring group is unsubstituted p-phenylene, and is represented by the formula (1)) The epoxy resin of Synthesis example 56 in which Z in (1) is a terminal group represented by the formula (7).

The 1 st material shown in table 2 and the 2 nd material shown in table 2 were weighed in a three-necked flask at the ratios shown in table 2, respectively, and dissolved in 1L of Tetrahydrofuran (THF) to obtain a 1 st mixed solution. Thereafter, the 1 st mixed solution was refluxed in a nitrogen stream to remove dissolved oxygen in the 1 st mixed solution. To this, potassium carbonate was added in an amount (mole number) 2 times as much as that of the 1 st raw material, and the reaction was carried out while maintaining a reflux state for 12 hours.

After completion of the reaction, 4-amino-m-cresol (36.9g, 0.3mol) as a 3 rd raw material and potassium carbonate (41.4g, 0.3mol) were added to the 1 st mixed solution to prepare a 2 nd mixed solution. Thereafter, the 2 nd mixed solution was refluxed for 12 hours. The resulting suspension was poured into water, stirred for 30 minutes, and the resulting precipitate was filtered and recovered. The recovered precipitate was vacuum-dried for 12 hours or more, dissolved in 1L of THF, and epichlorohydrin (400g) was added to prepare a 3 rd mixed solution. Thereafter, the 3 rd mixed solution was refluxed in a nitrogen stream to remove dissolved oxygen in the 3 rd mixed solution. Subsequently, a 50% aqueous solution (60g) of sodium hydroxide was added to the 3 rd mixed solution, and the mixture was refluxed for 12 hours to carry out a reaction.

After completion of the reaction, the obtained suspension was poured into water, stirred for 30 minutes, and the resulting precipitate was collected by filtration. The recovered precipitate was vacuum-dried for 12 hours or more to obtain an epoxy resin of Synthesis example 56.

Synthesis example 57 "

An epoxy resin represented by the general formula (1), namely Ar in the formula (1), was synthesized by the method shown below₁The first aromatic ring group is p-phenylene having 1 methyl group, Ar₂A second aromatic ring group and Ar₃An epoxy resin of synthesis example 57 in which the third aromatic ring group shown is an unsubstituted p-phenylene group, and Z in formula (1) is a terminal group represented by formula (7).

The 1 st material shown in table 2 and the 2 nd material shown in table 2 were weighed in a three-necked flask at the ratios shown in table 2, respectively, and dissolved in 1L of Tetrahydrofuran (THF) to obtain a 1 st mixed solution. Thereafter, the 1 st mixed solution was refluxed in a nitrogen stream to remove dissolved oxygen in the 1 st mixed solution. To this, potassium carbonate was added in an amount (mole number) 2 times as much as that of the 1 st raw material, and the reaction was carried out while maintaining a reflux state for 12 hours.

After completion of the reaction, 4-aminophenol (32.7g, 0.3mol) and potassium carbonate (41.4g, 0.3mol) as the 3 rd raw material were added to the first mixed solution to prepare a 2 nd mixed solution. Thereafter, the 2 nd mixed solution was refluxed for 12 hours. The resulting suspension was poured into water, stirred for 30 minutes, and the resulting precipitate was filtered and recovered. The recovered precipitate was vacuum-dried for 12 hours or more, dissolved in 1L of THF, and epichlorohydrin (400g) was added to prepare a 3 rd mixed solution. Thereafter, the 3 rd mixed solution was refluxed in a nitrogen stream to remove dissolved oxygen in the 3 rd mixed solution. Subsequently, a 50% aqueous solution (60g) of sodium hydroxide was added to the 3 rd mixed solution, and the mixture was refluxed for 12 hours to carry out a reaction.

After completion of the reaction, the obtained suspension was poured into water, stirred for 30 minutes, and the resulting precipitate was collected by filtration. The recovered precipitate was vacuum-dried for 12 hours or more to obtain an epoxy resin of Synthesis example 57.

Synthesis example 58 "

An epoxy resin represented by the general formula (1), namely Ar in the formula (1), was synthesized by the method shown below₁The first aromatic ring group is p-phenylene having 1 methyl group, Ar₂A second aromatic ring group and Ar₃An epoxy resin of synthesis example 58 in which the third aromatic ring group shown is an unsubstituted p-phenylene group, and Z in formula (1) is a terminal group represented by formula (8).

The 1 st material shown in table 2 and the 2 nd material shown in table 2 were weighed in a three-necked flask at the ratios shown in table 2, respectively, and dissolved in 1L of Tetrahydrofuran (THF) to obtain a 1 st mixed solution. Thereafter, the 1 st mixed solution was refluxed in a nitrogen stream to remove dissolved oxygen in the 1 st mixed solution. Subsequently, a 50% aqueous solution (80g) of sodium hydroxide was added to the mixed solution 1, and the mixture was refluxed for 12 hours to carry out a reaction.

After the reaction, the obtained reaction solution was cooled to room temperature, adjusted with hydrochloric acid so that the pH became 4 to 6, stirred for 30 minutes, and the resulting precipitate was collected by filtration. The recovered precipitate was vacuum-dried for 12 hours or more, dissolved in 1L of THF, and epichlorohydrin (300g) was added to prepare a 2 nd mixed solution. Thereafter, the 2 nd mixed solution was refluxed in a nitrogen gas flow, and dissolved oxygen in the 2 nd mixed solution was removed. Subsequently, potassium tert-butoxide (t-BuOK) (33.7g, 0.3mol) was added to the mixed solution 2, and the reaction was carried out while maintaining the reflux state for 12 hours.

After completion of the reaction, the obtained suspension was poured into water, stirred for 30 minutes, and the resulting precipitate was collected by filtration. The recovered precipitate was vacuum-dried for 12 hours or more to obtain an epoxy resin of Synthesis example 58.

[ Table 1]

[ Table 2]

1-1 to 1-16 in the 1 st raw materials shown in tables 1 to 2 are the following compounds.

[1 st Material ]

(1-1) Methylhydroquinone (Methylhydroquinone)

(1-2) Hydroquinone (Hydroquinone)

(1-3) Tetramethylhydroquinone

(1-4) Trimethylhydroquinone (Trimethylhydroquinone)

(1-5)2- (trifluoromethyl) -1, 4-benzenediol (2- (trifluoromethylphenyl) -1, 4-bezene diol)

(1-6) Fluorohydroquinone (Fluorohydroquinone)

(1-7) ChloroHydroquinone (Chlorohydroquinone)

(1-8) Bromohydrohydroquinone (Bromohydroquinone)

(1-9)2, 5-Dihydroxynitrobenzene (2, 5-Dihydroxynitrobenzene)

(1-10) Tetrafluorohydroquinone

(1-11) Tetrachlorohydroquinone

(1-12) tetrabromohydroquinone

(1-13)2, 6-Dihydroxynaphthalene (2,6-Dihydroxynaphthalene)

(1-14)1, 5-Dihydroxynaphthalene (1,5-Dihydroxynaphthalene)

(1-15)4, 4'-Dihydroxybiphenyl (4,4' -Dihydroxybiphenol)

(1-16)3, 3',5,5' -Tetramethylbiphenyl-4,4'-diol (3,3',5,5 '-tetramethyllbiphenyl-4, 4' -diol)

2-1 to 2-15 of the starting materials shown in tables 1 to 2 are the following compounds.

[2 nd starting Material ]

(2-1) α, α '-dichloro-p-xylene (α, α' -p-Dichloroxylene)

(2-2)1, 4-bis (chloromethyl) -2-METHYLBENZENE (1,4-bis (chloromethyl) -2-METHYLBENZENE)

(2-3)3, 6-bis (chloromethyl) durene (3,6-bis (chloromethyl) durene)

(2-4)1, 4-bis (bromomethyl) -2-fluorobenzene (1,4-bis (bromomethyl) -2-fluorobenzene)

(2-5)1, 4-bis (bromomethyl) -2-chlorobenzene (1,4-bis (bromomethyl) -2-chlorobenzene)

(2-6) 2-bromo-1,4-bis (bromomethyl) benzene (2-bromo-1,4-bis (bromomothyl) bezene)

(2-7)1, 4-bis (chloromethyl) -2-nitrobenzene (1,4-bis (chloromethyl) -2-nitrobenzene)

(2-8)1, 4-bis (bromomethyl) -2,3,5,6-tetrafluorobenzene (1,4-bis (bromomethyl) -2,3,5, 6-tetrafluorobenezene)

(2-9) α, α ', 2,3,5,6-Hexachloro-p-xylene (α, α', 2,3,5,6-Hexachloro-p-xylene)

(2-10)1,2,4, 5-tetrabromo-3,6-bis (bromomethyl) benzene (1,2,4,5-tetrabromo-3,6-bis-bromomethyl-benzene)

(2-11)1, 2-dibromo-3,6-bis (chloromethyl) -4,5-dimethylbenzene (1, 2-dibromoo-3, 6-bis (chloromethyl) -4, 5-dimethyllbenzene)

(2-12)1, 4-bis (bromomethyl) -2,5-dimethylbenzene (1,4-bis (bromomethyl) -2, 5-dimethyllbenzene)

(2-13)4, 4'-bis (chloromethyl) biphenyl (4,4' -bis (chloromethyl) biphenyl)

(2-14)2, 6-bis (bromomethyl) naphthalene (2,6-bis (bromomethyl) naphthalene)

(2-15)1, 5-bis (chloromethyl) naphthalene (1,5-bis (chloromethyl) naphthalene)

The epoxy resins obtained in synthesis examples 1 to 58 were confirmed for their structures by the following methods using a Gel Permeation Chromatograph (GPC) and a matrix assisted laser desorption/ionization time of flight mass spectrometer (MALDI TOF-MS).

First, the epoxy resins of Synthesis examples 1 to 58 were analyzed by using a Gel Permeation Chromatograph (GPC) (manufactured by Shimadzu corporation), a GPC column (GPC KF-2001 (manufactured by SHODEX)) as a column, and THF as an eluent, respectively, and as a result, it was found that the epoxy resins of Synthesis examples 1 to 57 were all mixtures of a plurality of epoxy resins having different molecular weights.

(measurement of the proportions (% by mol) of the respective components having different repeating units n)

The epoxy resins of synthesis examples 1 to 58 were separated by components (epoxy resins) having different molecular weights using a Gel Permeation Chromatograph (GPC). Then, for each component having a different molecular weight, the mass was measured in the cation detection mode using a matrix assisted laser desorption ionization time of flight mass spectrometer (MALDI TOF-MS) (manufactured by japan electronics), and the value of the peak having the strongest intensity was taken as the molecular weight. Then, the epoxy resins of Synthesis examples 1 to 58 were identified by comparing the measurement results of the molecular weights obtained and the molecular weights of the estimated molecular structures.

The measurement results of the molecular weight and the molecular weight of the estimated molecular structure are shown in tables 3 to 7.

The structures of the compounds identified in synthesis examples 1 to 58 are shown below.

The compounds of Synthesis examples 1 to 9 and 14 to 29 are represented by the general formula (C).

(in the formula (C), R_A、R_BAre the substituents shown in Table 8. Me in Table 8 represents a methyl group. n is a numerical value shown in tables 3 to 5. )

[ Table 8]

	Substituent RA	Substituent RB
			Synthesis example 1	Me	H
Synthesis example 2	Me	H
			Synthesis example 3	Me	H
Synthesis example 4	Me	H
			Synthesis example 5	Me	H
Synthesis example 6	Me	H
			Synthesis example 7	H	H
Synthesis example 8	H	Me
			Synthesis example 9	Me	Me
Synthesis example 14	CF3	H
			Synthesis example 15	F	H
Synthesis example 16	Cl	H
			Synthesis example 17	Br	H
Synthesis example 18	NO2	H
			Synthesis example 19	CF3	Me
Synthesis example 20	F	Me
			Synthesis example 21	Cl	Me
Synthesis example 22	Br	Me
			Synthesis example 23	NO2	Me
Synthesis example 24	Me	F
			Synthesis example 25	Me	Cl
Synthesis example 26	Me	Br
			Synthesis example 27	Me	NO2
Synthesis example 28	F	F
			Synthesis example 29	F	Cl

The compounds of Synthesis examples 10 to 12 and 30 to 38 are represented by the general formula (D).

(in the formula (D), R_C、R_DAre the substituents shown in Table 9. Me in Table 9 represents a methyl group. n is a numerical value shown in table 3, table 5 to table 6. )

[ Table 9]

	Substituent RC	Substituent RD
			Synthesis example 10	Me	H
Synthesis example 11	H	Me
			Synthesis example 12	Me	Me
Synthesis example 30	F	H
			Synthesis example 31	Cl	H
Synthesis example 32	Br	H
			Synthesis example 33	H	F
Synthesis example 34	H	Cl
			Synthesis example 35	H	Br
Synthesis example 36	F	F
			Synthesis example 37	Cl	Cl
Synthesis example 38	Br	Br

The compound of Synthesis example 13 is represented by the general formula (E).

(in the formula (E), n is a numerical value shown in Table 4.)

The compound of Synthesis example 39 is represented by the general formula (F).

(in the formula (F), n is a numerical value shown in Table 6.)

The compound of Synthesis example 40 is represented by the general formula (G).

(in the formula (G), n is a numerical value shown in Table 6.)

The compounds of Synthesis examples 43 to 52 are shown by the general formula (1)In the formula (1), Ar₁、Ar₂Are respectively aromatic ring groups shown in Table 10 or Table 11, Ar₃And Ar₁The same is true. Z is an epoxy-containing terminal group represented by the above formula (3). n is a numerical value shown in tables 6 to 7. ).

[ Table 10]

[ Table 11]

The compound of Synthesis example 53 is represented by the general formula (H).

(in the formula (H), n is a numerical value shown in Table 7.)

The compound of synthesis example 54 was represented by the following general formula (I) (in formula (I), n is a number shown in table 7. a is O.).

The compound of synthesis example 55 was represented by the following general formula (I) (in formula (I), n is a number shown in table 7. a is NH.).

The compound of Synthesis example 56 was represented by the following general formula (J) (in the formula (J), n is a number shown in Table 7. R is-CH₃。)。

The compound of Synthesis example 57 was represented by the following general formula (J) (in the formula (J), n is a number shown in Table 7. R is-H.).

The compound of Synthesis example 58 is represented by the general formula (K).

(in the formula (K), n is a numerical value shown in Table 6.)

As a result of identifying the compounds of synthesis examples 1 to 58, as described above, the epoxy resins of synthesis examples 1 to 58 contained a first aromatic ring unit composed of a first aromatic ring group and 2 ether oxygens bonded to the first aromatic ring group, a second aromatic ring unit composed of a second aromatic ring group and 2 methylene groups bonded to the second aromatic ring group, and a third aromatic ring unit composed of a third aromatic ring group and an epoxy-containing terminal group bonded to the third aromatic ring group, contained a skeleton in which the first aromatic ring unit and the second aromatic ring unit were alternately arranged, had the first aromatic ring unit arranged at both ends of the skeleton and bonded to the third aromatic ring group via the methylene groups, or a structure in which the second aromatic ring unit is disposed at both ends of the skeleton and bonded to the third aromatic ring group via an ether oxygen.

From the results of the molecular weight measurement, the average polymerization degree as an average value of the number of repeating units of the epoxy resins of synthesis examples 1 to 58 was calculated.

Further, the solutions containing components (epoxy resins) having different molecular weights separated by GPC were dried and cured, and the masses thereof were measured to calculate the proportions (mol%) of the components contained in the epoxy resins of synthesis examples 1 to 58.

Tables 1 to 2 show the proportions of the respective components (epoxy resins) having different numbers of repeating units ("the proportions (mol%) of the respective components having different numbers of repeating units n") and the average polymerization degrees contained in the epoxy resins of synthesis examples 1 to 58.

< production of resin composition >

Examples 1 to 15, 18 to 22, 25 to 29 and 32 to 83 "

Epoxy resins shown in tables 12 to 14, curing agents shown in tables 12 to 14, and curing accelerators shown in tables 12 to 14 were mixed in the proportions shown in tables 12 to 14, respectively, to obtain resin compositions of examples 1 to 15, 18 to 22, 25 to 29, and 32 to 83.

2E4MZ as a resin curing agent shown in tables 12 to 14 is 2-ethyl-4-methylimidazole.

"examples 16, 23, 30"

As the epoxy resin, an epoxy resin obtained by mixing the epoxy resin of synthesis example 5 and the epoxy resin of synthesis example 6 in a mass ratio of 1:1 was used, and the curing agent shown in table 12 and the curing accelerator shown in table 12 were mixed in the proportions shown in table 12, respectively, to obtain resin compositions of examples 16, 23, and 30.

"examples 17, 24, 31"

As the epoxy resins, epoxy resins obtained by mixing the epoxy resins of synthesis examples 1,3, 4, and 5 in a mass ratio of 1:1:1:1 were used, and the curing agents shown in tables 12 to 13 and the curing accelerators shown in tables 12 to 13 were mixed in the ratios shown in tables 12 to 13, respectively, to obtain resin compositions of examples 17, 24, and 31.

[ Table 12]

[ Table 13]

[ Table 14]

The resin compositions of examples 1 to 83 thus obtained were each measured for thermal conductivity by the following method. The results are shown in tables 12 to 14.

(measurement of thermal conductivity)

The density, specific heat and thermal diffusivity of the cured resin were measured by the following methods, and the thermal conductivity was determined by multiplying the measured values.

The density was determined by the archimedes method.

Specific Heat was calculated at 25 ℃ in accordance with JIS K7123 using a Differential Scanning Calorimeter (DSC) (manufactured by Hitachi High-Tech Science Corporation).

The thermal diffusivity was determined using a xenon flash thermal diffusivity measuring apparatus (ADVANCE RIKO, Inc.).

For the measurement of thermal diffusivity, a measurement sample produced by the method shown below was used. That is, the resin composition was rapidly melt-mixed in an aluminum cup at a temperature of 180 ℃ and cooled to room temperature. Thereafter, the uncured resin composition was cured by heating at 100 ℃ for 1 hour, at 150 ℃ for 1 hour, and at 180 ℃ for 30 minutes in this order. The obtained cured resin was processed into a cylindrical shape having a diameter of 10mm and a thickness of 0.5mm, and used as a sample for measurement.

As shown in tables 12 to 14, the cured products of the resin compositions of examples 1 to 83 all had a thermal conductivity of 0.5W/(mK) or more and a high thermal conductivity.

Industrial applicability of the invention

Disclosed is an epoxy resin which enables to obtain a cured product having high thermal conductivity.

Description of symbols:

10 … resin substrate

12 … resin sheet

20 … cured product

22 … resin composition

30 … core material

50 … laminate substrates.