JP2018172458A - Compound, resin composition, resin sheet, resin cured product, resin substrate, and multilayer substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound which is excellent in solubility in a solvent and compatibility with a curative, has high thermal conductivity, and provide a cured product with good heat resistance.SOLUTION: A compound has an epoxy group, a phenolic hydroxyl group, and a mesogen. A compound has an epoxy group and one mesogen, where the mesogen preferably has one or more phenolic hydroxyl groups. Especially preferably, the compound is represented by the formula 13.SELECTED DRAWING: None

Description

  The present invention relates to a compound, a resin composition, a resin sheet, a cured resin, a resin substrate, and a laminated substrate.

In recent years, with the demand for miniaturization of electronic devices, high-functionality and high-density mounting of components has been promoted. Therefore, it is important to treat heat generated from electronic components and the like.
Heat generated from electronic components and the like is radiated to the outside mainly through the substrate. In a power supply laminated substrate in which a resin substrate is laminated, since particularly high heat dissipation is required, inorganic particles such as alumina, boron nitride, and magnesium oxide are added to the resin to enhance thermal conductivity.

  However, if the content of inorganic particles in the resin is increased in order to improve the thermal conductivity, a problem arises in process applicability during substrate molding. Therefore, even if the inorganic particle content in the resin is suppressed and process applicability is ensured, development of a resin capable of obtaining a cured product with high thermal conductivity is advanced so that a substrate having high heat dissipation can be obtained. ing.

  As a design guideline for a resin having a high thermal conductivity, there is one that increases the thermal conductivity by increasing the crosslinking density of the resin and securing a large number of heat conduction paths. In addition, as a design guideline for a resin having high thermal conductivity, there is one that increases the thermal conductivity by introducing a mesogen skeleton into the resin and forming a liquid crystal structure (see, for example, Non-Patent Document 1).

  Conventionally, a compound containing an epoxy group and a phenolic hydroxyl group in the same molecule has been reported (for example, see Patent Document 1).

European Patent Application No. 2826777

Takezawa Yoshitaka, Polymer 65, February, p65-67, 2016

However, a technique for increasing the crosslinking density of the resin cannot provide a cured product having a sufficiently high thermal conductivity.
On the other hand, a cured product having a high thermal conductivity can be obtained by curing a resin having a mesogenic skeleton introduced therein. However, a resin in which a mesogenic skeleton is introduced has poor solubility in a solvent and compatibility with a curing agent. For this reason, the resin in which the mesogen skeleton is introduced has insufficient workability when a cured product is formed using the resin, and it is difficult to obtain a uniform cured product.

  Moreover, as for resin used as a material of a resin substrate, the hardened | cured material which hardened this needs to have sufficient heat resistance.

The present invention has been made in view of the above problems, and provides a compound that is excellent in solubility in a solvent and compatibility with a curing agent, has a high thermal conductivity, and has a heat-resistant cured product. Is an issue.
Another object of the present invention is to provide a resin composition, a resin sheet, a cured resin, a resin substrate, and a laminated substrate containing the compound of the present invention.

In order to solve the above problems, the present inventor has conducted extensive studies as described below.
As a result, it has been found that any compound having an epoxy group, a phenolic hydroxyl group, and a mesogen in one molecule may be used.
That is, the present invention relates to the following inventions.

[1] A compound having an epoxy group, a phenolic hydroxyl group, and a mesogen.
[2] A compound having an epoxy group and one mesogen, wherein the mesogen has one or more phenolic hydroxyl groups.

[3] A first linking group made of any one selected from —O—, —CH ₂ —, —CO—, —COO—, and —OCO— is disposed between the epoxy group and the mesogen. ,
[1] The compound according to [2], wherein one end of the first linking group is bonded to an end of the mesogen on the epoxy group side.
[4] between the mesogen and the epoxy _{group, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 - second linking group comprising any one selected from the disposed ,
The compound according to [2] or [3], wherein one end of the second linking group is bonded to the epoxy group.

[5] The compound according to any one of [2] to [4], wherein the mesogen is represented by the following formula (1) or (2).

（式（１）において、Ｒ１〜Ｒ４はそれぞれ独立に水素原子またはメチル基である。Ｒ５〜Ｒ９はそれぞれ独立に水素原子、メチル基、水酸基の何れかであり、Ｒ５〜Ｒ９のいずれか１つ以上が水酸基である。）

(In the formula (1), R1 to R4 are each independently a hydrogen atom or a methyl group. R5 to R9 are each independently a hydrogen atom, a methyl group, or a hydroxyl group, and any one of R5 to R9. The above is a hydroxyl group.)

（式（２）において、Ｒ１０〜Ｒ１３はそれぞれ独立に水素原子またはメチル基である。Ｒ１４〜Ｒ１８はそれぞれ独立に水素原子、メチル基、水酸基の何れかであり、Ｒ１４〜Ｒ１８のいずれか１つ以上が水酸基である。Ｘは下記式（３）〜（１２）の何れかである）。

(In Formula (2), R10 to R13 are each independently a hydrogen atom or a methyl group. R14 to R18 are each independently a hydrogen atom, a methyl group, or a hydroxyl group, and any one of R14 to R18) The above is a hydroxyl group, and X is any one of the following formulas (3) to (12).

（式（３）において、Ｒ１９〜Ｒ２２はそれぞれ独立に水素原子またはメチル基である。）

(In Formula (3), R19 to R22 are each independently a hydrogen atom or a methyl group.)

（式（４）において、Ｒ２３およびＲ２４はそれぞれ独立に水素原子またはメチル基である。）

(In Formula (4), R23 and R24 are each independently a hydrogen atom or a methyl group.)

（式（５）において、Ｒ２５は水素原子またはメチル基である。）

(In Formula (5), R25 is a hydrogen atom or a methyl group.)

[6] A compound represented by the following formula (13):

[7] A resin composition comprising the compound according to any one of [1] to [6].
[8] A resin sheet obtained by molding the resin composition according to [7].
[9] A cured resin containing a cured product of the resin composition according to [7].
[10] A resin substrate comprising a cured product of the resin composition according to [7].
[11] A laminated substrate in which a plurality of resin substrates are laminated, and at least one of the plurality of resin substrates includes a cured product of the resin composition according to [7].

The compound of the present invention has an epoxy group, a phenolic hydroxyl group, and a mesogen. Since the compound of the present invention has a low polarity epoxy group and a high polarity phenolic hydroxyl group in one molecule, it exhibits good solubility in various solvents from low polarity to high polarity, Excellent compatibility. Therefore, when forming hardened | cured material using the compound of this invention, the uniform resin composition containing a compound can be manufactured easily, and a uniform hardened | cured material is easily obtained by hardening a resin composition.
Moreover, since the compound of this invention has an epoxy group, a phenolic hydroxyl group, and a mesogen, it will become a hardened | cured material which has the orientation in which the smectic liquid crystal structure was formed by hardening this. As a result, a cured product having high thermal conductivity and good heat resistance is obtained.

FIG. 1 is a perspective view of a resin sheet and a resin substrate. 2 is a cross-sectional view taken along the line II-II of the resin sheet and the resin substrate of FIG. FIG. 3 is a perspective view of the multilayer substrate. 4 is a cross-sectional view taken along the line IV-IV of the multilayer substrate of FIG.

  Hereinafter, the present invention will be described in detail with appropriate reference to the drawings. In the drawings used in the following description, in order to make the characteristics of the present invention easier to understand, there are cases where the characteristic parts are enlarged for convenience. Therefore, the dimensional ratios of the components described in the drawings may be different from actual ones. The materials, dimensions, and the like exemplified in the following description are merely examples, and the present invention is not limited to these, and can be implemented with appropriate modifications without departing from the scope of the invention.

"Compound"
The compound of the present embodiment (hereinafter sometimes referred to as “compound A”) has an epoxy group, a phenolic hydroxyl group, and a mesogen in one molecule.
The “mesogen” in the present embodiment is a functional group having an orientation necessary for exhibiting liquid crystallinity, and means a structural unit that can be a liquid crystal structure.

The number of phenolic hydroxyl groups possessed by compound A is not particularly limited and is preferably 1 to 3, and is most preferably one because it can prevent the compound A from having a high melting point due to hydrogen bonding. .
The number of epoxy groups possessed by compound A is not particularly limited, and is preferably 1 to 3. In order to make a highly ordered structure necessary for a highly oriented structure, active hydrogen value and epoxy value It is most preferable that the number is one.

In the compound A, a first linking group consisting of any one selected from —O—, —CH ₂ —, —CO—, —COO—, and —OCO— is disposed between an epoxy group and a mesogen, One end of the first linking group is preferably bonded to the end of the mesogen on the epoxy group side. When the first linking group is any one of the above, it is preferable from the viewpoint of simplicity of synthesis of Compound A, chemical stability, and suppression of increase in melting point.

Compound A, between the epoxy groups and the _{mesogenic, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 - second linking group comprising any one selected from is arranged, It is preferable that one end of the second linking group is bonded to an epoxy group. When the second linking group is any one of the above, the molecular weight of the compound A is not excessively increased, and this is preferable from the viewpoint of suppressing the addition amount and the balance between hydrophilicity / hydrophobicity.

The mesogen possessed by the compound A may be a structural unit capable of forming a liquid crystal structure, and examples thereof include those composed of rigid components such as an aromatic ring. The mesogen preferably has one or more phenolic hydroxyl groups.
When the mesogen has one or more phenolic hydroxyl groups, the compound A preferably has only one mesogen. In this case, since one or more phenolic hydroxyl groups are bonded to and integrated with only one mesogen, it is difficult for compound A to be excessively organically modified, and the molecular weight can be prevented from becoming too large. . Compound A having a small molecular weight is preferable because good miscibility with the resin is easily obtained.

  The mesogen having one or more phenolic hydroxyl groups is preferably one represented by the following formula (1) or (2).

（式（１）において、Ｒ１〜Ｒ４はそれぞれ独立に水素原子またはメチル基である。Ｒ５〜Ｒ９はそれぞれ独立に水素原子、メチル基、水酸基の何れかであり、Ｒ５〜Ｒ９のいずれか１つ以上が水酸基である。）

(In the formula (1), R1 to R4 are each independently a hydrogen atom or a methyl group. R5 to R9 are each independently a hydrogen atom, a methyl group, or a hydroxyl group, and any one of R5 to R9. The above is a hydroxyl group.)

In the mesogen represented by the formula (1), R1 to R4 are each independently a hydrogen atom or a methyl group, and R5 to R9 are each independently a hydrogen atom, a methyl group, or a hydroxyl group. It is not too much and is preferable.
The mesogen represented by the formula (1) is particularly preferable because when R1 to R4 are all hydrogen atoms and R5 to R9 are each independently a hydrogen atom or a hydroxyl group, the compound has a low molecular weight.

The number of hydroxyl groups of the mesogen represented by the formula (1) is preferably 1 to 3 because it is a compound having better solubility in a solvent and compatibility with a curing agent. Most preferred.
One or more hydroxyl groups of the mesogen represented by the formula (1) are compounds having more excellent solubility in a solvent and compatibility with a curing agent. Therefore, among R5 to R9, particularly a position including the position of R8. It is preferable that it is couple | bonded with.

（式（２）において、Ｒ１０〜Ｒ１３はそれぞれ独立に水素原子またはメチル基である。Ｒ１４〜Ｒ１８はそれぞれ独立に水素原子、メチル基、水酸基の何れかであり、Ｒ１４〜Ｒ１８のいずれか１つ以上が水酸基である。Ｘは下記式（３）〜（１２）の何れかである）。

(In Formula (2), R10 to R13 are each independently a hydrogen atom or a methyl group. R14 to R18 are each independently a hydrogen atom, a methyl group, or a hydroxyl group, and any one of R14 to R18) The above is a hydroxyl group, and X is any one of the following formulas (3) to (12).

（式（３）において、Ｒ１９〜Ｒ２２はそれぞれ独立に水素原子またはメチル基である。）

(In Formula (3), R19 to R22 are each independently a hydrogen atom or a methyl group.)

（式（４）において、Ｒ２３およびＲ２４はそれぞれ独立に水素原子またはメチル基である。）

(In Formula (4), R23 and R24 are each independently a hydrogen atom or a methyl group.)

（式（５）において、Ｒ２５は水素原子またはメチル基である。）

(In Formula (5), R25 is a hydrogen atom or a methyl group.)

In the mesogen represented by the formula (2), R10 to R13 are each independently a hydrogen atom or a methyl group, and R14 to R18 are each independently a hydrogen atom, a methyl group, or a hydroxyl group. It is not too much and is preferable.
The mesogen represented by the formula (2) is particularly preferable because when R10 to R13 are all hydrogen atoms and R14 to R18 are each independently a hydrogen atom or a hydroxyl group, the compound has a low molecular weight.

The number of hydroxyl groups of the mesogen represented by the formula (2) is preferably 1 to 3 because it is a compound having better solubility in a solvent and compatibility with a curing agent. Most preferred.
One or more hydroxyl groups possessed by the mesogen represented by formula (2) are compounds having better solubility in solvents and compatibility with curing agents, and therefore, among R14 to R18, positions including R17 in particular. It is preferable that it is couple | bonded with.

  In the formulas (3) to (5), R19 to R25 are each a hydrogen atom or a methyl group, and are preferably a hydrogen atom because they are compounds having better solubility in solvents and compatibility with curing agents. .

  The compound A is preferably one represented by the following formula (13). The compound represented by the formula (13) is preferable because it is a compound having the smallest molecular weight among compounds having an epoxy group, a phenolic hydroxyl group, and a mesogen in the same molecule and can be easily synthesized.

The compound A of this embodiment can be manufactured by the method shown below, for example.
Hereinafter, the case of producing a compound having one epoxy group and one mesogen having one phenolic hydroxyl group will be described as an example of the production method of Compound A.
First, a compound B having a mesogen corresponding to the mesogen of compound A to be synthesized and having a phenolic hydroxyl group at both ends is prepared.
Further, the compound A is arranged between the epoxy group and the mesogen of the compound A to be synthesized and has one end corresponding to the second linking group bonded to the epoxy group, one end being a Br group and the other end being a vinyl group. A compound C is prepared.

Then, the compound B and the compound C are reacted to synthesize a compound D in which the hydrogen of the phenolic hydroxyl group arranged at one end of the compound B is replaced with a structure obtained by removing the Br group from the compound C.
Next, the vinyl group of compound D is oxidized using hydrogen peroxide or the like, and an epoxy group is introduced into compound D. This gives compound A.

  Compound A has an epoxy group, a phenolic hydroxyl group, and a mesogen. For this reason, while showing favorable solubility with respect to various solvents of low polarity to high polarity, it is excellent in compatibility with a hardening | curing agent. Moreover, since the compound A has an epoxy group, a phenolic hydroxyl group, and a mesogen, by curing it, a cured product having an orientation in which a smectic liquid crystal structure is formed is obtained. As a result, a cured product having high thermal conductivity and good heat resistance is obtained.

  On the other hand, for example, a compound containing an epoxy group and a phenolic hydroxyl group described in Patent Document 1 in the same molecule does not use a skeleton that can function as a mesogen, so that sufficient thermal conductivity cannot be expected.

"Resin composition"
The resin composition of the present embodiment preferably contains the above-described compound A, and further contains a resin component other than the compound A, a curing agent, and a curing accelerator (catalyst).
Examples of the resin component other than Compound A include one compound such as an epoxy compound such as 4,4′-biphenol diglycidyl ether, a compound having an amino group such as p-phenylenediamine, and a compound having an amide group such as sulfanilamide. Or you may contain 2 or more types.

  The proportion of Compound A in the total of Compound A and resin components other than Compound A in the resin composition of the present embodiment is preferably 10% by weight or more, and more preferably 50% by weight or more. When the proportion of the compound A is 10% by weight or more, the compatibility between the resin components becomes good and the orientation of the resin can be effectively improved. Moreover, the effect by including the compound A becomes more remarkable as the ratio of the compound A is 50% by weight or more.

  The curing agent only needs to have at least two functional groups capable of undergoing a curing reaction with an epoxy group in the molecule. For example, an amine curing agent in which the functional group is an amino group, and the functional group is a hydroxyl group. A certain phenol type curing agent, an acid anhydride type curing agent in which the functional group is a carboxyl group, and the like can be mentioned.

  Examples of amine curing agents include aliphatic polyamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine, such as p-xylenediamine and m-xylene. Diamine, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 4,4'- Aromatic polyamines such as diaminodiphenyl ether, 1,1-bis (4-aminophenyl) cyclohexane, 4,4′-diaminodiphenylsulfone, bis (4-aminophenyl) phenylmethane, such as 4,4′-diaminodi Cyclohexane, , 3-bis alicyclic polyvalent amines such as (aminomethyl) cyclohexane, for example, dicyandiamide and the like.

Examples of the phenolic curing agent include 4,4′-biphenol, hydroquinone, 2,6-dihydroxynaphthalene, bisphenol F, phenol resin, phenol aralkyl resin (having a phenylene skeleton, diphenylene skeleton, etc.), naphthol aralkyl resin, polyoxy A styrene resin etc. are mentioned.
Examples of the acid anhydride curing agent include maleic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and the like.

  In the curing agent, the total amount of functional groups capable of undergoing a curing reaction with an epoxy group is usually 0.5 to 1.5 equivalent times the total amount of epoxy groups in the resin component other than Compound A and Compound A, preferably An amount of 0.9 to 1.1 equivalent times is used.

As the curing accelerator, for example, a basic organic compound having a high boiling point can be used. Specific examples include those having a boiling point of 200 ° C. or higher selected from tertiary amines, tertiary phosphines, DMAP and imidazoles. Among these, it is preferable to use 1- (2-cyanoethyl) -2-phenylimidazole, which is an imidazole-based epoxy resin curing agent, as a curing accelerator because of ease of handling.
The content of the curing accelerator in the resin composition is, for example, 0 to 5 parts by mass with respect to 100 parts by mass in total of the resin components other than Compound A and Compound A and the curing agent.

  The resin composition of this embodiment may contain inorganic particles as necessary. Examples of the inorganic particles include boron nitride particles, magnesium oxide particles, alumina particles, aluminum hydroxide particles, aluminum nitride particles, and silica particles. One of these can be used alone or in combination of two or more.

  The content of the inorganic particles is preferably 200 to 700 parts by mass, more preferably 300 to 600 parts by mass with respect to 100 parts by mass in total of the resin composition components other than the inorganic particles. When the content of the inorganic particles is 200 parts by mass or more, the effect of improving the thermal conductivity in the cured product of the resin composition becomes remarkable. Further, when the content of the inorganic particles is 700 parts by mass or less, sufficient moldability is obtained when the resin substrate is molded using the cured product of the resin composition.

If necessary, the resin composition of the present embodiment includes ketones such as acetone and methyl ethyl ketone (MEK), alcohols such as methanol, ethanol and isopropanol, aromatic compounds such as toluene and xylene, tetrahydrofuran (THF) and Solvents such as ethers such as 1,3-dioxolane, esters such as ethyl acetate and γ-butyrolactone, amides such as N, N-dimethylformamide (DMF) and N-methylpyrrolidone may be contained.
The content of the solvent in the resin composition is, for example, 0 to 500 parts by mass with respect to 100 parts by mass in total of the resin components other than Compound A and Compound A and the curing agent.

  The resin composition may contain arbitrary components other than the above-mentioned components as needed. Examples of optional components include coupling agents such as silane coupling agents and titanate coupling agents, flame retardants such as halogens, plasticizers, and lubricants.

  The resin composition of this embodiment can be manufactured by, for example, a method of mixing Compound A, a resin component other than Compound A, a curing agent, a curing accelerator, and other components contained as necessary.

  The resin composition of this embodiment has good uniformity because the above-described compound A exhibits good solubility in various solvents having low to high polarity. Therefore, by heating and melting the resin composition of the present embodiment, a uniform molten state with no undissolved residue is obtained, and a cured product with good uniformity is obtained.

FIG. 1 is a perspective view of a resin sheet according to an embodiment. The resin sheet 12 is a sheet obtained by molding a resin composition. The resin sheet 12 may contain the resin composition as it is, or a part or all of the resin composition may be contained in a B-stage (semi-cured) state.
2 is a cross-sectional view taken along line II-II in FIG. FIG. 2 shows a cross section when the resin sheet 12 is cut along the thickness direction. The resin sheet 12 contains a core material 30 and a resin component 22 that is impregnated in the core material 30 and covers both surfaces of the core material 30. The circles in FIG. 2 indicate the glass fibers contained in the core material 30. The resin component 22 may be an uncured resin composition, or a part or all of the resin component 22 may be a semi-cured product of the resin composition.

  Examples of the core material 30 include woven fabrics and nonwoven fabrics containing at least one fiber selected from glass fibers, carbon fibers, metal fibers, natural fibers, and synthetic fibers such as polyester fibers or polyamide fibers. However, the core material 30 is not limited to these.

  The resin sheet 12 can be manufactured as follows. The core material 30 is impregnated with the resin composition by a technique such as coating or dipping. When the resin composition contains a solvent, the core material 30 is impregnated with the resin composition, and then heated and dried to remove the solvent. The heating conditions at this time can be, for example, about 60 to 150 ° C. for about 1 to 120 minutes, and preferably about 70 to 120 ° C. for about 3 to 90 minutes. The resin sheet 12 which has the resin component 22 which consists of a resin composition which is uncured or at least partially cured by the above process is obtained.

  Since the resin sheet 12 shown in FIG. 1 is obtained by molding the resin composition of the present embodiment, the resin composition is cured by heat-treating the resin composition so as to have good uniformity and high thermal conductivity. And a cured resin having good heat resistance can be obtained. Therefore, the resin sheet 12 shown in FIG. 1 is suitable as a material for the resin substrate.

  The resin sheet 12 may have the core material 30 or may be formed of only the resin component 22 without the core material 30. In addition, a metal foil such as a copper foil may be laminated on the surface of the resin sheet 12.

  The resin sheet 12 can be used as a precursor of a resin substrate (resin cured product) containing a cured product of the resin composition. Specifically, the resin sheet 12 is heated to further cure the resin component 22 in an uncured or semi-cured state to obtain a cured product (thermoset). The heating condition at this time is preferably about 100 to 250 ° C. for about 1 to 300 minutes, for example. Heating may be performed under pressure or reduced pressure as necessary. The resin substrate 10 including the cured product 20 of the resin composition is obtained through the above steps.

  The resin substrate 10 (resin cured product) of the present embodiment includes a cured product of the resin composition of the present embodiment. Therefore, it has good uniformity. In addition, the resin substrate 10 (cured resin product) of the present embodiment has an orientation in which a liquid crystal structure is formed because the resin composition used as a material contains the compound A having a mesogen. Therefore, it has high thermal conductivity and good heat resistance.

  The resin substrate 10 includes a core material 30 and a cured product 20 that covers the core material 30. In another some embodiment, the resin substrate may be comprised only with the hardened | cured material of the resin composition.

  The resin cured product may be manufactured by a method in which the resin sheet 12 formed into a sheet shape as described above is used as a precursor and the resin sheet 12 is heated. For example, when the resin composition is used as an adhesive, Thus, you may manufacture by heating an amorphous resin composition.

FIG. 3 is a perspective view of the multilayer substrate according to the embodiment. 4 is a cross-sectional view taken along line IV-IV in FIG. FIG. 4 shows a cross section when cut along the lamination direction of the laminated substrate. As shown in FIGS. 3 and 4, the laminated substrate 50 is formed by laminating a plurality of the resin substrates 10 shown in FIG.
The laminated substrate 50 is obtained, for example, by heating and / or pressing in a state where a plurality of resin substrates 10 or resin sheets 12 are overlapped. The heating condition can be, for example, about 100 to 250 ° C. for about 1 to 300 minutes. The pressurizing condition is, for example, about 0.1 to 10 MPa. Note that pressurization is not essential, and heating may be performed under reduced pressure or under vacuum.

Since the laminated substrate 50 is a laminate of the resin substrates 10, it has good uniformity, high thermal conductivity, and good heat resistance.
The plurality of resin substrates included in the multilayer substrate 50 may all be the resin substrate 10 containing the cured product 20, or may be the resin substrate 10 containing only the cured product 20.

  The multilayer substrate 50 may be a metal-clad laminate having a metal layer on the main surface. Various known materials can be appropriately selected and used for the metal layer. The metal layer may be, for example, a metal plate or metal foil such as copper, nickel, or aluminum. The thickness of a metal layer is not specifically limited, For example, it can be set as about 3-150 micrometers. The laminated substrate may be obtained by etching and / or punching a metal-clad laminate.

  The embodiments of the present invention have been described in detail with reference to the drawings. However, the configurations and combinations of the embodiments in the embodiments are examples, and the addition and the omission of the configurations are within the scope not departing from the gist of the present invention. , Substitutions, and other changes are possible.

"Example 1"
By performing the steps of (Synthesis 1) and (Synthesis 2) shown below, a compound having an epoxy group, a phenolic hydroxyl group, and a mesogen was produced.
(Synthesis 1)
4,4′-biphenol (25 g) represented by the following formula (14) was weighed into a three-necked flask and dissolved in N, N-dimethylformamide (DMF) (200 mL). Potassium carbonate (18.5 g) and 4-bromo-1-butene (18 g) were added thereto to obtain a mixture. Thereafter, the mixture was kept at 85 ° C. and reacted overnight.

  After completion of the reaction, the precipitate was removed from the resulting reaction solution by filtration, and the filtrate was concentrated by a rotary evaporator. Distilled water (1 L) was poured into the concentrated reaction solution to form a precipitate. The resulting precipitate was collected by suction filtration and washed with distilled water. The obtained solid was dissolved in methanol, and insoluble matters were removed by filtration. The obtained filtrate was dried and separated by silica gel column chromatography (chloroform / acetone = 98/2 (volume ratio)), and the first distillate was collected. The solvent was removed from the recovered first distillate to obtain 17.2 g of a compound represented by the following formula (15) as a target product as a white powder. The yield was 53%. The chemical reaction formula in (Synthesis 1) is shown below.

(Synthesis 2)
The compound (17.2 g) represented by the formula (15) obtained in Synthesis 1 and sodium hydrogen carbonate (5.0 g) were added to methanol (100 mL), acetonitrile (50 mL), and 35 wt% aqueous hydrogen peroxide (200 mL). Dissolved and allowed to react with continued stirring at room temperature for 18 hours.
After completion of the reaction, the reaction solution was concentrated by a rotary evaporator until the amount of the obtained reaction solution was about half. Then, it extracted 3 times with ethyl acetate (100 mL). The organic phase was washed with a saturated aqueous sodium thiosulfate solution and distilled water. The organic phase was then dried over anhydrous magnesium sulfate. The desiccant was removed from the organic phase by filtration, and the solvent was removed with a rotary evaporator.

  The obtained crude was separated by silica gel column chromatography (chloroform / acetone = 98/2 (volume ratio)), and the second distillate was recovered. The solvent was removed from the second distillate and dissolved in a small amount of acetone while warming. Toluene was added until a slight precipitate formed with warming. The fine suspension was allowed to cool to room temperature, and the precipitate was collected by filtration. The collected precipitate was dried to obtain 7.1 g of the target compound as a white powder. The yield was 35%.

Next, the target compound thus obtained was identified using an NMR (nuclear magnetic resonance) method. The results are shown below. From the following results, it was confirmed that the compound was represented by the formula (16) (4 ′-[2- (oxiran-2-yl) ethoxy] biphenyl-4-ol).
¹ H NMR 500 MHz (DMSO-6d): 1.78-1.85 ppm multiplet (1H), 1.89-1.96 ppm multiplet (1H), 2.44-2.45 ppm multiplet (1H), 2.68 ppm triplet (1H), 3.00-3.03 ppm multiplet (1H), 4.03-4.05 ppm multiplet (2H), 6.73-6.76 ppm multiplet (2H), 6.90-6.93 ppm multiplet (2H ), 7.33-7.36 ppm multiplet (2H), 7.41-7.43 ppm multiplet (2H), 9.37 ppm singlet (1H)
LC / MS (APCI): 255 (-H ^<+> )
Cul. MASS: 256
The chemical reaction formula in (Synthesis 2) is shown below.

Next, using the compound represented by the formula (16), the following resin composition was produced and cured by the method described below to obtain a cured product of Example 1.
Compound (0.5 g) represented by formula (16), epoxy compound (0.33 g) represented by formula (17), and 4,4′-biphenol (0) represented by formula (14) as a curing agent .17 g) and 1- (2-cyanoethyl) -2-phenylimidazole (2PZ-CN (trade name: manufactured by Shikoku Kasei Kogyo Co., Ltd.)) (0.02 g), which is a curing accelerator, are mixed to obtain a resin composition. I got a thing.

The obtained resin composition was melt-mixed on a hot plate heated to 150 ° C. The temperature was maintained as it was, and the resin composition was cured to obtain a cured product of Example 1.
The uniformity in the resin composition of Example 1 was visually evaluated according to the following criteria. The results are shown in Table 1.
"Standard"
○: A uniform molten state was obtained by heating and melt mixing.
X: Unmelted residue was present when heated and melted, and a uniform molten state could not be obtained.

"Example 2"
The compound (0.5 g) represented by the formula (16), the epoxy compound (0.34 g) represented by the formula (17), and 2,6-dihydroxynaphthalene (0 .16 g) and 2PZ-CN (trade name: manufactured by Shikoku Kasei Kogyo Co., Ltd.) (0.02 g) as a curing accelerator were mixed to obtain a resin composition.
The obtained resin composition was melt-mixed on a hot plate heated to 150 ° C. The temperature was maintained as it was, and the resin composition was cured to obtain a cured product of Example 2.
The uniformity in the resin composition of Example 2 was visually evaluated according to the above criteria. The results are shown in Table 1.

"Example 3"
A compound (0.3 g) represented by the formula (16), an epoxy compound (0.23 g) represented by the formula (17), a hydroquinone (0.07 g) represented by the formula (19) as a curing agent, 2PZ-CN (trade name: manufactured by Shikoku Kasei Kogyo Co., Ltd.) (0.02 g) which is a curing accelerator was mixed to obtain a resin composition.
The obtained resin composition was melt-mixed on a hot plate heated to 150 ° C. The temperature was maintained as it was, and the resin composition was cured to obtain a cured product of Example 3.
The uniformity in the resin composition of Example 3 was visually evaluated according to the above criteria. The results are shown in Table 1.

"Comparative Example 1"
Epoxy compound (0.66 g) represented by formula (17), 4,4′-biphenol (0.34 g) represented by formula (14) as a curing agent, and 2PZ-CN (commercial product) as a curing accelerator Name: Shikoku Kasei Kogyo Co., Ltd. (0.02 g) was mixed to obtain a resin composition.
The obtained resin composition was melt-mixed on a hot plate heated to 180 ° C. The resin composition did not become a uniform melt, and a uniform cured product could not be obtained.
The uniformity in the resin composition of Comparative Example 1 was visually evaluated according to the above criteria. The results are shown in Table 1.

"Comparative Example 2"
An epoxy compound (0.65 g) represented by the formula (17), a 4,4′-biphenol (0.17 g) represented by the formula (14) which is a curing agent, and a formula (20) which is a curing agent. Bisphenol F (0.18 g) and 2PZ-CN (trade name: manufactured by Shikoku Kasei Kogyo Co., Ltd.) (0.02 g) as a curing accelerator were mixed to obtain a resin composition.
The obtained resin composition was melt-mixed on a hot plate heated to 180 ° C. The resin composition did not become a uniform melt, and a uniform cured product could not be obtained.
The uniformity in the resin composition of Comparative Example 2 was visually evaluated according to the above criteria. The results are shown in Table 1.

“Comparative Example 3”
An epoxy compound (0.64 g) represented by the formula (17), a 4,4′-biphenol (0.07 g) represented by the formula (14) which is a curing agent, and a formula (20) which is a curing agent. Bisphenol F (0.29 g) and 2PZ-CN (trade name: manufactured by Shikoku Kasei Kogyo Co., Ltd.) (0.02 g) as a curing accelerator were mixed to obtain a resin composition.
The obtained resin composition was melt-mixed on a hot plate heated to 180 ° C. The temperature was maintained as it was, and the resin composition was cured to obtain a cured product of Comparative Example 3.
The uniformity in the resin composition of Comparative Example 3 was visually evaluated according to the above criteria. The results are shown in Table 1.

“Comparative Example 4”
Epoxy compound (0.69 g) represented by formula (17), 2,6-dihydroxynaphthalene (0.31 g) represented by formula (18) as a curing agent, and 2PZ-CN (commercial product) as a curing accelerator Name: Shikoku Kasei Kogyo Co., Ltd. (0.02 g) was mixed to obtain a resin composition.
The obtained resin composition was melt-mixed on a hot plate heated to 180 ° C. The temperature was maintained as it was, and the resin composition was cured to obtain a cured product of Comparative Example 4.
The uniformity in the resin composition of Comparative Example 4 was visually evaluated according to the above criteria. The results are shown in Table 1.

“Comparative Example 5”
Epoxy compound (0.76 g) represented by formula (17), hydroquinone (0.24 g) represented by formula (19) as a curing agent, and 2PZ-CN (trade name: Shikoku Kasei Kogyo) as a curing accelerator Co., Ltd.) (0.02 g) was mixed to obtain a resin composition.
The obtained resin composition was melt-mixed on a hot plate heated to 150 ° C. The temperature was maintained as it was, and the resin composition was cured to obtain a cured product of Comparative Example 5.
The uniformity in the resin composition of Comparative Example 5 was visually evaluated according to the above criteria. The results are shown in Table 1.

About the hardened | cured material of Examples 1-3 and Comparative Examples 3-5, the heat conductivity, heat resistance, and the presence or absence of the liquid crystal structure were investigated with the method shown below. The results are shown in Table 1.
"Thermal conductivity"
As thermal conductivity of the hardened | cured material of Examples 1-3 and Comparative Examples 3-5, the heat conductivity was calculated | required with the method shown below.
The thermal conductivity of the cured product was calculated by multiplying the thermal diffusivity, specific heat, and density.
For the measurement of the thermal diffusivity, a xenon flash method thermal diffusivity measuring device TD-1 HTV (manufactured by Advance Riko Co., Ltd.) was used. Specific heat (25 degreeC) was calculated | required using MDSC Q2000 (made by TA Instrumental). The density was determined by the Archimedes method.

"Heat-resistant"
The glass transition temperature of the hardened | cured material of Examples 1-3 and Comparative Examples 3-5 was measured by the method shown below. The inflection point of the linear expansion coefficient was calculated | required using Thermo plus TMA8310 (made by Rigaku), and it was set as the glass transition temperature.
"With or without liquid crystal structure"
As a result of observing the hardened | cured material of Examples 1-3 and Comparative Examples 3-5 with the polarization microscope, it has confirmed that all have the orientation in which the smectic liquid crystal structure was formed.

As shown in Table 1, the resin compositions of Examples 1 to 3 containing Compound A having an epoxy group, a phenolic hydroxyl group, and a mesogen in the same molecule are all evaluated for uniformity and cured. Excellent compatibility with the agent and good uniformity.
In contrast, the resin compositions of Comparative Example 1 and Comparative Example 2 that did not contain Compound A had a uniformity evaluation of x, and a uniform cured product could not be obtained.

As shown in Table 1, the cured products of the resin compositions of Examples 1 to 3 had good thermal conductivity of 0.4 W / m · k or more. Moreover, the glass transition temperature was over 200 degreeC and heat resistance was favorable.
On the other hand, the hardened | cured material of the resin composition of Comparative Examples 3-5 was inadequate that thermal conductivity was less than 0.4 W / m * k. Moreover, the glass transition temperature was 150 ° C. or less, and the heat resistance was insufficient.

DESCRIPTION OF SYMBOLS 10 ... Resin board | substrate, 12 ... Resin sheet, 20 ... Hardened | cured material, 22 ... Resin component, 30 ... Core material, 50 ... Laminated substrate.

Claims (11)

  A compound having an epoxy group, a phenolic hydroxyl group, and a mesogen.   A compound having an epoxy group and one mesogen, wherein the mesogen has one or more phenolic hydroxyl groups. Between the epoxy group and the mesogen, a first linking group consisting of any one selected from —O—, —CH ₂ —, —CO—, —COO—, and —OCO— is disposed,
The compound according to claim 2, wherein one end of the first linking group is bonded to a terminal of the mesogen on the epoxy group side. Between the mesogen and the epoxy _{group, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 - second linking group comprising any one selected from is arranged,
The compound according to claim 2 or 3, wherein one end of the second linking group is bonded to the epoxy group. The said mesogen is shown by following formula (1) or (2), The compound as described in any one of Claims 2-4 characterized by the above-mentioned.

(In the formula (1), R1 to R4 are each independently a hydrogen atom or a methyl group. R5 to R9 are each independently a hydrogen atom, a methyl group, or a hydroxyl group, and any one of R5 to R9. The above is a hydroxyl group.)

(In Formula (2), R10 to R13 are each independently a hydrogen atom or a methyl group. R14 to R18 are each independently a hydrogen atom, a methyl group, or a hydroxyl group, and any one of R14 to R18) The above is a hydroxyl group, and X is any one of the following formulas (3) to (12).

(In Formula (3), R19 to R22 are each independently a hydrogen atom or a methyl group.)

(In Formula (4), R23 and R24 are each independently a hydrogen atom or a methyl group.)

(In Formula (5), R25 is a hydrogen atom or a methyl group.)

A compound represented by the following formula (13):

  A resin composition comprising the compound according to any one of claims 1 to 6.   A resin sheet obtained by molding the resin composition according to claim 7.   A cured resin comprising a cured product of the resin composition according to claim 7.   A resin substrate comprising a cured product of the resin composition according to claim 7.   A laminated substrate comprising a plurality of resin substrates, wherein at least one of the plurality of resin substrates includes a cured product of the resin composition according to claim 7.

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