JP2023085845A - Vinyl compound, method for producing vinyl compound, vinyl composition, cured vinyl resin, prepreg, resin-coated film, resin-coated metal foil, metal-clad laminate, and printed wiring board - Google Patents

Abstract

To provide a novel compound that can produce a resin suitable as a constituent material of a printed wiring board, having high thermal conductivity and low dielectric loss.SOLUTION: Provided is a vinyl compound represented by formula (1) (In the formula, A1, A2 and A3 are the same or different and represent a saturated or unsaturated 6-membered cyclic group described under formula (1). Q1 and Q2 are the same or different and represent a single bond, a linear or a branched alkylene group having 1 to 18 carbon atoms, or a divalent group represented by formula (2). Ar represents an aromatic group.).SELECTED DRAWING: None

Description

The present invention relates to a vinyl compound, a method for producing a vinyl compound, a vinyl composition, a cured vinyl resin, a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a printed wiring board.

2. Description of the Related Art The amount of data handled by communication devices and the communication speed are increasing year by year. When the amount of data handled by a communication device is large, the amount of heat generated by the electronic operation components in the communication device increases, and if the heat accumulates on the printed wiring board, problems will occur. Therefore, printed wiring boards are required to have high heat dissipation.

As a printed wiring board with high heat dissipation, for example, by increasing the thickness of the copper that forms the circuit (that is, the copper pattern), it is possible to release more heat through this copper. , so-called thick copper substrates are known. However, since this thick copper substrate is thick as a whole, there is a problem that it is not suitable for communication equipment that requires reduction in size and weight.

As a printed wiring board with high heat dissipation, a so-called metal base board is also known, in which a metal plate is provided on one surface of the board so that more heat can be dissipated through the metal plate. However, since the metal base substrate requires an increased number of manufacturing steps, there is a problem that the manufacturing cost of the communication device increases.

On the other hand, as with printed wiring boards, resin is used as a main constituent material, and as a member with high heat dissipation, a member containing a filler with high thermal conductivity is known. However, there is a problem that materials containing fillers are not suitable for manufacturing printed wiring boards due to their poor workability.

As a material that can solve these problems, a resin with high thermal conductivity is disclosed (Patent Document 1). Electronic materials used in high-speed communication devices are required to have low dielectric loss in addition to high heat dissipation. The resin disclosed in Patent Document 1 itself has high thermal conductivity, Dielectric loss is also low.

U.S. Patent Application Publication No. 2019/0194408

However, the thermal conductivity of the resin disclosed in Patent Document 1 is not sufficient, and there is still room for improvement.

An object of the present invention is to provide a novel compound that is suitable as a constituent material of a printed wiring board and from which a resin having high thermal conductivity and low dielectric loss can be produced.

The present invention employs the following configurations.
[1] Formula (1)

（式中、Ａ^１、Ａ^２およびＡ^３はそれぞれ同一または相異なって、下記式

(Wherein, A ¹ , A ² and A ³ are the same or different, and

で示されるいずれかの二価基を表す。ここで、Ｒは水素原子、炭素数１～１８のアルキル基または炭素数１～１８のアルコキシ基を表し、前記アルキル基およびアルコキシ基は直鎖状であってもよいし、分岐鎖状であってもよく、前記アルキル基およびアルコキシ基において、隣接しない１以上のメチレン基が酸素原子に置き換わっていてもよい。ａは１～１０の整数を、ｂおよびｃは１～８の整数を、ｄ、ｅ、ｆおよびｇは１～６の整数を、ｈは１～４の整数をそれぞれ表す。前記二価基において、Ｒが複数のとき、すべてのＲが同一の基を表してもよいし、異なる基を表してもよい。Ｑ^１およびＱ^２はそれぞれ同一または相異なって、単結合、炭素数１～１８の直鎖状もしくは分岐鎖状のアルキレン基または式（２）

Represents any divalent group represented by Here, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and the alkyl group and alkoxy group may be linear or branched. In the alkyl group and alkoxy group, one or more non-adjacent methylene groups may be replaced with oxygen atoms. a represents an integer of 1 to 10, b and c represent an integer of 1 to 8, d, e, f and g represent an integer of 1 to 6, and h represents an integer of 1 to 4. In the divalent group, when there are a plurality of R's, all the R's may represent the same group or different groups. Q ¹ and Q ² are each the same or different and are a single bond, a linear or branched alkylene group having 1 to 18 carbon atoms, or formula (2)

で示される二価基を表す。ここで、Ａｒは芳香族基を表す。前記式（２）中のメチレン基は、前記式（１）中の酸素原子に結合している。）
で示されるビニル化合物。
［２］前記式（１）で示されるビニル化合物が、式（３）

Represents a divalent group represented by Here, Ar represents an aromatic group. The methylene group in formula (2) is bonded to the oxygen atom in formula (1). )
A vinyl compound represented by
[2] The vinyl compound represented by the formula (1) is represented by the formula (3)

（式中、Ａ^４は、下記式

(In the formula, A ⁴ is the following formula

で示されるいずれかの二価基を表し、Ｒ、ａ、ｃ、ｈ、Ｑ^１およびＱ^２は上記と同一の意味を表す。）
で示されるビニル化合物である、［１］に記載のビニル化合物。
［３］前記式（３）で示されるビニル化合物において、前記Ｑ^１およびＱ^２がそれぞれ同一または相異なって、前記式（２）で示される二価基である、［２］に記載のビニル化合物。
［４］［１］に記載のビニル化合物を製造する方法であって、式（４）

and R, a, c, h, Q ¹ and Q ² have the same meanings as above. )
The vinyl compound according to [1], which is a vinyl compound represented by
[3] The vinyl according to [2], wherein in the vinyl compound represented by formula (3), ^Q1 and ^Q2 are the same or different and are divalent groups represented by formula (2). Compound.
[4] A method for producing the vinyl compound according to [1], which comprises formula (4)

（式中、Ａ^１、Ａ^２およびＡ^３はそれぞれ上記と同一の意味を表す。）
で示される化合物と、式（５）

(In the formula, A ¹ , A ² and A ³ each have the same meaning as above.)
A compound represented by the formula (5)

（式中、Ｑ^１は上記と同一の意味を表し、Ｘ^１はハロゲン原子を表す。）
で示される化合物と、式（６）

(In the formula, Q ¹ has the same meaning as above, and X ¹ represents a halogen atom.)
A compound represented by the formula (6)

（式中、Ｑ^２は上記と同一の意味を表し、Ｘ^２はハロゲン原子を表し、前記Ｘ^１と同一であってもよいし、異なっていてもよい。）
で示される化合物と、を塩基の存在下で反応させる、ビニル化合物の製造方法。
［５］［１］～［３］のいずれか一項に記載のビニル化合物を含有するビニル組成物。
［６］［１］～［３］のいずれか一項に記載のビニル化合物、［５］に記載のビニル組成物を硬化してなるビニル樹脂硬化物。
［７］［１］～［３］のいずれか一項に記載のビニル化合物もしくはその半硬化物、または［５］に記載のビニル組成物もしくはその半硬化物と、繊維質基材と、を備えるプリプレグ。
［８］［１］～［３］のいずれか一項に記載のビニル化合物もしくはその半硬化物、または［５］に記載のビニル組成物もしくはその半硬化物を含む樹脂層と、支持フィルムと、を備える樹脂付きフィルム。
［９］［１］～［３］のいずれか一項に記載のビニル化合物もしくはその半硬化物、または［５］に記載のビニル組成物もしくはその半硬化物を含む樹脂層と、金属箔と、を備える樹脂付き金属箔。
［１０］［１］～［３］のいずれか一項に記載のビニル化合物の硬化物、［５］に記載のビニル組成物の硬化物、または［７］に記載のプリプレグの硬化物を含む絶縁層と、金属箔と、を備える金属張積層板。
［１１］［１］～［３］のいずれか一項に記載のビニル化合物の硬化物、［５］に記載のビニル組成物の硬化物、または［７］に記載のプリプレグの硬化物を含む絶縁層と、導体配線と、を備えるプリント配線板。

(In the formula, Q ² has the same meaning as above, X ² represents a halogen atom, and may be the same as or different from X ¹ above.)
A method for producing a vinyl compound, comprising reacting a compound represented by in the presence of a base.
[5] A vinyl composition containing the vinyl compound according to any one of [1] to [3].
[6] A vinyl resin cured product obtained by curing the vinyl compound according to any one of [1] to [3] and the vinyl composition according to [5].
[7] The vinyl compound or semi-cured material thereof according to any one of [1] to [3], or the vinyl composition or semi-cured material thereof according to [5], and a fibrous base material Prepare prepreg.
[8] a resin layer containing the vinyl compound or semi-cured material thereof according to any one of [1] to [3], or the vinyl composition or semi-cured material thereof according to [5], and a support film; A resin-coated film comprising:
[9] a resin layer containing the vinyl compound or its semi-cured material according to any one of [1] to [3], or the vinyl composition according to [5] or its semi-cured material; and a metal foil , a metal foil with resin.
[10] A cured product of the vinyl compound according to any one of [1] to [3], a cured product of the vinyl composition according to [5], or a cured product of the prepreg according to [7]. A metal-clad laminate comprising an insulating layer and a metal foil.
[11] A cured product of the vinyl compound according to any one of [1] to [3], a cured product of the vinyl composition according to [5], or a cured product of the prepreg according to [7]. A printed wiring board comprising an insulating layer and conductor wiring.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a novel compound that is suitable as a constituent material for printed wiring boards and from which a resin having high thermal conductivity and low dielectric loss can be produced.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically an example of the laminated structure obtained using the vinyl compound which concerns on one Embodiment of this invention. FIG. 4 is a cross-sectional view schematically showing another example of a laminated structure obtained using the vinyl compound according to one embodiment of the present invention. FIG. 4 is a cross-sectional view schematically showing still another example of a laminated structure obtained using the vinyl compound according to one embodiment of the present invention. FIG. 4 is a cross-sectional view schematically showing still another example of a laminated structure obtained using the vinyl compound according to one embodiment of the present invention.

<<vinyl compound>>
The vinyl compound of this embodiment has the formula (1)

（式中、Ａ^１、Ａ^２およびＡ^３はそれぞれ同一または相異なって、下記式

(Wherein, A ¹ , A ² and A ³ are the same or different, and

で示されるいずれかの二価基を表す。ここで、Ｒは水素原子、炭素数１～１８のアルキル基または炭素数１～１８のアルコキシ基を表し、前記アルキル基およびアルコキシ基は直鎖状であってもよいし、分岐鎖状であってもよく、前記アルキル基およびアルコキシ基において、隣接しない１以上のメチレン基が酸素原子に置き換わっていてもよい。ａは１～１０の整数を、ｂおよびｃは１～８の整数を、ｄ、ｅ、ｆおよびｇは１～６の整数を、ｈは１～４の整数をそれぞれ表す。前記二価基において、Ｒが複数のとき、すべてのＲが同一の基を表してもよいし、異なる基を表してもよい。Ｑ^１およびＱ^２はそれぞれ同一または相異なって、単結合、炭素数１～１８の直鎖状もしくは分岐鎖状のアルキレン基または式（２）

Represents any divalent group represented by Here, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and the alkyl group and alkoxy group may be linear or branched. In the alkyl group and alkoxy group, one or more non-adjacent methylene groups may be replaced with oxygen atoms. a represents an integer of 1 to 10, b and c represent an integer of 1 to 8, d, e, f and g represent an integer of 1 to 6, and h represents an integer of 1 to 4. In the divalent group, when there are a plurality of R's, all the R's may represent the same group or different groups. Q ¹ and Q ² are each the same or different and are a single bond, a linear or branched alkylene group having 1 to 18 carbon atoms, or formula (2)

で示される二価基を表す。ここで、Ａｒは芳香族基を表す。前記式（２）中のメチレン基は、前記式（１）中の酸素原子に結合している。）
で示される。
本明細書においては、本実施形態の式（１）で示されるビニル化合物を「ビニル化合物（１）」ということがある。

Represents a divalent group represented by Here, Ar represents an aromatic group. The methylene group in formula (2) is bonded to the oxygen atom in formula (1). )
is indicated by
In this specification, the vinyl compound represented by Formula (1) of this embodiment is sometimes referred to as "vinyl compound (1)".

The vinyl compound (vinyl compound (1)) of the present embodiment is a polymerizable monomer, and forms a vinyl resin cured product described later by polymerization (also referred to as “curing” in the present specification).

The structure in which the A ¹ , A ² and A ³ are linked in the vinyl compound (1) is a mesogenic skeleton. The greater the number of hydrogen rings, the higher the degree of orientation. The resin, which is the cured product of vinyl compound (1), has high thermal conductivity due to having such a structure with a high degree of orientation.

On the other hand, it is known that resins having hydroxyl groups at or near their ends have high dielectric loss. For example, a resin, which is a cured product of a compound (monomer) having an epoxy group at its end, has a hydroxyl group at or near its end and has a high dielectric loss. On the other hand, the vinyl compound (1) has a vinyl group (ethenyl group) at both ends and does not have an epoxy group or a hydroxyl group. With no hydroxyl groups near or near the ends, such resins have low dielectric loss.

Examples of the alkyl group having 1 to 18 carbon atoms in R include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl straight-chain or branched-chain alkyl groups having 1 to 18 carbon atoms such as groups, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group.

Examples of the alkoxy group having 1 to 18 carbon atoms in R include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n -pentyloxy group, isopentyloxy group, neopentyloxy group, tert-pentyloxy group, n-hexyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 2,2-dimethylbutyloxy group, 2,3-dimethylbutyloxy group, n-heptyloxy group, 2-methylhexyloxy group, 3-methylhexyloxy group, 2,2-dimethylpentyloxy group, 2,3-dimethylpentyloxy group, 2,4 -dimethylpentyloxy group, 3,3-dimethylpentyloxy group, 3-ethylpentyloxy group, 2,2,3-trimethylbutyloxy group, n-octyloxy group, isooctyloxy group, 2-ethylhexyloxy group , n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy straight-chain or branched-chain alkoxy groups having 1 to 18 carbon atoms, such as groups, n-heptadecyloxy groups, and n-octadecyloxy groups.

In the alkyl group having 1 to 18 carbon atoms and the alkoxy group having 1 to 18 carbon atoms in R, one or more non-adjacent methylene groups ( _--CH.sub.2-- ) may be replaced with an oxygen atom (--O--). .
In the alkyl group and alkoxy group, when methylene groups are substituted with oxygen atoms, the number thereof (the number of methylene groups substituted with oxygen atoms) is less than the number of carbon atoms in the alkyl group and alkoxy group, and the carbon Although it is determined according to the number, usually 1 to 3 is preferable.

A ¹ and A ³ are the same or different, and are represented by the following formula

（式中、Ｒおよびｈは上記と同一の意味を表す。）
で示される二価基であることが好ましく、それぞれ同一または相異なって、１，４－フェニレン基、３－メチル－１，４－フェニレン基または２－メチル－１，４－フェニレン基であることがより好ましい。

(Wherein, R and h have the same meanings as above.)
is preferably a divalent group represented by and is the same or different and is a 1,4-phenylene group, a 3-methyl-1,4-phenylene group or a 2-methyl-1,4-phenylene group is more preferred.

A ² is represented by the following formula

で示されるいずれかの二価基であることが好ましい。ここでＲ、ａ、ｃおよびｈは上記と同一の意味を表す。

Any divalent group represented by is preferred. Here, R, a, c and h have the same meanings as above.

Examples of the linear or branched alkylene group having 1 to 18 carbon atoms in Q ¹ and Q ² include methylene group, ethylene group, trimethylene group (1,3-propylene group), 1,2-propylene group, tetramethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, pentamethylene group, 1-methyl-1,4 -butylene group, 2-methyl-1,4-butylene group, hexamethylene group, heptamethylene group, octamethylene group, 2-ethyl-1,6-hexylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptadecamethylene group, octadecamethylene group and the like.

The aromatic group for Ar is a divalent aromatic group, and specific examples thereof include 1,4-phenylene group and 1,3-phenylene group.

When Q ¹ or Q ² is a divalent group represented by the formula (2), the methylene group (—CH ₂ —) in the formula (2) is the oxygen atom in the formula (1). and Ar (aromatic group) in the formula (2) is bonded to the vinyl group (CH ₂ =CH-) in the formula (1).

The Q ¹ and Q ² are preferably the same or different and are preferably divalent groups represented by the formula (2), and the same or different and Ar is a 1,4-phenylene group or 1 , 3-phenylene group is more preferably a divalent group represented by the formula (2).

The vinyl compound (1) has the formula (3)

（式中、Ａ^４は、下記式

(In the formula, A ⁴ is the following formula

で示されるいずれかの二価基を表し、Ｒ、ａ、ｃ、ｈ、Ｑ^１およびＱ^２は上記と同一の意味を表す。）
で示されるビニル化合物（本明細書においては、「ビニル化合物（３）」ということがある）であることが好ましい。

and R, a, c, h, Q ¹ and Q ² have the same meanings as above. )
is preferably a vinyl compound represented by (in this specification, sometimes referred to as "vinyl compound (3)").

In the vinyl compound (3), Q ¹ and Q ² are preferably the same or different and are preferably divalent groups represented by the formula (2), and the same or different and Ar is More preferably, it is a divalent group represented by the above formula (2) when it is a 1,4-phenylene group or a 1,3-phenylene group.

<<Method for producing vinyl compound>>
Vinyl compound (1) has, for example, formula (4)

（式中、Ａ^１、Ａ^２およびＡ^３はそれぞれ上記と同一の意味を表す。）
で示される化合物（本明細書においては、「化合物（４）」ということがある）と、式（５）

(In the formula, A ¹ , A ² and A ³ each have the same meaning as above.)
A compound represented by (in this specification, sometimes referred to as "compound (4)"), and formula (5)

（式中、Ｑ^１は上記と同一の意味を表し、Ｘ^１はハロゲン原子を表す。）
で示される化合物（本明細書においては、「化合物（５）」ということがある）と、式（６）

(In the formula, Q ¹ has the same meaning as above, and X ¹ represents a halogen atom.)
A compound represented by (in this specification, sometimes referred to as "compound (5)"), and formula (6)

（式中、Ｑ^２は上記と同一の意味を表し、Ｘ^２はハロゲン原子を表し、前記Ｘ^１と同一であってもよいし、異なっていてもよい。）
で示される化合物（本明細書においては、「化合物（６）」ということがある）と、を塩基の存在下で反応させることで製造できる。

(In the formula, Q ² has the same meaning as above, X ² represents a halogen atom, and may be the same as or different from X ¹ above.)
It can be produced by reacting a compound represented by (in this specification, sometimes referred to as "compound (6)") in the presence of a base.

Examples of the compound (4) include 1,4-bis(4-hydroxyphenyl)-1-cyclohexene, 1-(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)-1- Cyclohexene, 1,4-bis(4-hydroxyphenyl)-2-cyclohexene, 1-(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)-2-cyclohexene, 1,4-bis( 4-hydroxyphenyl)-2,5-cyclohexadiene, 1-(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)-2,5-cyclohexadiene, 1,4-bis(4- hydroxyphenyl)-1,5-cyclohexadiene, 1-(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)-1,5-cyclohexadiene, 1,4-bis(4-hydroxyphenyl )-1,4-cyclohexadiene, 1-(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)-1,4-cyclohexadiene, 1,4-bis(4-hydroxyphenyl)- 1,3-cyclohexadiene, 1-(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)-1,3-cyclohexadiene, 1,4-bis(4-hydroxyphenyl)benzene, 1 -(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1-(3-methyl-4-hydroxyphenyl)-4- (4-Hydroxyphenyl)cyclohexane and the like. Compound (4) is, for example, JP-A-1-168632, JP-A-1-168634, US Pat. 2002-308809, JP-A-2002-363117, JP-A-2003-12585, etc., according to known methods.

X ¹ and X ² are the same or different and represent a halogen atom, and examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.
The compounds (5) and (6) may be the same or different.
Examples of compound (5) and compound (6) include 2-vinylbenzyl bromide, 3-vinylbenzyl bromide, 4-vinylbenzyl bromide, vinyl chloride, vinyl bromide, 2-vinylbenzyl chloride, 3-vinylbenzyl chloride, 4-vinylbenzyl chloride, 1-propenyl chloride, 1-propenyl bromide, 1-butenyl chloride, 1-butenyl bromide, 1-pentenyl chloride, 1-pentenyl bromide, 1-hexenyl chloride, 1-hexenyl bromide, 1- heptenyl chloride, 1-heptenyl bromide, 1-octenyl chloride, 1-octenyl bromide, 1-nonenyl chloride, 1-nonenyl bromide, 1-decenyl chloride, 1-decenyl bromide, 1- undecenyl chloride, 1-undecenyl bromide, 1-dodecenyl chloride, 1-dodecenyl bromide, 1-tridecenyl chloride, 1-tridecenyl bromide, 1-tetradecenyl chloride, 1-tetradecenyl bromide, 1-pentadecenyl chloride, 1-pentadecenyl bromide, 1-hexadecenyl chloride, 1-hexadecenyl bromide, 1-heptadecenyl chloride, 1- heptadecenyl bromide, 1-octadecenyl chloride, 1-octadecenyl bromide and the like.

When compound (5) and compound (6) are the same, the amount to be used is generally preferably 2 to 100-fold mol, more preferably 2 to 50-fold mol, relative to compound (4). When compound (5) and compound (6) are different, the amount of compound (5) to be used is generally preferably 1 to 50-fold mol, more preferably 1 to 25-fold mol, relative to compound (4), The amount of compound (6) to be used is generally preferably 1- to 50-fold mol, more preferably 1 to 25-fold mol, relative to compound (4).

The base may be either an inorganic base or an organic base.
Examples of the inorganic base include alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali carbonates such as sodium carbonate and potassium carbonate. A metal salt etc. are mentioned. Examples of the organic base include pyridine and the like. The amount of the base to be used is generally preferably 2- to 5-fold mol of compound (4). When using an organic base that is liquid under the reaction conditions, such an organic base may be used in excess to serve as the reaction solvent.

The reaction of compound (4), compound (5) and compound (6) is usually carried out by mixing compound (4), compound (5), compound (6) and a base in a solvent. The mixing order is not particularly limited.

The solvent is not particularly limited as long as it is inert to the reaction, but a hydrophilic solvent is preferable because the formation of by-products is easily suppressed. Examples of the hydrophilic solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol and propylene glycol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; aprotic polar solvents such as dimethylsulfoxide and N-methylpyrrolidone; and ether solvents such as tetrahydrofuran, dioxane, methoxymethyl ether, diethoxyethane and the like alone or mixed solvents. Further, as described above, when an organic base that is liquid under the reaction conditions is used as the base, the organic base may be used as the reaction solvent.
Among these, the solvent is preferably an ether solvent, an aprotic polar solvent, or a mixed solvent thereof, more preferably an aprotic polar solvent, and particularly preferably N,N-dimethylformamide.
The amount of solvent used is preferably 1 to 20 mL, more preferably 2 to 10 mL, per 1 g of compound (4).

Reaction of compound (4) with compound (5), whether or not compound (5) and compound (6) are identical; intermediates that are reactants of compound (4) and compound (5) and the reaction of the compound (6); the reaction of the compound (4) and the compound (6); the reaction intermediate between the compound (4) and the compound (6) and the compound (5) Both reactions may be carried out via a halogen exchange reaction in the presence of a catalyst.
Examples of the catalyst include alkali metal halides such as sodium iodide and potassium iodide; and quaternary ammonium halides such as tetrabutylammonium iodide.
When a catalyst is used, its amount is generally preferably 0.05 to 1-fold mass, more preferably 0.1 to 0.5-fold mass, relative to the amount of compound (4) used.

The reaction of compound (4), compound (5) and compound (6) may be carried out in the presence of a polymerization inhibitor. Examples of the polymerization inhibitor include 2,6-di(tert-butyl)-p-cresol. When a polymerization inhibitor is used, the amount used is usually preferably 0.002 to 0.05 times by mass, more preferably 0.004 to 0.05 times the total amount of compound (5) and compound (6) used. It is 0.02 mass times.

The reaction may be carried out under normal pressure conditions or under reduced pressure conditions. The reaction temperature is usually preferably 10 to 150°C. In this reaction, water may be produced as a by-product as the reaction progresses. It is preferable to carry out the reaction at the reaction temperature and reaction pressure that are eliminated. The reaction time is generally preferably 1 to 24 hours.

After completion of the reaction, for example, the reaction solution is cooled, water or a mixed solvent containing water is added, the precipitated solid is separated by filtration, and if necessary, a known post-treatment operation is performed once or twice or more. Thus, a vinyl compound (1) is obtained. Examples of the post-treatment operation include stirring and washing the solid in water, a mixed solvent containing water, or an organic solvent; extraction (liquid separation) of a solution in which the solid is dissolved; The resulting vinyl compound (1) may be further purified by conventional purification means, if necessary.

The structure of the obtained vinyl compound (1) can be confirmed by a known method such as nuclear magnetic resonance (NMR) method.

<<vinyl composition>>
The vinyl composition of the present embodiment contains vinyl compound (1).
In this specification, the vinyl composition of this embodiment is sometimes referred to as "vinyl composition (1)".

The vinyl composition (1) has curability and may contain only the vinyl compound (1), or contains the vinyl compound (1) and does not impair the effects of the present invention. , may contain other components than the vinyl compound (1). Vinyl compound (1) is cured by heating. When curing the vinyl compound (1), pressure may be applied to the vinyl compound (1).

The number of vinyl compounds (1) contained in the vinyl composition (1) may be one, or two or more.

<Other ingredients>
Other components contained in the vinyl composition (1) include, for example, a radical initiator; a filler; an additive; a solvent; resins other than the polymer (cured product) of the vinyl compound (1) (in this specification, sometimes referred to as "another resin"), and the like.

Examples of the additives include silane coupling agents, colorants, low-stress components, release agents, antioxidants, antifoaming agents, flow control agents, and the like.

Examples of the radical initiator include azo compounds and organic peroxides.

Examples of the filler include silica powder such as fused crushed silica powder, fused spherical silica powder, crystalline silica powder, and secondary aggregated silica powder; metals such as alumina, titanium oxide, zinc oxide, tungsten carbide, and magnesium oxide; glass cloth (glass fiber); carbon fiber; nitrides such as boron nitride, aluminum nitride, silicon nitride and titanium nitride; silicon carbide; aluminum hydroxide; talc;

Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane.
Examples of the coloring agent include carbon black.
Examples of the low-stress component include silicone oil and silicone rubber.
Examples of the release agent include natural waxes, synthetic waxes, higher fatty acids, metal salts of higher fatty acids, and paraffin.

Examples of the solvent contained in the vinyl composition (1) include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; aprotic polar solvents such as dimethyl sulfoxide and N-methylpyrrolidone; ester solvents; glycol solvents such as propylene glycol monomethyl ether; aromatic solvents such as toluene.

The other vinyl compound is not particularly limited as long as it has a vinyl group and is not a vinyl compound (1).
The other resin is not particularly limited as long as it is a resin other than the polymer of vinyl compound (1).

The other components contained in the vinyl composition (1) may be of one kind or may be of two or more kinds.

The content of the other component in the vinyl composition (1) can be arbitrarily selected according to the type of the other component.
In the vinyl composition (1), the ratio of the content of the vinyl compound (1) to the total content of components other than the solvent is preferably 80% by mass or more, for example, 85% by mass or more, 90% by mass. Any one of 95% by mass or more, 97% by mass or more, or 99% by mass or more may be used. On the other hand, the said ratio is 100 mass % or less. The vinyl composition (1) in which the proportion is 80% by mass or more exhibits a higher effect due to the inclusion of the vinyl compound (1).

The vinyl compound (1) obtained by the above method can be used as the vinyl composition (1) as it is. The vinyl composition (1) containing the other components is obtained by mixing the vinyl compound (1) with the other components.

<<Vinyl resin cured product>>
The vinyl resin cured product of the present embodiment is obtained by curing vinyl compound (1) or vinyl composition (1).
In this specification, the vinyl resin cured product of this embodiment is sometimes referred to as "vinyl resin cured product (1)".

The vinyl resin cured product has high thermal conductivity and low dielectric loss due to the use of the vinyl compound (1), so it is suitable as a constituent material for printed wiring boards, especially for printed wiring boards. It is particularly suitable as an insulating material for

When the vinyl resin cured product (1) is a cured product of the vinyl compound (1), the vinyl resin cured product (1) may be a cured product of one kind of the vinyl compound (1), or two or more kinds. may be a cured product of the vinyl compound (1).
When the vinyl resin cured product (1) is a cured product of the vinyl composition (1), the vinyl resin cured product (1) may be a cured product of one kind of the vinyl composition (1). It may be a cured product of a mixture of more than one vinyl composition (1).

Vinyl resin cured product (1) is obtained by, for example, curing vinyl compound (1) or vinyl composition (1) by heating vinyl compound (1) or vinyl composition (1) as it is at a predetermined temperature; vinyl compound (1) or vinyl composition (1). or, if necessary, the powder is melted, poured into a mold, and heated for a predetermined time while applying a predetermined pressure with a press or the like; vinyl compound (1) or vinyl composition (1) is heated and melted and poured into a mold or the like, and the mold is further heated to mold; A method of injecting into a mold and curing; Partially curing the vinyl compound (1) or the vinyl composition (1), pulverizing the resulting partially cured product, and filling the mold with the powder obtained. A method of melt-molding a powder; the vinyl compound (1) or vinyl composition (1) is dissolved in a solvent as it is, or if necessary, partially cured while stirring, and after casting the obtained solution, the solvent is It can be manufactured by a method of drying and removing by air drying or the like, and heating for a predetermined time while applying a predetermined pressure with a press or the like as necessary.

The heating temperature (curing temperature) at which vinyl compound (1) or vinyl composition (1) is cured by heating is not particularly limited. In terms of increasing the temperature, the temperature is preferably 140° C. or higher, and more preferably 150° C. or higher. The heating temperature is preferably 200° C. or lower in order to avoid excessive heating.

The heating time (curing time) when the vinyl compound (1) or the vinyl composition (1) is cured by heating is not particularly limited. From the point of view of increasing the time, the time is preferably 1 hour or longer, and more preferably 2 hours or longer. The heating time is preferably 10 hours or less in order to avoid unnecessary curing work.

The applied pressure (pressure during curing) when the vinyl compound (1) or the vinyl composition (1) is cured by pressing is not particularly limited, but the vinyl compound (1) or the vinyl composition (1) is cured. It is preferably 0.7 MPa or more, more preferably 1.2 MPa or more, in terms of increasing the strength. The pressurization pressure is preferably 3 MPa or less in order to avoid excessive pressurization.

The thermal diffusivity of the cured vinyl resin (1) is preferably 2.0×10 ⁻⁷ m ² /s or more, more preferably 2.2×10 ⁻⁷ m ² /s or more, More preferably, it is 2.4×10 ⁻⁷ m ² /s or more. ^The upper limit of the thermal diffusivity of ^the cured vinyl resin (1) is not particularly limited. It may be 10 ⁻⁷ m ² /s or less, or may be 3.2×10 ⁻⁷ m ² /s or less.
Thermal diffusivity of cured vinyl resin (1) is, for example, 2.0×10 ⁻⁷ to 4.0×10 ⁻⁷ m ² /s, 2.2×10 ⁻⁷ to 3.6×10 ⁻⁷ m ² /s, and 2.4×10 ⁻⁷ to 3.2×10 ⁻⁷ m ² /s.

The thermal diffusivity of the cured vinyl resin (1) can be measured by temperature wave thermal analysis (TWA method).

The dielectric loss tangent of the cured vinyl resin (1) at a frequency of 100 MHz is preferably 0.005 or less, more preferably 0.0048 or less, even more preferably 0.0046 or less. The lower limit of the dielectric loss tangent of the cured vinyl resin (1) is not particularly limited, and the dielectric loss tangent may be 0.001 or more, 0.002 or more, or 0.002 or more. 003 or more.
The dielectric loss tangent of the cured vinyl resin (1) at a frequency of 100 MHz may be, for example, any one of 0.001 to 0.005, 0.002 to 0.0048, and 0.003 to 0.0046. . However, these are examples of the dielectric loss tangent of the cured vinyl resin (1).

The dielectric loss tangent of the vinyl resin cured product (1) at a frequency of 100 MHz can be measured under the following conditions by a capacitance method using an impedance analyzer.
・Measurement method: capacitance method ・Electrode model: 16453A
・Measurement environment: 23°C, 50% RH
・Applied voltage: 1V

<<Prepreg>>
The prepreg of this embodiment comprises a vinyl compound (1) or a semi-cured product thereof, or a vinyl composition (1) or a semi-cured product thereof, and a fibrous base material.
In this specification, the prepreg of this embodiment may be referred to as "prepreg (1)". By using the prepreg (1), a laminate or the like can be easily produced by a normal method. For example, a desired laminate can be obtained by stacking a plurality of prepregs (1) to form a laminate, molding the laminate under pressure while heating, and integrating the laminate.
The printed wiring board (resin layer in the printed wiring board) obtained using the prepreg (1) or the laminate has high thermal conductivity and low dielectric loss due to the use of the vinyl compound (1). is low.

The prepreg (1) is prepared by coating or impregnating a fibrous base material with a solution in which the vinyl compound (1) is dissolved in a solvent, or by diluting the vinyl composition (1) or the vinyl composition (1) with a solvent. It can be produced by coating or impregnating a fibrous base material with the diluted product, and then heating the coated or impregnated fibrous base material to semi-cure the vinyl compound (1) or the vinyl composition (1). .

The heating temperature (semi-curing temperature) and heating time (semi-curing time) for semi-curing vinyl compound (1) or vinyl composition (1) are the same as those described above for vinyl compound (1) or vinyl composition (1). Curing conditions (heating temperature and heating time) can be appropriately set so that vinyl compound (1) or vinyl composition (1) is not completely cured.

The fibrous base material is not particularly limited as long as it is a fibrous base material, and may be a known one. More specific examples of the fibrous base material include woven fabrics and non-woven fabrics of inorganic fibers such as glass fibers, and woven fabrics and non-woven fabrics of organic fibers such as polyester.

<<Film with resin>>
The resin-coated film of the present embodiment comprises a resin layer containing vinyl compound (1) or its semi-cured material or vinyl composition (1) or its semi-cured material, and a support film. More specifically, the resin-coated film of the present embodiment includes, for example, a resin-coated film including the resin layer and the support film provided on one side or both sides of the resin layer. . A laminated sheet is obtained by using a plurality of resin-coated films of the present embodiment, removing the support film, superimposing them to form a laminate, and molding and integrating the laminate by applying pressure while heating. . The resin layer in the resin-coated film of the present embodiment and the printed wiring board (resin layer in the printed wiring board) obtained by using the resin layer or the laminated sheet are obtained by using the vinyl compound (1). , its high thermal conductivity and low dielectric loss.

Examples of the support film include polyethylene terephthalate (PET) films.
In the resin-coated film, when support films are provided on both sides of the resin layer, these support films may be the same or different. In the present specification, not only in the case of the resin-coated film, but the two layers of support films are different from each other means that at least one of the material and thickness of the two layers of support films is different from each other.

The resin-coated film of the present embodiment is prepared by applying a solution of the vinyl compound (1) dissolved in a solvent to the support film, or by applying the vinyl composition (1) or by diluting the vinyl composition (1) with a solvent. It can be produced by applying the diluted product to the support film, then heating the layer of this applied product, and semi-curing the vinyl compound (1) or vinyl composition (1) in this applied product. The conditions for semi-curing the vinyl compound (1) or the vinyl composition (1) at this time are the same as the conditions for the prepreg production described above.

<<Metal foil with resin>>
The resin-coated metal foil of this embodiment includes a resin layer containing vinyl compound (1) or its semi-cured material, or vinyl composition (1) or its semi-cured material, and metal foil. More specifically, the resin-coated metal foil of the present embodiment is, for example, a resin-coated metal foil comprising the resin layer and the metal foil provided on one side or both sides of the resin layer. mentioned. For example, by using the metal foil with resin of the present embodiment, the semi-cured material is further cured to obtain a cured material, and the metal foil is patterned to form a circuit, whereby a printed wiring board can be obtained. Also, using the metal foil with resin of the present embodiment, the metal foil is patterned to form a circuit, resin layers having such a circuit are laminated with the direction of the circuit aligned, and pressed while being heated. and further curing the semi-cured product to obtain a multilayer printed wiring board having a resin layer containing a cured product of the vinyl compound (1) or a cured product of the vinyl composition (1) as an insulating layer. can be done. The resin layer in the resin-coated metal foil of the present embodiment and the printed wiring board (resin layer in the printed wiring board) obtained using the resin-coated metal foil are obtained by using the vinyl compound (1). , its high thermal conductivity and low dielectric loss.

As said metal foil, copper foil etc. are mentioned, for example.
In the resin-coated metal foil, when metal foils are provided on both sides of the resin layer, these metal foils may be the same or different. In this specification, not only in the case of the resin-coated metal foil, but two layers of metal foil differ from each other means that at least one of the material and thickness of the two layers of metal foil is different from each other.

The resin-coated metal foil of this embodiment can be produced by the same method as the resin-coated film, except that the metal foil is used instead of the support film.

<<Metal clad laminate>>
The metal-clad laminate of the present embodiment includes an insulating layer containing a cured product of vinyl compound (1), a cured product of vinyl composition (1), or a cured product of prepreg (1), and a metal foil. As the metal-clad laminate of the present embodiment, more specifically, for example, a metal-clad laminate comprising the insulating layer and the metal foil provided on one side or both sides of the insulating layer. mentioned. The metal-clad laminate of the present embodiment can be made into a printed wiring board by, for example, patterning the metal foil therein to form a conductor wiring (circuit). Furthermore, a multilayer printed wiring board can be obtained by laminating a plurality of such printed wiring boards via a separately prepared insulating layer and applying pressure while heating. The insulating layer in the metal-clad laminate of the present embodiment and the printed wiring board obtained using the metal-clad laminate (insulating layer in the printed wiring board) are obtained by using the vinyl compound (1). , its high thermal conductivity and low dielectric loss.

The metal foil included in the metal-clad laminate of the present embodiment is the same as the metal foil included in the resin-coated metal foil described above.
In the metal-clad laminate, when metal foils are provided on both sides of the insulating layer, these metal foils may be the same or different.

The insulating layer separately used when laminating the printed wiring board may be a known one, the resin layer in the resin-coated film, or the laminated sheet that is a laminate of a plurality of the resin layers. It may be the prepreg (1) described above, or the laminate obtained by laminating a plurality of prepregs (1). Alternatively, in the resin layer, laminated sheet, prepreg (1), or laminated plate, the insulating layer may be obtained by further curing the vinyl compound (1) or the vinyl composition (1).

The metal-clad laminate of the present embodiment can be produced, for example, by laminating a metal foil on one side or both sides of the prepreg (1) and applying pressure while heating the laminate thus obtained. The vinyl compound (1) or a semi-cured product thereof, or the vinyl composition (1) or a semi-cured product thereof in 1) is further cured to form a cured product to form an insulating layer, and the prepreg (1) and the metal It can be manufactured by fusing foils.
For the metal-clad laminate of the present embodiment, for example, the vinyl compound (1) or the vinyl composition (1) is used to produce the prepreg (1) by the method described above, and the prepreg (1) is used to You may manufacture by said method.
The metal-clad laminate of the present embodiment can be obtained, for example, by heating the above metal foil with resin to obtain the vinyl compound (1) in the resin layer or a semi-cured product thereof, or the vinyl composition (1) or a semi-cured product thereof. It can also be produced by further curing the product to form an insulating layer containing a cured product of vinyl compound (1) or a cured product of vinyl composition (1).

<<Printed wiring board>>
The printed wiring board of the present embodiment includes an insulating layer containing a cured product of vinyl compound (1), a cured product of vinyl composition (1), or a cured product of prepreg (1), and conductor wiring. More specifically, the printed wiring board of the present embodiment includes, for example, a printed wiring board including the insulating layer and the conductive wiring provided on one surface or both surfaces of the insulating layer. . A multilayer printed wiring board can be obtained by laminating a plurality of printed wiring boards according to the present embodiment via an insulating layer prepared separately and applying pressure while heating. The printed wiring board (insulating layer in the printed wiring board) of the present embodiment has high thermal conductivity and low dielectric loss due to the use of the vinyl compound (1).

The material of the conductor wiring is the same as the metal of the metal foil included in the metal-clad laminate described above. The insulating layer separately used when laminating the printed wiring board of the present embodiment is the insulating layer described above.
In the printed wiring board, when conductor wirings are provided on both sides of the insulating layer, the material and thickness of these conductor wirings may be the same or different.

The printed wiring board of the present embodiment can be produced, for example, by patterning the metal foil in the metal-clad laminate described above to form conductor wiring (circuits).
The printed wiring board of the present embodiment can be produced, for example, by heating the metal foil with resin described above to obtain the vinyl compound (1) in the resin layer or a semi-cured product thereof, or the vinyl composition (1) or a semi-cured product thereof. is further cured to form an insulating layer containing the cured product of the vinyl compound (1) or the cured product of the vinyl composition (1), and the metal foil is patterned to form a conductor wiring (circuit). It can also be manufactured.
The metal foil can be patterned by a known method such as etching.

FIG. 1 is a cross-sectional view schematically showing an example of the laminated structure of the present embodiment obtained using vinyl compound (1). It should be noted that, in the drawings used in the following description, in order to make the features of the present invention easier to understand, there are cases where the essential parts are enlarged for the sake of convenience, and the dimensional ratio of each component is the same as the actual one. not necessarily.

The laminated structure 1 shown here includes a first layer 11 and a second layer 12 provided on one surface 11 a of the first layer 11 . The first layer 11 is a layer obtained using vinyl compound (1). The second layer 12 is selected according to the type of laminated structure 1 . Both the first layer 11 and the second layer 12 are film-like or sheet-like. The second layer 12 may be provided on the entire one surface 11a of the first layer 11, or may be provided on a partial area.

Laminated structure in which the first layer 11 is a resin layer containing the vinyl compound (1) or its semi-cured material, or the vinyl composition (1) or its semi-cured material, and the second layer 12 is a support film 1 is a film with resin.
Laminated structure in which the first layer 11 is a resin layer containing the vinyl compound (1) or its semi-cured material, or the vinyl composition (1) or its semi-cured material, and the second layer 12 is a metal foil 1 is a metal foil with resin.
When the first layer 11 is an insulating layer containing a cured product of the vinyl compound (1), a cured product of the vinyl composition (1), or a cured product of the prepreg (1), and the second layer 12 is a metal foil The laminate structure 1 of is a metal-clad laminate.

FIG. 2 is a cross-sectional view schematically showing another example of the laminated structure of the present embodiment obtained using the vinyl compound (1). In the drawings after FIG. 2, the same constituent elements as those shown in already explained figures are given the same reference numerals as in the already explained figures, and detailed explanations thereof will be omitted.

The laminated structure 2 shown here includes a first layer 11 and a second layer 22 provided on one surface 11 a of the first layer 11 . The second layer 22 is linear, and in FIG. 2 , the cross section of the laminated structure 2 is formed including the cross section along the line length direction of the second layer 22 . The number of linear second layers 22 may be one, or may be two or more. The laminated structure 2 is the same as the laminated structure 1 shown in FIG.
When the first layer 11 is an insulating layer containing a cured product of the vinyl compound (1), a cured product of the vinyl composition (1), or a cured product of the prepreg (1), and the second layer 22 is a conductor wiring The laminated structure 2 of is a printed wiring board.

Both the laminated structure 1 and the laminated structure 2 shown in FIGS. It may have layers.

FIG. 3 is a cross-sectional view schematically showing still another example of the laminated structure of the present embodiment obtained using the vinyl compound (1).
The laminated structure 3 shown here includes a first layer 11, a second layer 12 provided on one surface 11a of the first layer 11, and a second layer 12 provided on the other surface 11b of the first layer 11. 3 layers 13 and . The third layer 13 is film-like or sheet-like, and is selected according to the type of the laminated structure 1, similar to the second layer 12. The arrangement of the third layer 13 on the other surface 11 b of the first layer 11 is the same as the arrangement of the second layer 12 on the one surface 11 a of the first layer 11 . The composition, shape, thickness and size of the third layer 13 may be the same as or different from the composition, shape, thickness and size of the second layer 12, respectively. For example, the third layer 13 may be provided on the entire area of the other surface 11b of the first layer 11, or may be provided on a partial area.

The first layer 11 is a resin layer containing the vinyl compound (1) or a semi-cured product thereof, or the vinyl composition (1) or a semi-cured product thereof, and the second layer 12 and the third layer 13 are support films. The laminated structure 3 in this case is a resin-coated film.
The first layer 11 is a resin layer containing the vinyl compound (1) or its semi-cured material, or the vinyl composition (1) or its semi-cured material, and the second layer 12 and the third layer 13 are metal foils. The laminated structure 3 in this case is a resin-coated metal foil.
The first layer 11 is an insulating layer containing a cured product of the vinyl compound (1), a cured product of the vinyl composition (1), or a cured product of the prepreg (1), and the second layer 12 and the third layer 13 are The laminate structure 3 in the case of metal foil is a metal-clad laminate.

FIG. 4 is a cross-sectional view schematically showing still another example of the laminated structure of the present embodiment obtained using the vinyl compound (1).
The laminated structure 4 shown here includes a first layer 11, a second layer 22 provided on one surface 11a of the first layer 11, and a second layer 22 provided on the other surface 11b of the first layer 11. 3 layers 23 and . The third layer 23 is linear, and in FIG. 4, the cross section of the laminated structure 4 includes a cross section along the line length direction of the second layer 22, a cross section along the line length direction of the third layer 23, It is formed by including both The manner of arrangement of the third layer 23 on the other surface 11 b of the first layer 11 is the same as the manner of arrangement of the second layer 22 on the one surface 11 a of the first layer 11 . The composition, length, thickness and number of the third layer 23 may be the same as or different from the composition, length, thickness and number of the second layer 22 . For example, the number of linear third layers 23 may be one, or two or more.
The first layer 11 is an insulating layer containing a cured product of the vinyl compound (1), a cured product of the vinyl composition (1), or a cured product of the prepreg (1), and the second layer 22 and the third layer 23 are The laminated structure 4 in the case of conductor wiring is a printed wiring board.

The present invention will be described in more detail below with reference to specific examples. However, the present invention is by no means limited to the examples shown below.

[Example 1]
<<Production of Vinyl Compound>>
In a 200 mL four-necked flask equipped with a thermometer, condenser and stirrer, 20 g of 1-(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)-1-cyclohexene, 2,6- 0.2 g of di(tert-butyl)-p-cresol, 40 g of potassium carbonate, 4.5 g of sodium iodide, 110 mL of N,N-dimethylformamide and 32.6 g of vinylbenzyl chloride were charged, and the internal temperature was about 80° C. for 4 hours. It was reacted for 5 hours. The vinylbenzyl chloride used here is a mixture of 3-vinylbenzyl chloride and 4-vinylbenzyl chloride.

After completion of the reaction, the reaction mixture was cooled to room temperature, 200 mL of water was added, and the precipitated solid was collected by filtration and washed with water. The washed solid obtained above was suspended in a mixed liquid obtained by mixing 180 mL of methanol, 180 mL of water, and 0.5 g of 2,6-di(tert-butyl)-p-cresol. After stirring with , it was collected by filtration and washed with water. The resulting solid was suspended in 180 mL of isopropyl alcohol and stirred at an internal temperature of 60° C. for 2 hours, after which the solid in the suspension was collected by filtration and dried under reduced pressure conditions.

A portion of 14.3 g of the solid obtained after drying, 0.15 g of 2,6-di(tert-butyl)-p-cresol, 334 g of toluene, and 71.7 g of silica gel were mixed, and the mixture was heated at an internal temperature of 45° C. for 30 minutes. After stirring, the mixture was filtered to remove insoluble matter. After toluene was removed from the resulting solution under reduced pressure, 158 g of methanol was added dropwise while stirring at an internal temperature of 50° C., and the mixture was further stirred for 1 hour and then cooled to room temperature. Precipitated crystals were collected by filtration, washed with methanol, and dried under reduced pressure conditions to obtain 8.6 g of vinyl compound (1)-1 represented by the following formula (1)-1. The purity of the vinyl compound (1)-1 was 91.4% in terms of area percentage in analysis data by high performance liquid chromatography.

¹ H-NMR data of vinyl compound (1)-1 are shown below.
¹ H-NMR (δ: ppm, CDCl ₃ solvent):
7.54-7.34 (m, 8H), 7.30-7.17 (m, 4H), 7.01-6.92 (m, 2H), 6.90-6.83 (m, 1H) ), 6.82-6.70 (m, 2H), 6.13 (bs, 1H), 5.85-5.74 (m, 2H), 5.33-5.25 (m, 2H), 5.13-5.05 (m, 4H) 2.91-2.79 (m, 1H), 2.62-2.44 (m, 3H), 2.39-2.27 (m, 4H) , 2.16-2.05 (m, 1H), 1.97-1.81 (m, 1H)

<<Production of hardened vinyl resin>>
The vinyl compound (1)-1 obtained above is poured into the plate-like hollow part of the mold, and after being pressurized at 160° C. for 1 hour under reduced pressure at a pressure of 1.5 MPa, it is further heated at 180° C. It was cured while applying a pressure of 1.5 MPa for 2 hours. Thus, a vinyl resin cured product (1)-1 was obtained.

[Example 2]
<<Production of Vinyl Compound>>
Into a 200 mL four-necked flask equipped with a thermometer, condenser and stirrer, 5.0 g of 1-(3-methyl-4-hydroxyphenyl)-4-(4-hydroxyphenyl)-1-cyclohexene, 2, 0.05 g of 6-di(tert-butyl)-p-cresol, 9.9 g of potassium carbonate, 1.1 g of sodium iodide, 33 mL of N,N-dimethylformamide and 8.2 g of 4-vinylbenzyl chloride were charged, and the internal temperature was It was made to react at about 60 degreeC for 3 hours.

After completion of the reaction, it was cooled to room temperature. After that, 41 mL of heptane and 41 mL of water were charged, and after stirring for 20 minutes, the precipitated solid was collected by filtration and washed with heptane. The total amount of the obtained solid, 0.05 g of 2,6-di(tert-butyl)-p-cresol, 340 g of toluene, and 46 g of silica gel were mixed, stirred at 50° C. for 30 minutes, filtered and insoluble. removed things. Water was added to the obtained solution, and after liquid separation was performed three times, toluene was removed under reduced pressure. After adding 336 g of toluene to the obtained solid and stirring at 50°C, the mixture was cooled to 10°C. Precipitated crystals were collected by filtration, washed with toluene, and dried under reduced pressure conditions to obtain 6.4 g of vinyl compound (1)-2 represented by the following formula (1)-2. The purity of vinyl compound (1)-2 was 96.2% in terms of area percentage in analysis data by high performance liquid chromatography.

¹ H-NMR data of vinyl compound (1)-2 are shown below.
¹ H-NMR (δ: ppm, CDCl ₃ solvent):
7.50-7.39 (m, 8H), 7.31-7.17 (m, 4H), 7.00-6.92 (m, 2H), 6.86 (d, J=8.4Hz , 1H), 6.79 (dd, J = 11.1Hz, J = 1.2Hz, 1H), 6.73 (dd, J = 10.8Hz, J = 1.2Hz, 1H), 6.16- 6.10 (m, 1H), 5.79 (d, J=17.7Hz, 2H), 5.29 (dd, 2H, J=10.8Hz, J=0.6Hz, 2H), 5.11 (s, 2H), 5.07 (s, 2H), 2.92-2.79 (m, 1H), 2.62-2.44 (m, 3H), 2.41-2.24 (m , 1H), 2.32 (s, 3H), 2.16-2.05 (m, 1H), 1.97-1.80 (m, 1H)

<<Production of hardened vinyl resin>>
Vinyl resin cured product (1)-2 was prepared in the same manner as in Example 1, except that vinyl compound (1)-2 obtained above was used instead of vinyl compound (1)-1. got

[Comparative Example 1]
<<Production of Vinyl Compound>>
In a 200 mL four-necked flask equipped with a thermometer, condenser and stirrer, 6.0 g of 4,4'-dihydroxy-2,2',3,3',5,5'-hexamethylbiphenyl, 2, 0.06 g of 6-di(tert-butyl)-p-cresol, 12 g of potassium carbonate, 1.3 g of sodium iodide, 34 mL of N,N-dimethylformamide and 10 g of 4-vinylbenzyl chloride were charged, and the internal temperature was about 60°C. The reaction was allowed to proceed for 3 hours. After completion of the reaction, 121 g of toluene and 34 mL of water were added, and the mixture was stirred and filtered to remove insoluble matter. The resulting solution was separated and washed with water three times. The resulting solution was filtered to remove insoluble matter, and then toluene was removed under reduced pressure. 56 mL of methanol and 0.07 g of 2,6-di(tert-butyl)-p-cresol were added to the obtained solid and stirred at room temperature. Solids in the suspension were collected by filtration and dried under reduced pressure conditions to obtain 9.4 g of vinyl compound (R)-1 represented by the following formula (R)-1. The purity of vinyl compound (R)-1 was 99.1% in terms of area percentage in analysis data by high performance liquid chromatography.

¹ H-NMR data of the vinyl compound (R)-1 are shown below.
¹ H-NMR (δ: ppm, CDCl ₃ solvent):
7.52-7.44 (m, 8H), 6.81 (s, 2H), 6.76 (dd, J = 17.7Hz, J = 10.8Hz, 2H), 5.79 (dd, J = 17.7Hz, J = 0.9Hz, 2H), 5.27 (dd, J = 10.8Hz, J = 0.9Hz, 2H), 4.83 (s, 4H), 2.30 (s, 6H), 2.27 (s, 6H), 1.93 (s, 6H)

<<Production of hardened vinyl resin>>
1 was obtained in the same manner as in Example 1, except that vinyl compound (R)-1 obtained above was used instead of vinyl compound (1)-1.

[Comparative Example 2]
<<Production of Epoxy Compound>>
According to Example 1 of JP-A-2009-249299, 1-(3-methyl-4-oxiranylmethoxyphenyl)-4-(4-oxiranylmethoxyphenyl) represented by the following formula (R)-2 -1-Cyclohexene (hereinafter referred to as "epoxy compound (R)-2") was obtained.

¹ H-NMR data of the epoxy compound (R)-2 are shown below.
¹ H-NMR (δ: ppm, CDCl ₃ solvent):
7.26-7.15 (m, 4H), 6.91-6.85 (m, 2H), 6.77 (d, J=8.7Hz, 1H), 6.12-6.07 (m , 1H), 4.27-4.16 (m, 2H), 4.02-3.93 (m, 2H), 3.41-3.32 (m, 2H), 2.94-2.88 (m, 2H), 2.89-2.74 (m, 3H), 2.58-2.41 (m, 3H), 2.34-2.21 (m, 1H), 2.26 (s , 3H), 2.12-2.02 (m, 1H), 1.93-1.78 (m, 1H)

<<Production of Epoxy Composition, Production of Cured Epoxy Resin>>
20 parts by mass of the epoxy compound (R)-2 obtained in Comparative Example 2 and 5 parts by mass of 4,4'-diaminodiphenylmethane (curing agent) were mixed to obtain an epoxy composition. The melted epoxy composition is poured into the plate-like hollow part of the mold, degassed at 140° C., kept at 140° C. for 1 hour, and further kept at 180° C. for 2 hours to cure. rice field. As described above, an epoxy resin cured product (R)-2 was obtained.

<<Evaluation of cured vinyl resin and cured epoxy resin>>
<Measurement of thermal diffusivity>
For the vinyl resin cured product (1)-1, vinyl resin cured product (1)-2, vinyl resin cured product (R)-1, and epoxy resin cured product (R)-2 obtained above, the thermal diffusivity Thermal diffusivity (m ² /s) was measured by temperature wave thermal analysis (TWA method) using a measuring device ("ai-phase mobile" manufactured by i-Phase Co., Ltd.). Table 1 shows the results.

<Measurement of dielectric loss tangent>
The vinyl resin cured product (1)-1, the vinyl resin cured product (1)-2, the vinyl resin cured product (R)-1, and the epoxy resin cured product (R)-2 obtained above were subjected to the following conditions. Then, the dielectric loss tangent was measured at a frequency of 100 MHz. Table 1 shows the results.
・Measurement method: capacitance method (equipment: impedance analyzer (manufactured by Agilent, model: E4991A))
・Electrode type: 16453A
・Measurement environment: 23°C, 50% RH
・Applied voltage: 1V

In Examples 1 and 2, the vinyl compound (1) was used, and the cured vinyl resin product (1)-1 and the cured vinyl resin product (1)-2 had a thermal diffusivity of 2.43×10 ⁻⁷ m. The dielectric loss tangent of cured vinyl resin (1)-1 and cured vinyl resin (1)-2 was 0.0044 or less, which was sufficiently high, and was sufficiently high, at ² /s or more.

On the other hand, in Comparative Example 1, the vinyl compound (R)-1 was used instead of the vinyl compound (1), and the thermal diffusivity of the cured vinyl resin (R)-1 was lower than that of the cured vinyl resin ( 1)-1, the thermal diffusivity of the cured vinyl resin (1)-2 is lower than that of the cured vinyl resin (R)-1, and the dielectric loss tangent of the cured vinyl resin (R)-1 is the cured vinyl resin (1)-1, the cured vinyl resin It was higher than the dielectric loss tangent of (1)-2.

In Comparative Example 2, epoxy compound (R)-2 was used instead of vinyl compound (1). It was significantly higher than the dielectric loss tangent of the cured resin (1)-2.
The only difference between vinyl compound (1)-1 and vinyl compound (1)-2 and epoxy compound (R)-2 is the functional group at the end of the molecule, and the group having a vinyl group (Examples 1 to 2) is changed to a group having an epoxy group (in the case of Comparative Example 2), the dielectric loss tangent of the cured resin material is remarkably increased. It was confirmed that the dielectric loss tangent of the vinyl resin cured product (1) was remarkably reduced.

The difference between the vinyl compound (1)-1 and vinyl compound (1)-2 and the vinyl compound (R)-1 is the number of linkages in the ring structure near the center in the length direction of the molecule, which constitutes the mesogenic skeleton. , and it was confirmed that the thermal diffusivity and the dielectric loss tangent of the vinyl resin cured product are improved when the number of connections is large.

INDUSTRIAL APPLICABILITY The present invention can be used for printed wiring boards in communication equipment, and is particularly suitable for use in printed wiring boards where communication equipment handles a large amount of data and is expected to generate a large amount of heat. is.

1, 2, 3, 4... Laminated structure, 11... First layer, 11a... One surface of first layer, 11b... Other surface of first layer, 12, 22. . . 2nd layer, 13, 23 . . . 3rd layer

Claims (11)

formula (1)

(Wherein, A ¹ , A ² and A ³ are the same or different, and

Represents any divalent group represented by Here, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and the alkyl group and alkoxy group may be linear or branched. In the alkyl group and alkoxy group, one or more non-adjacent methylene groups may be replaced with oxygen atoms. a represents an integer of 1 to 10, b and c represent an integer of 1 to 8, d, e, f and g represent an integer of 1 to 6, and h represents an integer of 1 to 4. In the divalent group, when there are a plurality of R's, all the R's may represent the same group or different groups. Q ¹ and Q ² are each the same or different and are a single bond, a linear or branched alkylene group having 1 to 18 carbon atoms, or formula (2)

Represents a divalent group represented by Here, Ar represents an aromatic group. The methylene group in formula (2) is bonded to the oxygen atom in formula (1). )
A vinyl compound represented by The vinyl compound represented by the formula (1) is represented by the formula (3)

(In the formula, A ⁴ is the following formula

and R, a, c, h, Q ¹ and Q ² have the same meanings as above. )
The vinyl compound according to claim 1, which is a vinyl compound represented by 3. The vinyl compound according to claim 2, wherein in the vinyl compound represented by formula (3), ^Q1 and ^Q2 are the same or different and are divalent groups represented by formula (2). A method for producing the vinyl compound according to claim 1, comprising formula (4)

(In the formula, A ¹ , A ² and A ³ each have the same meaning as above.)
A compound represented by the formula (5)

(In the formula, Q ¹ has the same meaning as above, and X ¹ represents a halogen atom.)
A compound represented by the formula (6)

(In the formula, Q ² has the same meaning as above, X ² represents a halogen atom, and may be the same as or different from X ¹ above.)
A method for producing a vinyl compound, comprising reacting a compound represented by in the presence of a base. A vinyl composition containing the vinyl compound according to any one of claims 1 to 3. A vinyl resin cured product obtained by curing the vinyl compound according to any one of claims 1 to 3 or the vinyl composition according to claim 5. A prepreg comprising the vinyl compound or semi-cured material thereof according to any one of claims 1 to 3, or the vinyl composition or semi-cured material thereof according to claim 5, and a fibrous base material. With a resin comprising a resin layer containing the vinyl compound according to any one of claims 1 to 3 or a semi-cured product thereof, or the vinyl composition according to claim 5 or a semi-cured product thereof, and a support film the film. With a resin comprising a resin layer containing the vinyl compound according to any one of claims 1 to 3 or a semi-cured product thereof, or the vinyl composition according to claim 5 or a semi-cured product thereof, and a metal foil metal foil. an insulating layer comprising a cured product of the vinyl compound according to any one of claims 1 to 3, a cured product of the vinyl composition according to claim 5, or a cured product of the prepreg according to claim 7; and a metal A metal clad laminate comprising a foil. An insulating layer comprising a cured product of the vinyl compound according to any one of claims 1 to 3, a cured product of the vinyl composition according to claim 5, or a cured product of the prepreg according to claim 7; and a conductor A printed wiring board comprising wiring.

Images