JP5708160B2 - Resin substrate for high frequency circuit board and high frequency circuit board - Google Patents

Description

  The present invention relates to a resin substrate for a high-frequency circuit board and a high-frequency circuit board including the same.

  In recent years, information transmission apparatuses such as network devices are increasingly demanded for high-speed signal transmission. In order to increase the speed of such a signal, it is necessary to improve the signal propagation speed and realize a low transmission loss in the high frequency range for the high frequency circuit board used in the information transmission apparatus. For this reason, development of a high-frequency circuit board having a low dielectric constant and low dielectric loss has been studied.

  In order to improve such low dielectric constant and low dielectric loss characteristics, it is important to improve the dielectric characteristics of the insulating layer constituting the high-frequency circuit board. Conventionally, an epoxy resin or a polyimide resin has been applied to a resin material constituting the insulating layer of the high-frequency circuit board.

  Patent Document 1 discloses that the dielectric constant and dielectric loss can be controlled by subjecting a thermoplastic liquid crystal polymer, which is a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, to a specific heat treatment after molding. Have been described.

JP 2006-137786 A

  However, epoxy resins and polyimide resins have a high hygroscopic property and have a problem that the dielectric constant easily changes in a high frequency range. Further, a resin material having a low dielectric constant and dielectric loss without requiring a specific heat treatment has been demanded.

  The present invention has been made to solve these problems, and an object of the present invention is to provide a resin substrate for forming a high-frequency circuit board having a high transmission speed and a low transmission loss in a high-frequency region.

As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by using a resin substrate having a specific dielectric constant and dielectric loss tangent within specific ranges, and have completed the present invention. .
That is, the present invention provides the following [1] to [6].

[1] At 26 ° C. and relative humidity 45% RH
A resin substrate for a high-frequency circuit board, wherein a relative dielectric constant at 1 GHz and 10 GHz is 3.2 or less, a dielectric loss tangent at 1 GHz is 0.0050 or less, and a dielectric loss tangent at 10 GHz is 0.010 or less.
[2] An aromatic polyether system in which the resin substrate has at least one structural unit (i) selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) The resin substrate according to [1], comprising a polymer.

（式（１）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、ａ〜ｄは、それぞれ独立に０〜４の整数を示す。）

(In Formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.)

（式（２）中、Ｒ¹〜Ｒ⁴およびａ〜ｄは、それぞれ独立に前記式（１）中のＲ¹〜Ｒ⁴およびａ〜ｄと同義であり、Ｙは単結合、−ＳＯ₂−または＞Ｃ＝Ｏを示し、Ｒ⁷およびＲ⁸は、それぞれ独立にハロゲン原子、炭素数１〜１２の１価の有機基またはニトロ基を示し、ｇおよびｈは、それぞれ独立に０〜４の整数を示し、ｍは０または１を示す。但し、ｍが０の時、Ｒ⁷はシアノ基ではない。）

(In the formula (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO ₂ -Or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 And m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.)

  [3] The aromatic polyether-based polymer further includes at least one structural unit (ii) selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4): The resin substrate according to [1] or [2], comprising:

（式（３）中、Ｒ⁵およびＲ⁶は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、Ｚは、単結合、−Ｏ−、−Ｓ−、−ＳＯ₂−、＞Ｃ＝Ｏ、−ＣＯＮＨ−、−ＣＯＯ−または炭素数１〜１２の２価の有機基を示し、ｅおよびｆは、それぞれ独立に０〜４の整数を示し、ｎは０または１を示す。）

(In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1 .)

（式（４）中、Ｒ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈは、それぞれ独立に前記式（２）中のＲ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈと同義であり、Ｒ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆは、それぞれ独立に前記式（３）中のＲ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆと同義である。）

(In the formula ^{(4), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f.)

[4] In the aromatic polyether polymer, the molar ratio of the structural unit (i) to the structural unit (ii) is 50:50 to 100: 0. The resin substrate in any one.
[5] In any one of [1] to [4], the polystyrene-equivalent weight average molecular weight of the aromatic polyether polymer by gel permeation chromatography (GPC) is 5,000 to 500,000. Resin substrate.
[6] A high-frequency circuit board comprising the resin substrate according to any one of [1] to [5].

According to the present invention, it is possible to easily obtain a resin substrate suitably used for a high-frequency circuit board having a low relative dielectric constant and dielectric loss tangent, in particular, a low relative dielectric constant and dielectric loss tangent in a high frequency band of 1 GHz or more and low hygroscopicity. Can do.
In addition, it is possible to obtain a resin substrate with little deterioration in electrical characteristics under high temperature and high humidity.
Furthermore, according to the present invention, it is possible to obtain a high-frequency circuit board having a high transmission speed and a small transmission loss.

FIG. 1 is a schematic cross-sectional view of a copper clad laminate produced when measuring transmission loss in an example of the present invention.

≪Resin board for high frequency circuit board≫
The resin substrate for a high-frequency circuit board of the present invention (hereinafter also referred to as “resin substrate”) has a relative dielectric constant of 3.2 or less at 1 GHz and 10 GHz at 26 ° C. and a relative humidity of 45% RH, and has a dielectric loss tangent at 1 GHz. The dielectric loss tangent at 0.0050 or less and 10 GHz is 0.010 or less.
By using such a resin substrate, it is possible to obtain a high-frequency circuit with a high transmission speed and low transmission loss in a high-frequency region.

The resin substrate at 26 ° C. and relative humidity 45% RH,
The relative dielectric constant at 1 GHz is preferably 3.1 or less,
The relative dielectric constant at 10 GHz is preferably 3.1 or less,
The dielectric loss tangent at 1 GHz is preferably 0.003 or less,
The dielectric loss tangent at 10 GHz is preferably 0.008 or less.
The relative dielectric constant and dielectric loss tangent of the resin substrate at a desired frequency are measured by a perturbation resonance method using a vector network analyzer Wiltron 37169A (manufactured by Wiltron) in an environment of 26 ° C. and a relative humidity of 45% RH.
Since the relative permittivity and dielectric loss tangent of the resin substrate in a high frequency band of 1 GHz or more are in the above ranges, a high frequency circuit with a higher transmission speed and a low transmission loss in the high frequency range can be obtained.

  Such a resin substrate is obtained by molding using a polymer having a relative dielectric constant and a dielectric loss tangent in a high frequency band of 1 GHz or higher, preferably a polymer having a structural unit with low water absorption. Can do. More preferably, the polymer is obtained by using a polymer that does not contain a functional group having high water absorption such as an amide group, an imide group, or an ester group. The functional group having low water absorption is preferably an ether group, and the polymer is a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (1)”) and the following formula (2). An aromatic polyether polymer (hereinafter referred to as “polymer (I)”) having at least one structural unit (i) selected from the group consisting of structural units represented by the following (hereinafter also referred to as “structural unit (2)”): It is also preferable.

  This polymer (I) has a small relative dielectric constant and dielectric loss tangent in a high frequency band of 1 GHz or more. For this reason, a circuit board with a high transmission speed and a small transmission loss can be obtained, and it is suitably used for a high-frequency circuit. Furthermore, since the polymer (I) has low hygroscopicity and excellent balance in heat resistance, mechanical strength, electrical properties, etc., the relative dielectric constant and the like even under harsh environments such as high temperature and / or high humidity. Deterioration of electrical characteristics such as increased dielectric loss tangent is unlikely to occur. For this reason, according to the resin substrate of the present invention, it is possible to obtain a high-frequency circuit board having a high transmission speed, a small transmission loss, and a small environmental dependency even under a severe environment.

In said formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently. a to d each independently represent an integer of 0 to 4, preferably 0 or 1.
The monovalent organic group having 1 to 12 carbon atoms includes a monovalent hydrocarbon group having 1 to 12 carbon atoms and 1 to 1 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. And 12 monovalent organic groups.

  Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and 6 to 12 carbon atoms. An aromatic hydrocarbon group etc. are mentioned.

  The linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferably a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and the linear or branched carbon group having 1 to 5 carbon atoms. A hydrogen group is more preferable.

  Preferable specific examples of the linear or branched hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and n-pentyl. Group, n-hexyl group, n-heptyl group and the like.

  As said C3-C12 alicyclic hydrocarbon group, a C3-C8 alicyclic hydrocarbon group is preferable, and a C3-C4 alicyclic hydrocarbon group is more preferable.

  Preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group; cyclobutenyl group, cyclopentenyl group, and cyclohexenyl group. And the like. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

  Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group. The bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

  Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom include an organic group consisting of a hydrogen atom, a carbon atom and an oxygen atom, and among them, a total carbon consisting of an ether bond, a carbonyl group or an ester bond and a hydrocarbon group. Preferable examples include organic groups of formulas 1 to 12.

  Examples of the organic group having 1 to 12 carbon atoms having an ether bond include an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, an alkynyloxy group having 2 to 12 carbon atoms, and 6 to 12 carbon atoms. And an aryloxy group having 1 to 12 carbon atoms and the like. Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, a cyclohexyloxy group, and a methoxymethyl group.

Moreover, as a C1-C12 organic group which has a carbonyl group, a C2-C12 acyl group etc. can be mentioned. Specific examples include an acetyl group, a propionyl group, an isopropionyl group, and a benzoyl group.
As a C1-C12 organic group which has an ester bond, a C2-C12 acyloxy group etc. are mentioned. Specific examples include an acetyloxy group, a propionyloxy group, an isopropionyloxy group, and a benzoyloxy group.

  Examples of the organic group having 1 to 12 carbon atoms including a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom and a nitrogen atom, and specifically, a cyano group, an imidazole group, a triazole group, a benzimidazole group and a benzine. A triazole group etc. are mentioned.

  Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom and a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom, an oxygen atom and a nitrogen atom. Specifically, an oxazole group, an oxadiazole group, Examples include a benzoxazole group and a benzoxadiazole group.

As R < ¹ > -R < ⁴ > in said Formula (1), a C1-C12 monovalent hydrocarbon group is preferable from the point of the water absorption of a polymer (I), and C6-C12 aromatic hydrocarbon A group is more preferable, and a phenyl group is more preferable.

In the formula (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO _2- or> C = O, R ⁷ and R ⁸ each independently represents a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group. g and h each independently represent an integer of 0 to 4, preferably 0.
Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic group having 1 to 12 carbon atoms in the formula (1).

The polymer (I) has a molar ratio of the structural unit (1) to the structural unit (2) (however, the sum of the structural unit (1) and the structural unit (2) is 100). However, from the viewpoint of optical properties, heat resistance and mechanical properties, it is preferable that the structural unit (1): structural unit (2) = 50: 50 to 100: 0, and the structural unit (1): structural unit (2). = 70: 30 to 100: 0 is more preferable, and structural unit (1): structural unit (2) is more preferably 80:20 to 100: 0.
Here, the mechanical properties refer to properties such as the tensile strength, breaking elongation and tensile elastic modulus of the polymer.

  The polymer (I) further has at least one structural unit (ii) selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). May be. It is preferable for the polymer (I) to have such a structural unit (ii) because the mechanical properties of the resin substrate containing the polymer (I) are improved.

In the formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, and n represents 0 or 1. e and f each independently represent an integer of 0 to 4, preferably 0.
Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic group having 1 to 12 carbon atoms in the formula (1).

  The divalent organic group having 1 to 12 carbon atoms includes a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom, and a nitrogen atom. A divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the above, and a divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. And halogenated organic groups.

  Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and Examples thereof include a bivalent aromatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a trimethylene group, an isopropylidene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group.

  Examples of the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkylene groups such as cyclopropylene group, cyclobutylene group, cyclopentylene group and cyclohexylene group; cyclobutenylene group, cyclopentenylene group and And cycloalkenylene groups such as a cyclohexenylene group.

  Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenylene group, a naphthylene group, and a biphenylene group.

  Examples of the divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms and a divalent halogenated fat having 3 to 12 carbon atoms. Examples thereof include a cyclic hydrocarbon group and a divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a difluoromethylene group, a dichloromethylene group, a tetrafluoroethylene group, a tetrachloroethylene group, a hexafluorotrimethylene group, and a hexachlorotrimethylene group. Group, hexafluoroisopropylidene group, hexachloroisopropylidene group and the like.

  As the divalent halogenated alicyclic hydrocarbon group having 3 to 12 carbon atoms, at least a part of the hydrogen atoms exemplified in the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is a fluorine atom. And a group substituted with a chlorine atom, a bromine atom or an iodine atom.

  As the divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms, at least a part of the hydrogen atoms exemplified in the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms is a fluorine atom, chlorine And a group substituted with an atom, a bromine atom or an iodine atom.

  Examples of the organic group having 1 to 12 carbon atoms including at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom include an organic group consisting of a hydrogen atom and a carbon atom and an oxygen atom and / or a nitrogen atom. And a divalent organic group having 1 to 12 carbon atoms and having an ether bond, a carbonyl group, an ester bond or an amide bond and a hydrocarbon group.

  The divalent halogenated organic group having 1 to 12 carbon atoms containing at least one kind of atom selected from the group consisting of oxygen atom and nitrogen atom is specifically selected from the group consisting of oxygen atom and nitrogen atom Examples include a group in which at least a part of the hydrogen atoms exemplified in the divalent organic group having 1 to 12 carbon atoms containing at least one atom is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. .

Z in the formula (3) is preferably a single bond, —O—, —SO ₂ —,> C═O or a divalent organic group having 1 to 12 carbon atoms, and the water absorbing property of the polymer (I). From the viewpoint, a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is more preferable.

In the formula (4), R ⁷ , R ⁸ , Y, m, g and h are each independently synonymous with R ⁷ , R ⁸ , Y, m, g and h in the formula (2), R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f. When m is 0, R ⁷ is not a cyano group.

In the polymer (I), the molar ratio between the structural unit (i) and the structural unit (ii) (however, the sum of both ((i) + (ii)) is 100) is an optical property. From the viewpoint of heat resistance and mechanical properties, (i) :( ii) = 50: 50 to 100: 0 is preferable, and (i) :( ii) = 70: 30 to 100: 0. More preferably, (i) :( ii) = 80: 20 to 100: 0 is more preferable.
Here, the mechanical properties refer to properties such as the tensile strength, breaking elongation and tensile elastic modulus of the polymer.

  The polymer (I) preferably contains 70 mol% or more of the structural unit (i) and the structural unit (ii) in the total structural units from the viewpoint of optical properties, heat resistance and mechanical properties. It is more preferable to contain 95 mol% or more.

  Examples of the polymer (I) include a compound represented by the following formula (5) (hereinafter also referred to as “compound (5)”) and a compound represented by the following formula (7) (hereinafter referred to as “compound (7)”). A component containing at least one compound selected from the group consisting of (hereinafter also referred to as “component (A)”) and a component containing a compound represented by the following formula (6) (hereinafter referred to as “component (B)”) It can also be obtained by reacting.

  In said formula (5), X shows a halogen atom independently and a fluorine atom is preferable.

In the formula ^{(7), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, X is independently synonymous with X in the formula (5).
However, when m is 0, R ⁷ is not a cyano group.

In the formula (6), each R ^a independently represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, a methanesulfonyl group or a trifluoromethylsulfonyl group, and among them, a hydrogen atom is preferable. In the formula (6), R ¹ to R ⁴ and a~d have the same meanings as R ¹ to R ⁴ and a~d each independently the formula (1).

  Specific examples of the compound (5) include 2,6-difluorobenzonitrile (DFBN), 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 2, Mention may be made of 5-dichlorobenzonitrile, 2,4-dichlorobenzonitrile and their reactive derivatives. In particular, 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferably used from the viewpoints of reactivity and economy. These compounds can be used in combination of two or more.

  Specific examples of the compound represented by the above formula (6) (hereinafter also referred to as “compound (6)”) include 9,9-bis (4-hydroxyphenyl) fluorene (BPFL) and 9,9-bis. (3-phenyl-4-hydroxyphenyl) fluorene, 9,9-bis (3,5-diphenyl-4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9, Examples include 9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, and reactive derivatives thereof. Among the above-mentioned compounds, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene are preferably used. These compounds can be used in combination of two or more.

  Specific examples of the compound (7) include 4,4′-difluorobenzophenone, 4,4′-difluorodiphenylsulfone (DFDS), 2,4′-difluorobenzophenone, 2,4′-difluorodiphenylsulfone, 2,2′-difluorobenzophenone, 2,2′-difluorodiphenylsulfone, 3,3′-dinitro-4,4′-difluorobenzophenone, 3,3′-dinitro-4,4′-difluorodiphenylsulfone, 4, 4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl sulfone, 2,4'-dichlorobenzophenone, 2,4'-dichlorodiphenyl sulfone, 2,2'-dichlorobenzophenone, 2,2'-dichlorodiphenyl sulfone, 3 , 3′-dinitro-4,4′-dichlorobenzophenone and 3,3′-dinitro-4, 4'-dichlorodiphenyl sulfone and the like can be mentioned. Among these, 4,4′-difluorobenzophenone and 4,4′-difluorodiphenyl sulfone are preferable. These compounds can be used in combination of two or more.

It is preferable that at least one compound selected from the group consisting of compound (5) and compound (7) is contained in 80 mol% to 100 mol% in 100 mol% of component (A), and 90 mol% to More preferably, it is contained at 100 mol%.
Moreover, it is preferable that (B) component contains the compound represented by following formula (8) as needed. Compound (6) is preferably contained in 100 mol% of component (B) in an amount of 50 mol% to 100 mol%, more preferably 80 mol% to 100 mol%, and more preferably 90 mol%. More preferably, it is contained in an amount of ˜100 mol%.

In the formula (8), R ⁵ , R ⁶ , Z, n, e and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in the formula (3), R ^a has the same meaning as R ^a each independently in the formula (6) in.

  Examples of the compound represented by the formula (8) include hydroquinone, resorcinol, 2-phenylhydroquinone, 4,4′-biphenol, 3,3′-biphenol, 4,4′-dihydroxydiphenylsulfone, and 3,3′-dihydroxy. Diphenylsulfone, 4,4′-dihydroxybenzophenone, 3,3′-dihydroxybenzophenone, 1,1′-bi-2-naphthol, 1,1′-bi-4-naphthol, 2,2-bis (4-hydroxy) Phenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and reactive derivatives thereof Etc. Among the above-mentioned compounds, resorcinol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy) Phenyl) -1,1,1,3,3,3-hexafluoropropane is preferred, and 4,4′-biphenol is suitably used from the viewpoint of reactivity and mechanical properties. These compounds can be used in combination of two or more.

More specifically, the polymer (I) can be synthesized by the method (I ′) shown below.
Method (I ′):
The alkali metal salt obtained after reacting the component (B) with an alkali metal compound in an organic solvent to obtain an alkali metal salt of the component (B) (compound (6) and / or compound (8), etc.) And (A) component are made to react. In addition, the alkali metal salt of (B) component and (A) component can also be made to react by performing reaction with (B) component and an alkali metal compound in presence of (A) component.

  Examples of the alkali metal compound used in the reaction include alkali metals such as lithium, potassium and sodium; alkali hydrides such as lithium hydride, potassium hydride and sodium hydride; lithium hydroxide, potassium hydroxide and sodium hydroxide And alkali metal carbonates such as lithium hydrogen carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate. These can be used alone or in combination of two or more.

In the alkali metal compound, the amount of metal atoms in the alkali metal compound is usually 1 to 3 times equivalent, preferably 1.1 to 2 times equivalent to all —O—R ^a in the component (B). Preferably it is used in an amount of 1.2 to 1.5 times equivalent.

  Examples of the organic solvent used in the reaction include N, N-dimethylacetamide (DMAc), N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ- Butyllactone, sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, dialkoxybenzene (1 to 4 carbon atoms of alkoxy group) and trialkoxybenzene (carbon number of alkoxy group) 1-4) etc. can be used. Among these solvents, polar organic solvents having a high dielectric constant such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone, and dimethylsulfoxide are particularly preferably used.

  Further, in the reaction, a solvent azeotropic with water such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole and phenetole can be further used.

  The proportion of component (A) and component (B) used is preferably 45 mol% or more and 55 mol% or less when component (A) is 100 mol% in total of component (A) and component (B). More preferably, it is 50 mol% or more and 52 mol% or less, more preferably more than 50 mol% and 52 mol% or less, and the component (B) is preferably 45 mol% or more and 55 mol% or less, more preferably 48 mol%. % Or more and 50 mol% or less, more preferably 48 mol% or more and less than 50 mol%.

  Moreover, reaction temperature becomes like this. Preferably it is 60 to 250 degreeC, More preferably, it is the range of 80 to 200 degreeC. The reaction time is preferably in the range of 15 minutes to 100 hours, more preferably 1 hour to 24 hours.

The polymer (I) preferably has a glass transition temperature (Tg) determined by differential scanning calorimetry (DSC, heating rate of 20 ° C./min) of 230 to 350 ° C., more preferably 240 to 330 ° C., and even more preferably 250. ~ 300 ° C.
The glass transition temperature of the polymer (I) is measured, for example, using a Rigaku 8230 type DSC measuring apparatus (temperature rising rate 20 ° C./min).

  The polymer (I) is a polystyrene-reduced weight average molecular weight (Mw) measured by a TOSOH HLC-8220 GPC apparatus (column: TSKgel α-M, developing solvent: tetrahydrofuran (hereinafter also referred to as “THF”)). However, Preferably it is 5,000-500,000, More preferably, it is 15,000-400,000, More preferably, it is 30,000-300,000.

  The polymer (I) has a thermal decomposition temperature measured by thermogravimetric analysis (TGA) of preferably 450 ° C. or higher, more preferably 475 ° C. or higher, and further preferably 490 ° C. or higher.

The polymer (I) at 26 ° C. and a relative humidity of 45% RH.
The relative dielectric constant at 1 GHz is preferably 3.2 or less, more preferably 3.1 or less,
The relative dielectric constant at 10 GHz is preferably 3.2 or less, more preferably 3.1 or less,
The dielectric loss tangent at 1 GHz is preferably 0.005 or less, more preferably 0.003 or less,
The dielectric loss tangent at 10 GHz is preferably 0.01 or less, more preferably 0.008 or less.
The relative permittivity and dielectric loss tangent at a desired frequency are measured by a perturbation resonance method using a vector network analyzer Wiltron 37169A (manufactured by Wiltron) in an environment of 26 ° C. and a relative humidity of 45% RH.
When the relative permittivity and dielectric loss tangent of the polymer (I) in the high frequency band of 1 GHz or more are in the above ranges, the resin substrate of the present invention can be easily manufactured, the transmission speed is high, and the low transmission in the high frequency area. It is possible to provide a resin substrate for forming a high-frequency circuit substrate with low loss and excellent electrical characteristics.

<Resin substrate manufacturing method>
The method for producing the resin substrate is not particularly limited, and includes a step of applying a composition containing the polymer (I) and an organic solvent on a support to form a coating film, and the organic film is formed from the coating film. And a step of obtaining a resin substrate by removing the solvent by evaporating.

  Although the said composition may contain additives, such as anti-aging agent, according to a desired use, it is preferable that it essentially consists only of the said polymer (I).

  As the composition, a mixture of the polymer (I) obtained by the method (I ′) and an organic solvent can be used as it is. The composition is prepared by isolating (purifying) the polymer (I) as a solid from the mixture of the polymer (I) obtained by the method (I ′) and the organic solvent, It can also be prepared by redissolving in

  The method for isolating (purifying) the polymer (I) as a solid component is, for example, reprecipitation of the polymer in a poor solvent of the polymer such as methanol, and subsequent filtration, and then drying the filtrate under reduced pressure. Can be performed.

  As the organic solvent for redissolving the polymer (I), a solvent that easily dissolves the polymer (I) is preferably selected. For example, methylene chloride, tetrahydrofuran, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and γ-butyrolactone are preferably used, and from the viewpoint of coating properties and economy, Methylene chloride, cyclohexanone, N, N-dimethylacetamide and N-methylpyrrolidone are preferably used. These solvents can be used alone or in combination of two or more.

  In addition, other organic solvents such as ether organic solvents, ester organic solvents, ketone organic solvents, hydrocarbon organic solvents, alcohols are aimed at improving the drying property, uniformity, and surface smoothness during coating. One kind selected from organic organic solvents, or two or more kinds of solvents can be used in appropriate combination. In this case, an organic solvent having a boiling point in the range of 40 to 250 ° C., further 50 to 150 ° C. under atmospheric pressure (1,013 hPa) is preferable, and the polymer (I) is uniformly dissolved and dispersed. It is preferable to be used within the range where it can be used.

  Preferred examples of these other organic solvents include glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate. Esters such as ethyl lactate and ethyl 2-hydroxypropionate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether; ketones such as methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone and methyl amyl ketone Class: γ-butyrolactone It is.

  The concentration of the polymer (I) in the composition is usually 1 to 40% by mass, preferably 5 to 25% by mass, although it depends on the molecular weight of the polymer. When the concentration of the polymer (I) in the composition is in the above range, it is possible to form a resin substrate that can be thickened, hardly causes pinholes, and has excellent surface smoothness.

  The viscosity of the composition depends on the molecular weight and concentration of the polymer, but is preferably 50 to 100,000 mPa · s, more preferably 500 to 50,000 mPa · s, and still more preferably 1000 to 20,000 mPa · s. s. When the viscosity of the composition is within the above range, the composition has excellent retention during film formation, and the thickness can be easily adjusted, so that the resin substrate can be easily molded.

  The anti-aging agent is used to further improve the durability of the resin substrate, and is preferably a hindered phenol compound.

  Examples of the hindered phenol compound include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) proonate], 1,6-hexanediol-bis [3- (3, 5-Di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -3,5- Triazine, pentaerythritol tetrakis [3- (3,5-tert-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris [2-methyl-4- [3- (3,5-di-tert) -Butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane, 2,2-thio-diethyl Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), N, N- Hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and 3,9-bis [2- [3- (3-tert-butyl- 4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, etc. It can be mentioned.

  When an anti-aging agent is added to the composition, the anti-aging agent is preferably added in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the polymer (I).

  Examples of a method for forming the coating film by applying the composition include a roll coating method, a gravure coating method, a spin coating method, a slit coating method, and a method using a doctor blade. Examples of the support include a polyethylene terephthalate (PET) film and a SUS plate.

  Although the thickness when apply | coating the said composition and forming a coating film is not specifically limited, For example, it is 1-250 micrometers, Preferably it is 2-150 micrometers, More preferably, it is 5-125 micrometers.

  Further, the method for removing the organic solvent from the coating film is not particularly limited, and examples thereof include a method of heating the coating film. By heating the coating film, the organic solvent in the coating film can be evaporated and removed. The heating conditions may be determined as long as the organic solvent evaporates, and may be appropriately determined according to the support and the polymer. It is more preferable that the temperature is 50 ° C to 230 ° C.

  Further, the heating time is preferably 10 minutes to 5 hours. Note that heating may be performed in two or more stages. Specifically, after drying at a temperature of 30 to 80 ° C. for 10 minutes to 2 hours, heating is further performed at 100 to 250 ° C. for 10 minutes to 2 hours. Moreover, you may dry in nitrogen atmosphere or pressure reduction as needed.

  The amount of residual solvent in the obtained resin substrate after the step of removing the organic solvent (thermogravimetric analysis: TGA), under a nitrogen atmosphere, the heating rate is 10 ° C./min) is 100% by weight of the resin substrate. Preferably it is 0-1.2 weight%, More preferably, it is 0-1 weight%. When the amount of residual solvent is within this range, a high-frequency circuit board that has excellent heat resistance and is unlikely to be deformed or reduced in mechanical strength even at high temperatures can be obtained.

  Depending on the type of support used, the obtained resin substrate can be peeled off from the support and used as a resin substrate for a high-frequency circuit board, or used as it is as a resin substrate for a high-frequency circuit board without being peeled off. However, it is preferable to peel the support from the support.

<Physical properties of resin substrate>
Although the thickness of the resin substrate of this invention is suitably selected according to a desired use, it is 1-250 micrometers, for example, Preferably it is 2-150 micrometers, More preferably, it is 5-125 micrometers.

The resin substrate of the present invention preferably has a glass transition temperature (Tg) of 230 to 350 ° C., 240 to 330 ° C. measured by a Rigaku 8230 DSC measuring device (temperature increase rate 20 ° C./min). More preferably, it is more preferably 250 to 300 ° C.
When the resin substrate of the present invention has such a glass transition temperature, heating, heat treatment, and solder reflow process for forming wirings and the like on the substrate can be performed at a high temperature. A circuit board can be easily manufactured.

  The resin substrate of the present invention preferably has a tensile strength of 50 to 200 MPa, and more preferably 80 to 150 MPa. The tensile strength can be measured using a tensile tester 5543 (manufactured by INSTRON).

  The resin substrate of the present invention has a breaking elongation of preferably 5 to 100%, more preferably 15 to 100%. The elongation at break can be measured using a tensile tester 5543 (manufactured by INSTRON).

  The resin substrate of the present invention preferably has a tensile modulus of 2.5 to 4.0 GPa, more preferably 2.7 to 3.7 GPa. The tensile elastic modulus can be measured using a tensile tester 5543 (manufactured by INSTRON).

  The resin substrate of the present invention has a linear expansion coefficient of preferably 80 ppm / K or less, more preferably 75 ppm / K or less, measured using an SSC-5200 type TMA measuring device manufactured by Seiko Instruments.

  The resin substrate of the present invention preferably has a humidity expansion coefficient of 15 ppm /% RH or less, and more preferably 12 ppm /% RH or less. The humidity expansion coefficient can be measured using MA (SII Nanotechnology, TMA-SS6100) humidity control option. When the expansion coefficient of the resin substrate is within the above range, it shows high dimensional stability (environmental reliability) and is stable even under high humidity, so it is used in high frequency circuit boards, especially in harsh environments. The high-frequency circuit board can be suitably used.

  When the thickness of the resin substrate of the present invention is 30 μm, the total light transmittance in the JIS K7105 transparency test method is preferably 85% or more, and more preferably 88% or more. The total light transmittance can be measured using a haze meter SC-3H (manufactured by Suga Test Instruments Co., Ltd.).

  When the thickness of the resin substrate of the present invention is 30 μm, the light transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 75% or more, and further preferably 80% or more. The light transmittance at a wavelength of 400 nm can be measured using an ultraviolet / visible spectrophotometer V-570 (manufactured by JASCO).

  When the thickness of the resin substrate of the present invention is 30 μm, the YI value (yellow index) is preferably 3.0 or less, more preferably 2.5 or less, and 2.0 or less. More preferably. The YI value can be measured using an SM-T color measuring device manufactured by Suga Test Instruments Co., Ltd.

  When the thickness of the resin substrate of the present invention is 30 μm, the YI value after heating for 1 hour at 230 ° C. in the air with a hot air dryer is preferably 3.0 or less. Or less, more preferably 2.0 or less.

<High-frequency circuit board>
The high-frequency circuit board includes the resin substrate. Specifically, it is obtained by providing a wiring part on one side or both sides of the resin substrate. Since such a high-frequency circuit board includes the resin substrate, the transmission speed is high, the transmission loss is small, and these electrical characteristics can be maintained even under harsh environments such as high temperature and high humidity. In addition, the resin substrate has a wiring pattern with a pitch width of 30 μm or less because it is excellent in transparency, heat resistance, heat resistance coloring property, mechanical strength, insulation, dimensional stability, adhesion to the wiring portion, and the like. It is also possible to manufacture a high-frequency circuit board.

As a method for forming the wiring portion, for example, a laminating method, a metalizing method, a sputtering method, a vapor deposition method, a coating method, a printing method, etc. are used, and a copper layer, indium tin oxide (ITO), polythiophene, polyaniline and A method of providing a wiring portion made of a conductive material such as polypyrrole can be given.
In addition, before forming a wiring part, you may modify | reform the surface of a resin substrate as needed.

  In the laminating method, for example, a resin substrate provided with a conductive layer can be manufactured by hot pressing a metal foil such as a copper foil on the resin substrate of the present invention, and a high frequency can be obtained by patterning the conductive layer. A circuit board can be manufactured.

  In the metalizing method, for example, a seed layer made of a Ni-based metal bonded to the resin substrate of the present invention is formed by vapor deposition or sputtering, and copper having a predetermined thickness is formed on the seed layer by wet plating or the like. By providing such a conductive layer, a resin substrate provided with a conductive layer can be manufactured, and a high-frequency circuit board can be manufactured by patterning this conductive layer. In addition, when using a metalizing method, in order to improve the adhesiveness of metals, such as Ni, it is preferable to surface-modify the resin substrate of this invention previously by plasma processing etc.

  In the sputtering method, for example, a DC high voltage or the like is applied between a resin substrate and a target (a material to be formed) such as indium tin oxide (ITO) while introducing an inert gas into a vacuum. Thus, a resin substrate provided with a conductive layer can be manufactured, and a high-frequency circuit substrate can be manufactured by patterning the conductive layer.

  In the vapor deposition method, for example, a high-frequency circuit board can be manufactured by vaporizing a precursor of a material to be formed and depositing it on a resin substrate.

  In the coating method and the printing method, for example, a solution containing a target conductive material is applied to a resin substrate using a roll coating method, a gravure coating method, a spin coating method, a doctor blade, a screen printing machine, an inkjet A high frequency circuit board can be manufactured by a method of printing with a printer, a dispenser, a flexographic printing machine, a gravure printing machine, or the like.

    EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

(1) Structural analysis The structural analysis of the polymers obtained in the following examples was performed by IR (ATR method, FT-IR, 6700 (manufactured by NICOLET)) and NMR (ADVANCE500 type, manufactured by BRUKAAR).

(2) Weight average molecular weight (Mw), number average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw), the number average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) of the polymers obtained in the following examples are measured by TOSOH HLC-8220 type GPC apparatus (column: TSKgelα-M, developing solvent). : THF).

(3) Dielectric property test Using the evaluation films obtained in the following examples and comparative examples, a perturbation resonance method using a vector network analyzer Wiltron 37169A (manufactured by Wiltron) at 26 ° C. and a relative humidity of 45% RH. Below, the relative dielectric constant and dielectric loss tangent at 1 GHz and 10 GHz were measured.

(4) Transmission loss measurement Using a vacuum press apparatus, a film for evaluation (30 μm thickness) and a copper foil (thickness 18 μm) obtained in the following examples and comparative examples were thermocompression bonded at 270 ° C. and a pressure of 40 kg / cm ^2. A copper clad laminate was obtained. The circuit board (Z ₀ (characteristic impedance) = 50Ω, transmission distance = 30 mm) shown in FIG. 1 was obtained by partially removing the copper foil with a ferric chloride aqueous solution. Using this circuit board, a transmission loss (S21 parameter) at a frequency of 10 GHz was measured using a network analyzer.

(5) Glass transition temperature (Tg)
The glass transition temperatures of the polymers or evaluation films obtained in the following examples and comparative examples were measured using a Rigaku 8230 type DSC measuring apparatus with a temperature increase rate of 20 ° C./min.

(6) Water Absorption Three films for evaluation obtained in the following Examples and Comparative Examples were cut into a size of 3 cm × 4 cm and dried at 180 ° C. under reduced pressure for 8 hours. After measuring the mass of the resin layer after drying, it was immersed in distilled water at 25 ° C. for 24 hours. After immersion, water droplets on the surface of the resin layer were wiped off, the water absorption was calculated from the mass change before and after immersion, and the average value of the three sheets was calculated.

[Example 1]
In a 3 L four-necked flask, component (A): 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile (hereinafter also referred to as “DFBN”), component (B): 9,9-bis (4- Hydroxyphenyl) fluorene (hereinafter also referred to as “BPFL”) 70.08 g (0.200 mol), resorcinol (hereinafter also referred to as “RES”) 5.51 g (0.050 mol), potassium carbonate 41.46 g (0.300 mol) ), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask.

Next, after the atmosphere in the flask was replaced with nitrogen, the obtained solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours.
After the reaction, the reaction mixture was cooled to room temperature (25 ° C.), the generated salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (polymer) (yield 95.67 g, yield 95%).

Table 1 shows the physical properties of the obtained polymer. The obtained polymer was subjected to structural analysis and measurement of the weight average molecular weight. As a result, the characteristic absorption of the infrared absorption spectrum is 3035 (C—H stretching), 2229 cm ⁻¹ (CN), 1574 cm ⁻¹ , 1499 cm ⁻¹ (aromatic ring skeleton absorption), 1240 cm ⁻¹ (—O—). The weight average molecular weight was 130,000. The obtained polymer had the structural units (1) and (3).

  Next, the obtained polymer was redissolved in DMAc to obtain a resin composition having a polymer concentration of 20% by mass. The resin composition is applied onto a substrate made of polyethylene terephthalate (PET) using a doctor blade, dried at 70 ° C. for 30 minutes, and then dried at 100 ° C. for 30 minutes to form a film. It peeled. Thereafter, the film was fixed to a metal frame and further dried at 230 ° C. for 2 hours to obtain an evaluation film having a thickness of 30 μm.

  Using the obtained film for evaluation, the relative dielectric constant and dielectric loss tangent at 1 GHz and 10 GHz were measured. Further, the circuit board was formed as described above, and the transmission loss (S21 parameter) at a frequency of 10 GHz was measured using the circuit board. The measurement results are shown in Table 1.

  As shown in Table 1, the film obtained in Example 1 shows lower values for both relative dielectric constant and dielectric loss tangent at 1 GHz and 10 GHz than the polyimide film obtained in Comparative Example 1, and exhibits good electrical characteristics. Became clear. Furthermore, the transmission loss of the circuit board using the film obtained in Example 1 was about 40% lower than that of the circuit board using the film of Comparative Example 1, and it was revealed that the transmission characteristics were good.

[Example 2]
The same procedure as in Example 1 was performed except that 11.41 g (0.050 mol) of 2,2-bis (4-hydroxyphenyl) propane was used instead of RES. Table 1 shows the physical properties of the obtained film for evaluation and circuit board.

[Example 3]
As component (B), instead of 70.08 g of BPFL and 5.51 g of RES, 78.84 g (0.225 mol) of BPFL and 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3- The same operation as in Example 1 was carried out except that 8.41 g (0.025 mol) of hexafluoropropane was used. Table 1 shows the physical properties of the obtained film for evaluation and circuit board.

[Example 4]
Example 1 except that 125.65 g (0.250 mol) of 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene was used as the component (B) instead of 70.08 g of BPFL and 5.51 g of RES. The same was done. Table 1 shows the physical properties of the obtained film for evaluation and circuit board.

[Example 5]
(B) It carried out like Example 1 except having used BPFL87.60g (0.250mol) instead of BPFL70.08g and RES5.51g as a component. Table 1 shows the physical properties of the obtained film for evaluation and circuit board.

[Example 6]
(B) Instead of using 70.08 g of BPFL and 5.51 g of RES, 78.84 g (0.225 mol) of BPFL and 6.71 g (0.025 mol) of 9,9-bis (4-hydroxyphenyl) cyclohexane were used. Was carried out in the same manner as in Example 1. Table 1 shows the physical properties of the obtained film for evaluation and circuit board.

[Example 7]
(A) It carried out like Example 5 except having used DFBN28.10g (0.202 mol) and 4,4-difluorobenzophenone 11.02g (0.051 mol) instead of DFBN35.12g. Table 1 shows the physical properties of the obtained film for evaluation and circuit board.

[Example 8]
(A) It carried out similarly to Example 7 except having changed the compounding quantity of the component into DFBN 17.56g (0.126mol) and 4,4-difluorobenzophenone 27.55g (0.126mol). Table 1 shows the physical properties of the obtained film for evaluation and circuit board.

[Example 9]
As component (A), the same procedure as in Example 5 was performed except that 78.84 g (0.250 mol) of 4,4-difluorodiphenylsulfone (DFDS) was used instead of 35.12 g of DFBN. Table 1 shows the physical properties of the obtained film for evaluation and circuit board.

[Comparative example]
The dielectric constant and dielectric loss tangent at 1 GHz and 10 GHz were measured in the same manner as in Example 1 except that a polyimide film (Kapton 100H, 25 μm) was used. Transmission loss at a frequency of 10 GHz (S21 parameter) using a circuit board ) Was measured. The measurement results are shown in Table 1.

Claims (5)

At 26 ° C. and relative humidity 45% RH,
The relative dielectric constant at 1 GHz and 10 GHz is 3.2 or less, the dielectric loss tangent at 1 GHz is 0.0050 or less, and the dielectric loss tangent at 10 GHz is 0.010 or less,
Comprising an aromatic polyether polymer having at least one structural unit (i) selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2):
Resin substrate for high-frequency circuit boards.

(In Formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.)

(In the formula (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO ₂ -Or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 And m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.) The aromatic polyether polymer further has at least one structural unit (ii) selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). The resin substrate according to claim 1.

(In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1 .)

(In the formula ^{(4), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f.) The molar ratio of the said aromatic polyether polymer, a pre-Symbol structural units (i), a pre-Symbol structural units (ii) (structural unit (i): a structural unit (ii)) is 50: 50 to 100: The resin substrate according to claim 2, which is zero.   The resin substrate according to any one of claims 1 to 3, wherein the aromatic polyether polymer has a polystyrene-equivalent weight average molecular weight of 5,000 to 500,000 by gel permeation chromatography (GPC). .   A high-frequency circuit board comprising the resin substrate according to claim 1.

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