JP6409643B2 - Thermosetting resin composition and use thereof - Google Patents

Description

  The present invention relates to a thermosetting resin composition having excellent dielectric properties such as low dielectric constant and dielectric loss tangent, and uses thereof such as a resin substrate and a circuit board.

In mobile communication devices typified by mobile phones, high-frequency electrical signals are used to increase the processing speed. In addition, in order to increase the propagation speed of electric signals, there is a method of reducing the length of the wiring by reducing the size of the semiconductor element or increasing the density of the mounting substrate, but the relative dielectric constant (ε _r ) Can also be reduced to increase the propagation speed. By the way, the electric signal tends to attenuate as the frequency becomes higher, and the transmission loss tends to increase. For this reason, it is required to lower the dielectric loss tangent (tan δ) of the substrate.

  As a material for forming the substrate, a thermosetting resin composition containing a dihydrobenzoxazine compound having a low relative dielectric constant and excellent heat resistance and flame retardancy is known (see, for example, Patent Document 1). Dihydrobenzoxazine compounds are known not to generate volatile substances because the dihydrobenzoxazine ring undergoes a ring-opening reaction and heat cures.

JP2012-241168A

  In a thermosetting resin composition containing a dihydrobenzoxazine compound, a ring-opening reaction with the dihydrobenzoxazine compound (see the following reaction formula) generates a hydroxyl group. Therefore, the relative permittivity and dielectric loss tangent of the resulting cured product are determined. Lowering is difficult.

上記式中、Ｒはアリール基等の有機基である。
本発明は、比誘電率（ε_r）および誘電正接（ｔａｎδ）の値が小さい樹脂基板を形成可能な熱硬化性樹脂組成物、ならびに前記組成物から形成された、前記誘電特性を有する樹脂基板を提供することを課題とする。

In the above formula, R is an organic group such as an aryl group.
The present invention relates to a thermosetting resin composition capable of forming a resin substrate having a small value of relative dielectric constant (ε _r ) and dielectric loss tangent (tan δ), and a resin substrate having the dielectric characteristics, formed from the composition It is an issue to provide.

  The present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the following thermosetting resin composition can solve the above problems, and have completed the present invention. That is, the present invention relates to the following [1] to [6], for example.

  [1] A thermosetting resin composition containing a polymer (A) having a structure represented by the formula (A1) and a compound (B) having a dihydro-1,3-benzoxazine structure.

［式（Ａ１）中、＊は結合手を示す。］
［２］重合体（Ａ）が、式（Ａ２）で表される構造単位を有する前記［１］に記載の熱硬化性樹脂組成物。

[In formula (A1), * indicates a bond. ]
[2] The thermosetting resin composition according to [1], wherein the polymer (A) has a structural unit represented by the formula (A2).

［式（Ａ２）中、Ｒ¹は水素原子または炭化水素基であり；Ｒ²は２価の有機基である。］
［３］式（Ａ２）中のＲ²が、式（ｇ１）で表される２価の基である前記［２］に記載の熱硬化性樹脂組成物。

[In Formula (A2), R ¹ is a hydrogen atom or a hydrocarbon group; R ² is a divalent organic group. ]
[3] The thermosetting resin composition according to [2], wherein R ² in the formula (A2) is a divalent group represented by the formula (g1).

［式（ｇ１）中、Ｒ³は、それぞれ独立に炭素数６〜２０のアリーレン基、または前記アリーレン基に含まれる１以上の水素原子が炭素数１〜２０のアルキル基で置換された基であり；Ｒ⁴は直接結合または２価の基であり；ｍは０または１である。］
［４］化合物（Ｂ）が、式（ｂ１）で表される化合物である前記［１］〜［３］のいずれか１項に記載の熱硬化性樹脂組成物。

[In Formula (g1), each R ³ is independently an arylene group having 6 to 20 carbon atoms, or a group in which one or more hydrogen atoms contained in the arylene group are substituted with an alkyl group having 1 to 20 carbon atoms. Yes; R ⁴ is a direct bond or a divalent group; m is 0 or 1; ]
[4] The thermosetting resin composition according to any one of [1] to [3], wherein the compound (B) is a compound represented by the formula (b1).

［式（ｂ１）中、Ｒ^B1は２価の基であり、Ｒ^B2は、それぞれ独立にハロゲン原子、または置換基を有してもよい炭化水素基であり、ｍおよびｎは、それぞれ独立に０〜４の整数である。］
［５］前記［１］〜［４］のいずれか１項に記載の熱硬化性樹脂組成物から製造される樹脂基板。
［６］前記［５］に記載の樹脂基板を有する回路基板。

[In the formula (b1), R ^B1 is a divalent group, R ^B2 is independently a halogen atom or a hydrocarbon group which may have a substituent, and m and n are each independently It is an integer of 0-4. ]
[5] A resin substrate produced from the thermosetting resin composition according to any one of [1] to [4].
[6] A circuit board having the resin substrate according to [5].

According to the present invention, a thermosetting resin composition capable of forming a resin substrate having small values of relative dielectric constant (ε _r ) and dielectric loss tangent (tan δ), and the dielectric characteristics formed from the composition are provided. A resin substrate can be provided.

FIG. 1 is a diagram for explaining a pressing process when manufacturing a resin substrate in the embodiment.

  In this specification, the structure or structural unit represented by the formula (n) is also referred to as “structure (n)” or “structural unit (n)”, respectively, and the compound represented by the formula (n) is represented by “compound ( n) ". The n is a formula number.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention contains a polymer (A) having a structure represented by the formula (A1) and a compound (B) having a dihydro-1,3-benzoxazine structure. The composition is also simply referred to as “the composition of the present invention”.

By using the composition of the present invention, a resin substrate having small values of relative dielectric constant (ε _r ) and dielectric loss tangent (tan δ) can be formed. Moreover, the obtained resin substrate has the characteristics of high heat resistance and high chemical resistance. The reason why a resin substrate having these characteristics is obtained will be described later.

<Polymer (A)>
The polymer (A) has a structure represented by the formula (A1).

式（Ａ１）中、＊は結合手を示す。
重合体（Ａ）は、式（Ａ２）で表される構造単位を有することが好ましい。

In formula (A1), * represents a bond.
The polymer (A) preferably has a structural unit represented by the formula (A2).

式（Ａ２）中、Ｒ¹は水素原子または炭化水素基である。Ｒ²は２価の有機基である。
Ｒ¹における炭化水素基としては、例えば、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数２〜２０のアルキニル基、炭素数３〜２０のシクロアルキル基、前記シクロアルキル基に含まれる１以上の水素原子が炭素数１〜２０のアルキル基で置換された基（以下「置換シクロアルキル基」ともいう）、炭素数３〜２０のシクロアルケニル基、前記シクロアルケニル基に含まれる１以上の水素原子が炭素数１〜２０のアルキル基で置換された基（以下「置換シクロアルケニル基」ともいう）、炭素数６〜２０のアリール基、または前記アリール基に含まれる１以上の水素原子が炭素数１〜２０のアルキル基で置換された基（以下「置換アリール基」ともいう）が挙げられる。

In formula (A2), R ¹ represents a hydrogen atom or a hydrocarbon group. R ² is a divalent organic group.
Examples of the hydrocarbon group in R ¹ include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and the above cyclo A group in which one or more hydrogen atoms contained in the alkyl group are substituted with an alkyl group having 1 to 20 carbon atoms (hereinafter also referred to as “substituted cycloalkyl group”), a cycloalkenyl group having 3 to 20 carbon atoms, the cycloalkenyl group A group in which one or more hydrogen atoms contained in 1 is substituted with an alkyl group having 1 to 20 carbon atoms (hereinafter also referred to as “substituted cycloalkenyl group”), an aryl group having 6 to 20 carbon atoms, or the aryl group And a group in which one or more hydrogen atoms are substituted with an alkyl group having 1 to 20 carbon atoms (hereinafter also referred to as “substituted aryl group”).

  Examples of the alkyl group include a linear or branched alkyl group, and specifically include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and an s-butyl group. Group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group and nonyl group.

  Examples of the alkenyl group include a vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, heptenyl group, and hexenyl group.

Examples of the alkynyl group include an ethynyl group and a 2-propenyl group.
Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

  Examples of the substituted cycloalkyl group include a methylcyclopropyl group, an ethylcyclopropyl group, a methylcyclohexyl group, an ethylcyclohexyl group, a methylcyclooctyl group, and an ethylcyclooctyl group.

Examples of the cycloalkenyl group include a cyclohexenyl group, and examples of the substituted cycloalkenyl group include a methylcyclohexenyl group.
Examples of the aryl group include monocyclic or bicyclic or more aryl groups, and specific examples include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group.

Examples of the substituted aryl group include a toluyl group and a xylyl group.
R ¹ is preferably a hydrocarbon group, more preferably an alkyl group having 1 to 20 carbon atoms, and still more preferably a methyl group, because the relative permittivity and dielectric loss tangent of the resulting cured product can be lowered.

Examples of the divalent organic group for R ² include linear or branched divalent hydrocarbon groups having 1 to 20 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and aromatics. And divalent organic groups containing a group ring.

  Examples of the linear or branched divalent hydrocarbon group include alkanediyl groups such as 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 include cycloalkanediyl groups such as cyclopropylene group, cyclobutylene group, cyclopentylene group, and cyclohexylene group; cyclobutenylene group, cyclopentenylene group, and cyclohexenylene. Cycloalkenediyl groups such as groups; groups in which one or more hydrogen atoms contained in the cycloalkanediyl group and the cycloalkenediyl group are substituted with an alkyl group having 1 to 20 carbon atoms.

  As the aromatic ring, for example, benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, fluorene ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrimidine ring, pyridazine ring, Examples include a pyrazine ring, a quinoline ring, an isoquinoline ring, an indole ring, a benzofuran ring, an acridine ring, a phenoxazine ring, and a phenothiazine ring.

  A substituent may be bonded to the aromatic ring. Examples of the substituent include halogen atom; cyano group; amino group; hydroxyl group; alkyl group, alkenyl group, alkynyl group, alkoxy group, alkenyloxy group, alkynyloxy group, alkanoyl group, alkoxycarbonyl group and the like. -12 organic groups;

  As the divalent organic group containing an aromatic ring, a divalent group represented by the formula (g1) is preferable because the relative permittivity and dielectric loss tangent of the obtained cured product can be lowered.

式（ｇ１）中、Ｒ³は、それぞれ独立に炭素数６〜２０のアリーレン基、または前記アリーレン基に含まれる１以上の水素原子が炭素数１〜２０のアルキル基で置換された基（以下「置換アリーレン基」ともいう）であり；Ｒ⁴は直接結合または２価の基であり；ｍは０または１である。

In formula (g1), each R ³ independently represents an arylene group having 6 to 20 carbon atoms, or a group in which one or more hydrogen atoms contained in the arylene group are substituted with an alkyl group having 1 to 20 carbon atoms (hereinafter referred to as “R ^3” ). R ⁴ is a direct bond or a divalent group; m is 0 or 1; also referred to as “substituted arylene group”.

  Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a phenanthrylene group. Preferably it is a C6-C10 arylene group. Examples of the substituted arylene group include a methylphenylene group and a dimethylphenylene group.

R ³ is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and even more preferably a phenylene group because the relative permittivity and dielectric loss tangent of the obtained cured product can be lowered. It is.

Examples of the divalent group for R ⁴ include —O—, —S—, —SO ₂ —, —CO—, —CONH—, —COO—, —C (CF ₃ ) ₂ —, and A linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent alicyclic ring having 3 to 20 carbon atoms, exemplified as a divalent organic group for R ² in formula (A2). Also included are the formula hydrocarbon groups.

R ⁴ is preferably a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably 1 carbon atom, since the dielectric constant and dielectric loss tangent of the resulting cured product can be lowered. -20 alkanediyl groups, more preferably a methylene group.
m is preferably 1.

The polymer (A) may be a polymer having one type of structural unit (A2), or may be a polymer having two or more types of structural units (A2).
The polymer (A) preferably has the structural unit (A2) of 50% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass or more. The content of the structural unit (A2) can be measured by NMR.

  The terminal structure of the polymer (A) is preferably a structure represented by an acetyl group and / or the formula (A3) from the viewpoint of suppressing coloring during heating.

式（Ａ３）中、Ｒ⁵およびＲ⁶は、それぞれ独立にニトロ基、ニトリル基または炭素数１〜１２の有機基を示し、Ｅは直接結合または２価の基であり、ｊは０〜４の整数であり、ｋは０〜５の整数であり、ｍは０または１である。

In formula (A3), R ⁵ and R ⁶ each independently represent a nitro group, a nitrile group or an organic group having 1 to 12 carbon atoms, E is a direct bond or a divalent group, and j is 0 to 4 K is an integer of 0 to 5, and m is 0 or 1.

Examples of the organic group having 1 to 12 carbon atoms in R ⁵ and R ⁶ include organic groups having 1 to 12 carbon atoms exemplified as the substituent that may be bonded to the aromatic ring in the description of the formula (A2). . R ⁵ and R ⁶ are particularly preferably a methoxy group and an acetyl group from the viewpoint of suppressing coloring during heating.

Examples of the divalent group in E include —O—, —S—, —SO ₂ —, —CO—, —CONH—, —COO—, —C (CF ₃ ) ₂ —, and Examples of the divalent organic group represented by R ² in the formula (A2) include a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms and a divalent alicyclic group having 3 to 20 carbon atoms. Also included are hydrocarbon groups.
m is preferably 0 and k is preferably 1.

  As the polymer (A), for example, in the case of a polymer having two ends, (i) one of the two ends of the polymer is a polymer in which one is an acetyl group, and (ii) one is a structure (A3). (Ii) a polymer in which both are acetyl groups, (iv) a polymer in which both are structures (A3), (v) one is an acetyl group and the other is a structure (A3) A polymer is mentioned.

As the terminal structure of the polymer (A), m is 0, k is 1, and R ^{6 in the} acetyl group or the formula (A3) in terms of suppression of coloring during heating and ease of synthesis. Is a structure in which is a methoxy group.

<< Characteristics of Polymer (A) >>
The polymer (A) has a polystyrene-equivalent weight average molecular weight (Mw) of usually 1,000 to 1,000,000, preferably 10,000 to 500,000, more preferably 30,000 to 200,000. It is. Moreover, molecular weight distribution (Mw / Mn) is 2-10 normally, Preferably it is 2-6, More preferably, it is 2-4. When Mw is within the above range, it is preferable from the viewpoints of heat resistance, chemical resistance and handling properties of the resin substrate. Mw can be measured by the method described in Examples by gel permeation chromatography (GPC).

  The content of the polymer (A) is usually 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass in 100% by mass of the solid content excluding the compound (B) in the composition of the present invention. % Or more. When the content of the polymer (A) is in the above range, it is possible to form a resin substrate that can be thickened when a coating film is formed, does not easily cause pinholes, and has excellent surface smoothness.

<< Synthesis Method of Polymer (A) >>
The polymer (A) can be synthesized, for example, by reacting the compound represented by the formula (a1) with the compound represented by the formula (a2). In this reaction, each of the compound (a1) and the compound (a2) may be used alone or in combination of two or more.

式（ａ１）中、Ｒ¹は、式（Ａ２）中の同一記号と同義であり、Ｘは、それぞれ独立にハロゲン原子であり、塩素原子またはフッ素原子が好ましい。

In the formula (a1), R ¹ has the same meaning as the same symbol in the formula (A2), each X is independently a halogen atom, preferably a chlorine atom or a fluorine atom.

  Examples of the compound (a1) include 2,4-dichloro-6-methoxy-1,3,5-triazine and 2,4-dichloro-6-ethoxy-1,3,5-triazine.

式（ａ２）中、Ｒ²は、式（Ａ２）中の同一記号と同義であり、Ｒ⁷は、それぞれ独立に水素原子、メチル基、エチル基、アセチル基、メタンスルホニル基またはトリフルオロメチルスルホニル基であり、水素原子が好ましい。
化合物（ａ２）としては、式（ａ２’）で表される化合物が好ましい。

In the formula (a2), R ² has the same meaning as the same symbol in the formula (A2), and R ⁷ each independently represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, a methanesulfonyl group or a trifluoromethylsulfonyl. And is preferably a hydrogen atom.
As the compound (a2), a compound represented by the formula (a2 ′) is preferable.

式（ａ２’）中、Ｒ³、Ｒ⁴およびｍは、それぞれ式（ｇ１）中の同一記号と同義であり、Ｒ⁷は、式（ａ２）中の同一記号と同義である。
化合物（ａ２）としては、例えば、ビスフェノールＡ、ビスフェノールＦが挙げられる。

In formula (a2 ′), R ³ , R ⁴ and m have the same meaning as the same symbol in formula (g1), and R ⁷ has the same meaning as the same symbol in formula (a2).
Examples of the compound (a2) include bisphenol A and bisphenol F.

The use ratio (molar ratio) of the compound (a1) and the compound (a2) may be 50:50, but preferably the compound (a1): from the viewpoint that the desired polymer (A) can be easily synthesized. Compound (a2) = 30: 70 to 70:30 (however, the sum of both is 100).
More specifically, the synthesis reaction of the polymer (A) can be performed in the presence of a solvent.

Examples of the solvent include water and organic solvents. Examples of the organic solvent include chloroform, 1,1,2,2-tetrachloroethane, toluene, mesitylene, cyclohexanone, cyclopentanone, N, N-dimethylacetamide, 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 (of alkoxy group) C1-C4) and trialkoxybenzene (C1-C4 of an alkoxy group) are mentioned. Among these, it is preferable to use water and an organic solvent in combination. A solvent may be used individually by 1 type and may use 2 or more types together.
The synthesis reaction of the polymer (A) can be preferably performed in the presence of a catalyst.

  Examples of the catalyst include alkali metals such as lithium, potassium and sodium; alkali hydrides such as lithium hydride, potassium hydride and sodium hydride; alkali metals such as lithium hydroxide, potassium hydroxide and sodium hydroxide; Examples thereof include alkali metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate; alkali metal-containing compounds such as alkali metal hydrogen carbonates such as lithium hydrogen carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate. A catalyst may be used individually by 1 type and may use 2 or more types together.

The above-exemplified catalyst can be used usually in an amount of 0.1 to 10 mol, preferably 0.2 to 5 mol, relative to 1 mol of the compound (a1).
When water and an organic solvent are used in combination, it is preferable to use a phase transfer catalyst. Examples of the phase transfer catalyst include tetraethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide (TBAB), tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, benzylcetyldimethylammonium chloride hydrated. Quaternary ammonium salts such as benzylcetyldimethylammonium chloride, benzyldimethylphenylammonium chloride, benzyldimethyltetradecylammonium chloride hydrate, benzyltributylammonium chloride, benzyltriethylammonium chloride, benzyltrimethylammonium chloride; tetrabutylphosphonium chloride, Tetrabutylphosphonium Quaternary phosphonium salts such as bromide, crown ethers.

  Among the phase transfer catalysts, a quaternary ammonium salt is preferable, and TBAB and benzylcetyldimethylammonium chloride hydrate are more preferable because a high molecular weight polymer can be obtained in a short time and in a high yield.

  The phase transfer catalyst is preferably used in such an amount that the molar concentration in the aqueous phase is 5 to 50 mol / L from the viewpoint that a high molecular weight polymer can be obtained in a short time and with a high yield. More preferably, it is used in an amount of / L.

  In the reaction of compound (a1) and compound (a2), the reaction temperature is preferably −10 to 200 ° C., more preferably −5 to 100 ° C., and the reaction time is preferably 0.5 to 60. Time, more preferably 1 to 10 hours. After completion of the reaction, the obtained polymer (A) can be purified by a known method.

  The polymer whose terminal structure is an acetyl group and / or structure (A3) can be synthesized, for example, by using a compound represented by formula (a3) and / or a compound represented by formula (a4). it can. Specifically, the reaction between the compound (a1) and the compound (a2) may be performed in the presence of the compound (a3) and / or (a4), or the compound (a1) and the compound (a2) are reacted. You may make the polymer obtained by making it react, and a compound (a3) and / or a compound (a4).

式（ａ３）中、Ｒ⁸は、水素原子、メチル基、エチル基、アセチル基、メタンスルホニル基またはトリフルオロメチルスルホニル基である。

In formula (a3), R ⁸ represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, a methanesulfonyl group or a trifluoromethylsulfonyl group.

式（ａ４）中、Ｒ⁵、Ｒ⁶、Ｅ、ｊ、ｋおよびｍは、それぞれ式（Ａ３）中の同一記号と同義であり、Ｒ^eは、ハロゲン原子または−ＯＲ⁸である。Ｒ⁸は、式（ａ３）中の同一記号と同義である．Ｒ^eは、化合物（ａ１）と化合物（ａ２）とのモル比や、化合物（ａ１）と化合物（ａ２）とを反応させて得られた重合体の末端構造に応じて、適宜選択すればよい。

Wherein ^{(a4), R 5, R} 6, E, j, k and m are as defined the same symbols for each formula (A3) in, R ^e is a halogen atom or -OR ^8. R ⁸ has the same meaning as the same symbol in formula (a3). R ^e is, compounds the molar ratio and the compound (a2) (a1), in accordance with the terminal structure of the compound (a1) with the compound (a2) and obtained by reacting a polymer, it may be suitably selected .

  The amount of compound (a3) or compound (a4) to be used is generally 0.005 to 15 mol, preferably 0.0075 to 12 mol, per 1 mol in total of compound (a1) and compound (a2). .

<Compound (B)>
Compound (B) has a dihydro-1,3-benzoxazine structure.
The dihydro-1,3-benzoxazine structure refers to a skeleton represented by the following formula.

上記式中、破線は結合手を示す。
化合物（Ｂ）は、重合体（Ａ）との硬化反応の観点から、ジヒドロ−１，３−ベンゾオキサジン構造を２以上有することが好ましく、より好ましくは２〜１０、さらに好ましくは２〜５であり、特に好ましくはジヒドロ−１，３−ベンゾオキサジン構造を２つ有する化合物である。

In the above formula, a broken line indicates a bond.
From the viewpoint of the curing reaction with the polymer (A), the compound (B) preferably has two or more dihydro-1,3-benzoxazine structures, more preferably 2 to 10, more preferably 2 to 5. And particularly preferred is a compound having two dihydro-1,3-benzoxazine structures.

  Examples of the compound (B) include a compound represented by the formula (b1) and a compound represented by the formula (b2). Moreover, the oligomer which several molecule polymerized at least 1 sort (s) selected from a compound (b1) and a compound (b2) is also mentioned.

式（ｂ１）および（ｂ２）中、Ｒ^B1は、２価の基である。Ｒ^B4は、直接結合または２価の基である。Ｒ^B2は、それぞれ独立にハロゲン原子、または置換基を有してもよい炭化水素基である。Ｒ^B3は、それぞれ独立に水素原子、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、前記シクロアルキル基に含まれる１以上の水素原子が炭素数１〜２０のアルキル基もしくはハロゲン原子で置換された基（以下「置換シクロアルキル基’」ともいう）、炭素数６〜２０のアリール基、または前記アリール基に含まれる１以上の水素原子が炭素数１〜２０のアルキル基もしくはハロゲン原子で置換された基（以下「置換アリール基’」ともいう）である。ｍおよびｎは、それぞれ独立に０〜４の整数であり、ｐおよびｑは、それぞれ独立に０〜３の整数である。

In formulas (b1) and (b2), R ^B1 is a divalent group. R ^B4 is a direct bond or a divalent group. R ^B2 is independently a halogen atom or a hydrocarbon group which may have a substituent. R ^B3 is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an alkyl group in which one or more hydrogen atoms contained in the cycloalkyl group are 1 to 20 carbon atoms. Alternatively, a group substituted with a halogen atom (hereinafter, also referred to as “substituted cycloalkyl group ′”), an aryl group having 6 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms in which one or more hydrogen atoms contained in the aryl group are substituted Or a group substituted with a halogen atom (hereinafter also referred to as “substituted aryl group ′”). m and n are each independently an integer of 0 to 4, and p and q are each independently an integer of 0 to 3.

Examples of the divalent group in R ^B1 and R ^B4, for example, -O -, - S -, - SO 2 -, - CO -, - CONH -, - COO -, - C (CF 3) 2 -, above A divalent group represented by the formula (g1) in the formula, and a linear or branched group having 1 to 20 carbon atoms exemplified as the divalent organic group in R ² in the formula (A2). A bivalent hydrocarbon group and a C3-C20 bivalent alicyclic hydrocarbon group are also mentioned.

Examples of the halogen atom in R ^B2 include a chlorine atom, a bromine atom, and a fluorine atom. Examples of the hydrocarbon group which may have a substituent in R ^B2 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and these And groups in which one or two or more hydrogen atoms contained in the group are substituted with any group selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a hydroxyl group.

In R ^B3 , specific examples of the alkyl group, cycloalkyl group, and aryl group include the groups exemplified as R ^{1 in} formula (A2). The alkyl group preferably has 1 to 12 carbon atoms, the cycloalkyl group preferably has 3 to 8 carbon atoms, and the aryl group preferably has 6 to 10 carbon atoms.

Specific examples of the substituted cycloalkyl group 'and the substituted aryl group' in R ^B3 include the groups exemplified as the substituted cycloalkyl group and the substituted aryl group of R ^{1 in} Formula (A2), as well as a chlorophenyl group and a bromophenyl group. Can be mentioned. The substituted cycloalkyl group 'preferably has 3 to 8 carbon atoms, and the substituted aryl group' preferably has 6 to 10 carbon atoms.
Specific examples of the compound (b1) and the compound (b2) are shown below.

上記式中、Ｐｈはフェニル基であり、ＰｈＭｅは４−メチルフェニル基である。
化合物（Ｂ）は、ジヒドロ−１，３−ベンゾオキサジン構造を有する重合体であってもよい。例えば、ジヒドロ−１，３−ベンゾオキサジン構造を側鎖中または主鎖中に有する重合体が挙げられる。

In the above formula, Ph is a phenyl group, and PhMe is a 4-methylphenyl group.
The compound (B) may be a polymer having a dihydro-1,3-benzoxazine structure. For example, a polymer having a dihydro-1,3-benzoxazine structure in the side chain or main chain can be mentioned.

  When the compound (B) is a polymer, the weight average molecular weight (Mw) in terms of polystyrene of the polymer is usually 1,000 to 100,000. Mw can be measured by the method described in Examples by gel permeation chromatography (GPC).

《Side chain polymer》
Examples of the polymer having a dihydro-1,3-benzoxazine structure in the side chain include a polymer (Ba) having a structural unit represented by the formula (B1). The structural unit represented by the formula (B1) is preferably a structural unit represented by the formula (B1 ′).

式（Ｂ１）および（Ｂ１’）中、Ｒ¹は水素原子または炭素数１〜２０のアルキル基である。Ａｒ¹は芳香族環を有する基である。Ｒ²は炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、置換アリール基、または−Ｒ³−Ｒ⁴で表される１価の基である。Ｒ³は炭素数１〜２０のアルカンジイル基であり、Ｒ⁴は炭素数６〜２０のアリール基または置換アリール基である。前記Ｒ²の中でも、炭素数１〜２０のアルキル基、または−Ｒ³−Ｒ⁴で表される１価の基が好ましい。

In formulas (B1) and (B1 ′), R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Ar ¹ is a group having an aromatic ring. R ² is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a substituted aryl group, or a monovalent group represented by —R ³ —R ⁴ . R ³ is an alkanediyl group having 1 to 20 carbon atoms, and R ⁴ is an aryl group or substituted aryl group having 6 to 20 carbon atoms. Among the R ² , an alkyl group having 1 to 20 carbon atoms or a monovalent group represented by —R ³ —R ⁴ is preferable.

In Ar ¹ , some or all of the ring carbons of the aromatic ring are ring constituent atoms that form a dihydro-1,3-benzoxazine structure. That is, the aromatic ring forms a dihydro-1,3-benzoxazine structure together with the oxazine ring. Examples of the group having an aromatic ring represented by Ar ¹ include an aromatic ring such as a benzene ring, a naphthalene ring, and an anthracene ring; one or more hydrogen atoms contained in the aromatic ring are substituted with a monovalent group Group. Examples of the monovalent group include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, a nitro group, and a cyano group.

The content ratio of the structural unit (B1) in all the structural units of the polymer (Ba) is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more. The said structural unit shows the unit which made the structural unit derived from the monomer used for the synthesis | combination of a polymer (Ba) 1 structural unit. The content ratio of the structural unit (B1) in all the structural units of the polymer (Ba) can be calculated from the integrated value of ¹ H NMR.

The polymer (Ba) includes, for example, a polymer (Ba ′) having a phenolic hydroxyl group having a structural unit represented by the formula (B1-1), and a primary amine represented by R ² —NH _2. It can be obtained by reacting formaldehyde as a raw material. In the synthesis reaction, 1 to 20 mol of primary amine and 2 to 40 mol of formaldehyde are usually used for 1 mol of the structural unit having a phenolic hydroxyl group of the polymer (Ba ′).

式（Ｂ１−１）中、Ｒ¹は式（Ｂ１）中の同一記号と同義である。Ａｒ²は芳香族環を有する２価の基であり、Ａｒ²に含まれる前記芳香族環には、式（Ｂ１−１）中に現れる−ＯＨ（フェノール性水酸基）が直結する。

In formula (B1-1), R ¹ has the same meaning as the same symbol in formula (B1). Ar ² is a divalent group having an aromatic ring, and —OH (phenolic hydroxyl group) appearing in the formula (B1-1) is directly connected to the aromatic ring contained in Ar ² .

Examples of the group having an aromatic ring represented by Ar ² include an aromatic ring such as a benzene ring, a naphthalene ring and an anthracene ring; one or more hydrogen atoms contained in the aromatic ring are substituted with a monovalent group Group. Examples of the monovalent group include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, a nitro group, and a cyano group.

  The reaction conditions in the synthesis reaction are as follows. The reaction temperature is usually 0 to 250 ° C., preferably 50 to 150 ° C .; the reaction time is usually 0.5 to 40 hours, preferably 1 to 30 hours. It is preferable to carry out the reaction while removing water under reduced pressure.

  The above synthesis reaction is usually performed in a reaction solvent. Examples of the reaction solvent include halogen solvents such as chloroform and dichloromethane; ether solvents such as tetrahydrofuran and dioxane; aromatic solvents such as xylene and toluene; and N-methyl-2-pyrrolidone.

  The above synthesis reaction can be carried out in the presence of a catalyst. Examples of the catalyst include an acid catalyst and a base catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as p-toluenesulfonic acid, xylenesulfonic acid and methanesulfonic acid; Lewis acids such as aluminum chloride and zinc chloride; activated clay, acidic clay, white Solid acids such as carbon, zeolite and silica alumina; acidic ion exchange resins. Examples of the base catalyst include diazabicycloundecene and pyridine.

R ² in primary amine represented by R ² -NH ₂ has the same meaning as R ² in the formula (B1). Examples of the primary amine include methylamine, ethylamine, butylamine, hexylamine, and phenylamine. A primary amine may be used individually by 1 type, and may use 2 or more types together.

The formaldehyde used for the synthesis can also be used as paraformaldehyde.
Examples of the polymer (Ba ′) include a homopolymer of a radical polymerizable monomer having a phenolic hydroxyl group, or a copolymer of a radical polymerizable monomer having a phenolic hydroxyl group and another radical polymerizable monomer. Coalescence is mentioned.

  Examples of the radical polymerizable monomer having a phenolic hydroxyl group include hydroxystyrene such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, and p-isopropenylphenol. Monomers, monomers obtained by substituting one or more hydrogen atoms bonded to the aromatic ring carbon of hydroxystyrene monomers with alkyl, alkoxyl, halogen, haloalkyl, nitro or cyano; vinyl hydroquinone, 5-vinyl pyrogallol, 6 -Vinyl pyrogallol is mentioned. Moreover, the monomer which protects the phenolic hydroxyl group of the said monomer with an alkyl group, a silyl group, etc. can also be mentioned. When using the monomer formed by protecting the phenolic hydroxyl group, a polymer (Ba ') having a phenolic hydroxyl group can be obtained by removing the protection after forming the polymer. One type of the monomer may be used alone, or two or more types may be used in combination.

  Other radical polymerizable monomers include, for example, styrene monomers such as styrene, α-methylstyrene, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; aromatic styrene monomers And monomers obtained by substituting one or more hydrogen atoms bonded to the ring carbon with alkyl, alkoxyl, halogen, haloalkyl, nitro or cyano. One type of the monomer may be used alone, or two or more types may be used in combination.

<< Main chain polymer >>
Examples of the polymer having a dihydro-1,3-benzoxazine structure in the main chain include a polymer (Bb) having a structural unit represented by the formula (B2).

式（Ｂ２）中、Ａｒ³は芳香族環を有する４価の基である。４価の基に含まれる芳香族環の一部または全部の環炭素が、ジヒドロ−１，３−ベンゾオキサジン構造を形成する環構成原子である。すなわち、前記芳香族環は、オキサジン環とともにジヒドロ−１，３−ベンゾオキサジン構造を形成している。Ｒ³は２価の炭化水素基である。２価の炭化水素基としては、例えば、脂肪族炭化水素基、脂環式炭化水素基が挙げられる。

In the formula (B2), Ar ³ is a tetravalent group having an aromatic ring. A part or all of the ring carbons of the aromatic ring contained in the tetravalent group are ring-constituting atoms that form a dihydro-1,3-benzoxazine structure. That is, the aromatic ring forms a dihydro-1,3-benzoxazine structure together with the oxazine ring. R ³ is a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include an aliphatic hydrocarbon group and an alicyclic hydrocarbon group.

The polymer (Bb) is obtained, for example, by reacting a compound represented by HO—Ar ⁴ —OH, a diamine represented by H ₂ N—R ³ —NH ₂ , and formaldehyde as raw materials. Wherein said R ³ has the same meaning as R ³ in the formula (B2), wherein Ar ⁴ is a divalent group leads to Ar ³ in the formula (B2).

  Specific examples of the polymer (Bb) include a thermosetting resin having a dihydrobenzoxazine structure in the main chain described in JP 2008-239649 A, and a synthesis method is also described in the document. A method can be mentioned.

<< Content of Compound (B) >>
In the composition of the present invention, the content of the compound (B) is dihydro-1,3-benzoxazine contained in the compound (B) with respect to 1 mol of the structure (A1) contained in the polymer (A). The amount is such that the structure is usually 0.1 to 2 mol, preferably 0.3 to 0.85 mol, more preferably 0.55 to 0.8 mol. When the content of the compound (B) is in the above range, it is preferable because the relative permittivity and dielectric loss tangent of the obtained cured product can be lowered and the chemical resistance is excellent.

<Other ingredients>
The thermosetting resin composition of the present invention may contain other components in addition to the polymer (A) and the compound (B) as long as the object of the present invention is not impaired. Examples of the other components include inorganic particles, resin components other than the polymer (A), flame retardants, anti-aging agents, thermal stabilizers, antioxidants, UV absorbers, surfactants, lubricants, and fillers. Can be mentioned.

<solvent>
The composition of the present invention may contain a solvent. The solvent is used for uniformly mixing the polymer (A), the compound (B) and other components to improve the handleability, adjust the viscosity of the composition, and improve the storage stability of the composition. Can be used.

  The solvent is preferably an organic solvent, for example, an aromatic hydrocarbon solvent such as toluene, xylene, or mesitylene; a halogenated hydrocarbon such as methylene chloride, chloroform, hexachlorobenzene, or perfluorohexane; 2-heptanone, 3-heptanone, Ketone solvents such as 4-heptanone and cyclohexanone; acetic acid alkyl ester solvents such as methyl acetate, ethyl acetate and n-butyl acetate; 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropane Amide, 3-hexyloxy-N, N-dimethylpropanamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2- Pyrrolidone, N-pentyl-2-pyrrolidone, N- ( Tokishipuropiru) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, amide-based solvents such as N- cyclohexyl-2-pyrrolidone; and the like.

A solvent may be used individually by 1 type and may use 2 or more types together.
In the composition of the present invention, the content of the solvent is such that the solid content concentration in the composition is usually 1 to 100% by mass, preferably 1 to 80% by mass, more preferably 5 to 60% by mass. is there. Here, solid content means all components other than the said solvent.

<Method for preparing thermosetting resin composition>
The thermosetting resin composition of this invention can be prepared by mixing each component uniformly. Moreover, in order to remove dust, after mixing each component uniformly, you may filter the obtained mixture with a filter.

  The viscosity of the composition of the present invention is usually 50 to 100,000 mPa · s, preferably 500 to 50,000 mPa · s, more preferably 1000 to 20,000 mPa · s. When the viscosity of the composition is within the above range, the composition has excellent retention during film formation such as when a coating film is formed, and the thickness can be easily adjusted, so that a desired resin substrate can be easily formed. Can do.

<Characteristics of the present invention>
By using the thermosetting resin composition of the present invention, a resin substrate having small values of relative dielectric constant (ε _r ) and dielectric loss tangent (tan δ) can be formed. Moreover, the obtained resin substrate has the characteristics of high heat resistance and high chemical resistance.

Hereinafter, the reason for presuming that the characteristics of the present invention are obtained will be described.
The composition of the present invention contains a polymer (A) having a structure (A1) and a compound (B) having a dihydro-1,3-benzoxazine structure. Here, when the structure (A1) contained in the polymer (A) is reacted with the dihydro-1,3-benzoxazine structure contained in the compound (B), an isocyanurate ring is formed (Macromolecules 2012.45.7461). reference). In this reaction, the hydroxyl group that should be generated by the ring-opening reaction of dihydro-1,3-benzoxazine does not occur.

  Hereinafter, an estimated curing reaction mechanism between a polymer represented by the following formula (1) and a compound having a dihydro-1,3-benzoxazine structure represented by the following formula (2) will be described.

まず、トリアジン構造中の電子豊富な窒素原子Ｎ^A1がベンゾオキサジン構造中の電子不足のメチレン炭素原子Ｃ（Ｏ^B1−ＣＨ₂−Ｎ^B1）にアタックし、その際に、電子豊富な酸素原子Ｏ^B1（ＣＨ₂−Ｏ^B1−Ｐｈ）が芳香族環炭素原子（Ａｒ−Ｏ^A1）にアタックする。前記芳香族環炭素原子は、酸素原子Ｏ^A1およびトリアジン構造の電子吸引特性により、電子不足である。

First, the electron-rich nitrogen atom N ^A1 in the triazine structure attacks the electron-deficient methylene carbon atom C (O ^B1 —CH ₂ —N ^B1 ) in the benzoxazine structure. ^B1 (CH ₂ —O ^B1 —Ph) attacks the aromatic ring carbon atom (Ar—O ^A1 ). The aromatic ring carbon atom is deficient in electrons due to the electron withdrawing characteristics of the oxygen atom O ^A1 and the triazine structure.

同様の反応が、トリアジン構造中の他の窒素原子についても起こる。上記反応により、アルキルイソシアヌレート構造およびジフェニルエーテル構造（Ｐｈ−Ｏ^B1−Ｐｈ）が形成される。このようにして、以下の構造が形成されると考えられる。

Similar reactions occur for other nitrogen atoms in the triazine structure. By the above reaction, an alkyl isocyanurate structure and a diphenyl ether structure (Ph—O ^B1 —Ph) are formed. In this way, it is considered that the following structure is formed.

このように重合体（Ａ）および化合物（Ｂ）の硬化反応では、通常のジヒドロベンゾオキサジンの開環反応で生成する水酸基が発生しないことから、比誘電率は小さい。しかも、前記硬化反応で生成するイソシアヌレート環は、双極子モーメントが小さいため、誘電正接も小さい。このため、上記特性を有する樹脂基板が得られると推定される。

In this way, in the curing reaction of the polymer (A) and the compound (B), the hydroxyl group generated by the usual ring-opening reaction of dihydrobenzoxazine does not occur, so the relative dielectric constant is small. Moreover, since the isocyanurate ring produced by the curing reaction has a small dipole moment, the dielectric loss tangent is also small. For this reason, it is estimated that the resin substrate which has the said characteristic is obtained.

[Resin substrate]
The resin substrate of this invention is manufactured from the thermosetting resin composition mentioned above.
Since the resin substrate of the present invention has a structure based on the polymer (A) and the compound (B), the values of relative permittivity (ε _r ) and dielectric loss tangent (tan δ) are small, and the heat resistance and chemical resistance are high. It has the characteristic that it is excellent in. For this reason, the resin substrate of this invention is especially suitable as a resin substrate for circuit boards.

  The resin substrate can be produced by removing the solvent from the composition and then proceeding with a curing reaction between the polymer (A) and the compound (B). Specifically, after forming a coating film of the composition of the present invention on a support, or after impregnating a reinforcing fiber substrate with the composition of the present invention, the solvent is removed as necessary, followed by A resin substrate can be produced by heating at a temperature at which the curing reaction of the polymer (A) and the compound (B) occurs.

  Examples of the method for forming a coating film of the composition include coating methods such as 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, a glass substrate, and a SUS plate. What is necessary is just to determine the thickness of the said coating film suitably with the film thickness of the resin substrate finally obtained, and it is 1-1000 micrometers normally.

  When the reinforcing fiber base material is impregnated with the above-described composition, examples of the reinforcing fiber base material include various glass cloths such as roving cloth, cloth, chopped mat, and surfacing mat; asbestos cloth, metal fiber cloth, and other synthetic or natural materials. Inorganic fiber cloth; Woven or non-woven fabric obtained from liquid crystal fibers such as wholly aromatic polyamide fiber, wholly aromatic polyester fiber, polybenzoxazole fiber; Natural fiber cloth such as cotton cloth, linen cloth, felt; Carbon fiber cloth, kraft paper Natural cellulose base materials such as cloth obtained from cotton paper, paper-glass mixed yarn, and polytetrafluoroethylene porous film. One type of reinforcing fiber base may be used alone, or two or more types may be used in combination.

  Examples of the method for removing the solvent include an air drying method and a heating method. The heating conditions are usually 20 to 150 ° C. and 10 minutes to 5 hours. If necessary, heating may be performed under a nitrogen atmosphere or under reduced pressure. The removal of volatile components may be performed by heating during the curing reaction.

  Curing reaction can be advanced by heating the reinforcing fiber substrate after impregnating the coating film or the composition. The heating conditions are such that the heating temperature is usually 150 ° C. or higher, preferably 150 to 300 ° C., more preferably 180 to 280 ° C., and the heating time is usually 0.1 to 10 hours, preferably 0.2 to 5 hours, more preferably 0.5 to 2 hours. Examples of the heating include a method of sandwiching the reinforcing fiber substrate after impregnating the coating film or the composition with a film and vacuum pressing.

  When a coating film of the above composition is formed on a support, the obtained resin substrate may be peeled off from the support and used as a circuit board resin substrate, or may be used as it is without being peeled off from the support. It may be used as a resin substrate.

When the reinforcing fiber base material is impregnated with the above composition, the content of the reinforcing fiber base material contained in the obtained resin substrate is usually 5 to 95% by mass, preferably 10 to 90% by mass, and more preferably. Is 15 to 85% by mass.
Examples of the shape of the resin substrate include a film shape and a sheet shape.

The thickness of the resin substrate of this invention can be suitably selected according to a desired use, and is 1-250 micrometers normally, Preferably it is 2-150 micrometers. The amount of residual solvent in the resin substrate is preferably 1.2% by mass or less, more preferably 1% by mass or less, with respect to 100% by mass of the resin substrate. When the residual solvent amount is within this range, a resin substrate having a small value of relative dielectric constant (ε _r ) and dielectric loss tangent (tan δ) can be obtained.

The relative dielectric constant (ε _r ) of the resin substrate of the present invention is usually 3.4 or less, preferably 1.8 to 3.2, more preferably 2.0 to 3.0.
The linear expansion coefficient of the resin substrate of the present invention is usually 60 ppm / ° C. or less, preferably 50 ppm / ° C. or less.

  The resin substrate of the present invention is excellent in chemical resistance against acetone, toluene, trichloromethane, dimethylacetamide, dimethyl sulfoxide, hydrochloric acid, and sodium hydroxide aqueous solution.

[Circuit board]
The circuit board of the present invention has the resin substrate of the present invention, and can be obtained, for example, by providing a wiring portion on one or both sides of the resin substrate. The circuit board has a resin substrate with small values of relative permittivity (ε _r ) and dielectric loss tangent (tan δ), has a high propagation speed and a small transmission loss, and therefore can be suitably used in a high frequency region. Since the circuit board of the present invention has the resin substrate, it is useful as a circuit board for precision equipment.

  As a method for forming the wiring portion, for example, copper, indium tin oxide (ITO), polythiophene, and the like on the resin substrate by a laminating method, a metalizing method, a sputtering method, a vapor deposition method, a coating method, a printing method, or the like. Examples thereof include a method of forming a metal layer made of a conductive material such as polyaniline and polypyrrole and patterning the metal layer. In addition, in order to improve the adhesion between the resin substrate and the metal layer before forming the metal layer, the surface of the resin substrate may be modified by plasma treatment or the like, and an adhesive is applied onto the resin substrate. You may keep it.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following description of Examples and the like, “part” is used to mean “part by mass” unless otherwise specified.

1. The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the synthetic polymer were measured by gel permeation chromatography (GPC) method under the following conditions.
Column: “TSKgel αM” manufactured by Tosoh Corporation
"TSKgel α2500" connected in series · Solvent: N-methyl-2-pyrrolidone with lithium bromide and phosphoric acid added · Temperature: 40 ° C
・ Detection method: Refractive index method ・ Standard material: Polystyrene ・ GPC apparatus: manufactured by Tosoh Corporation, apparatus name “HLC-8020-GPC”
The structure of the polymer was measured by ² H-NMR and ¹³ C-NMR analysis. Using an apparatus name “ECP-400P” (manufactured by JEOL), measurement was performed using deuterated chloroform as a deuterated solvent.

[Synthesis Example 1] Synthesis of Polymer (A1-1) Polymer (A1-1) was synthesized according to a synthesis scheme shown in the following formula.

５モルのビスフェノールＦと、０．６３モルのベンジルセチルジメチルアンモニウムクロリド水和物と、１５モルの水酸化ナトリウムを含む水溶液と、５モルの２，４−ジクロロ−６−メトキシ−１，３，５−トリアジンを含むクロロホルム溶液１３０Ｌとを混合し、０℃で２時間攪拌した。この溶液に４−メトキシフェノールを０．１モル加え、０℃で３０分攪拌し反応させた。反応終了後、反応液を水洗し、アセトンに投じて再沈殿させ、濾物を単離した。得られた濾物を乾燥し、重合体（Ａ１−１’）を得た。

An aqueous solution containing 5 moles of bisphenol F, 0.63 moles of benzylcetyldimethylammonium chloride hydrate, 15 moles of sodium hydroxide, 5 moles of 2,4-dichloro-6-methoxy-1,3, The mixture was mixed with 130 L of 5-triazine-containing chloroform solution and stirred at 0 ° C. for 2 hours. 4-Moleic phenol 0.1 mol was added to this solution, and it was made to react by stirring at 0 degreeC for 30 minutes. After completion of the reaction, the reaction solution was washed with water and poured into acetone for reprecipitation, and the filtrate was isolated. The obtained filtrate was dried to obtain a polymer (A1-1 ′).

  3.9 mol of the polymer (A1-1 ′), 41 mol of acetic anhydride, and 21.2 L of 1,1,2,2-tetrachloroethane solution containing 6.1 mol of pyridine were mixed at 45 ° C. And stirred for 2 hours. After completion of the reaction, the reaction solution was poured into a mixed solution of acetone and methanol (volume ratio: acetone / methanol = 2/1) to reprecipitate, and the filtrate was isolated. The obtained filtrate was dried to obtain a polymer (A1-1). Mw of the polymer (A1-1) was 180,000, and Mw / Mn was 2.9. From the NMR spectrum, it was confirmed that the obtained polymer (A1-1) had a structural unit represented by the final formula in the above scheme.

2. Production Examples 1 to 3 of Thermosetting Resin Composition and Resin Substrate In methylene chloride, the polymer (A1-1) obtained in Synthesis Example 1 and dihydro-1,3- The benzoxazine compound (B1-1) was mixed so that the molar ratio of the structure (A1) (triazine ring) and the dihydro-1,3-benzoxazine ring shown in Table 1 was reached, and the solid content concentration was 20 mass. % Thermosetting resin composition was produced.

  In Comparative Example 1, the polymer (A1-1) obtained in Synthesis Example 1 was blended with methylene chloride to produce a thermosetting resin composition having a solid content concentration of 20% by mass. In Comparative Example 2, a dihydro-1,3-benzoxazine compound (B1-1) represented by the following formula was blended with methylene chloride to produce a thermosetting resin composition having a solid content concentration of 20% by mass.

前記熱硬化性樹脂組成物を、ガラス製のシャーレにキャストし、次いで風乾し、樹脂基板前駆体を得た。得られた樹脂基板前駆体２０を、図１に示すように、ポリイミドフィルム カプトン（登録商標）１０に載置し、樹脂基板前駆体２０およびポリイミドフィルム１０を２枚のポリテトラフルオロエチレンフィルム３０で挟み（右側の図では樹脂基板前駆体２０は図示せず）、２４０℃で３０分間、真空プレスし、樹脂基板（サイズ：５０ｍｍ×５０ｍｍ、厚さ：１３０μｍ）を製造した。

The thermosetting resin composition was cast into a glass petri dish and then air-dried to obtain a resin substrate precursor. As shown in FIG. 1, the obtained resin substrate precursor 20 is placed on a polyimide film Kapton (registered trademark) 10, and the resin substrate precursor 20 and the polyimide film 10 are made of two polytetrafluoroethylene films 30. A resin substrate (size: 50 mm × 50 mm, thickness: 130 μm) was manufactured by sandwiching (resin substrate precursor 20 is not shown in the drawing on the right side) and vacuum pressing at 240 ° C. for 30 minutes.

3. Evaluation of Resin Substrate The obtained resin substrates were evaluated as shown in the following 3-1 to 3-5.
The evaluation results are shown in Table 1.

3-1. Glass transition temperature (Tg)
The resin substrate was measured with a DMS tester (Seiko Instruments Inc., apparatus name “EXSTAR6000”) in a temperature range of 23 ° C. to 350 ° C. (temperature increase rate: 5 ° C./min) under measurement conditions of 1 Hz. The temperature of the Tan δ peak at that time was evaluated as the glass transition temperature.

3-2. Thermal decomposition temperature (Td5%)
The thermal decomposition temperature of the resin substrate (5 wt% heat loss temperature, Td 5%) was measured using a DSC measuring device (device name “8230”, manufactured by Rigaku) in a nitrogen atmosphere under a heating rate of 10 ° C./min. Measured under conditions.

3-3. Linear expansion coefficient (CTE)
The linear expansion coefficient of the resin substrate was measured using a TMA measuring device (device name “SSC-5200”, manufactured by Seiko Instruments). The measurement was performed as follows. After raising the temperature to the glass transition point (Tg) of the resin substrate, the linear expansion coefficient was calculated from the gradient at 200 to 100 ° C. when the temperature was lowered at 3 ° C./min.

3-4. Dielectric constant (ε _r ) and dielectric loss tangent (tan δ)
The relative dielectric constant (εr) and dielectric loss tangent (tan δ) of the resin substrate were measured by a perturbation resonance method under the conditions of temperature condition (23 ° C.), relative humidity (45% RH), and frequency condition (1 GHz). For the measurement, a device name “DPS18” manufactured by KEYCOM was used.

3-5. The chemical-resistant resin substrate was immersed in various solvents shown in Table 1 for 24 hours, and the film whose weight change before and after immersion was less than 1% was “◯”, and the film having a weight change of 1% or more was “x”.

表１中の「−」は、未評価であることを示す。

"-" In Table 1 indicates that it has not been evaluated.

10 ... Polyimide film Kapton (registered trademark)
20 ... Precursor of resin substrate 30 ... Polytetrafluoroethylene film

Claims (4)

A polymer (A) having a structural unit represented by the formula (A 2 );
A thermosetting resin composition comprising a compound (B) having a dihydro-1,3-benzoxazine structure.

[In Formula (A2), R ¹ is a hydrogen atom or a hydrocarbon group; R ² is a divalent group represented by Formula (g1). ]

[In Formula (g1) , each R ³ is independently an arylene group having 6 to 20 carbon atoms, or a group in which one or more hydrogen atoms contained in the arylene group are substituted with an alkyl group having 1 to 20 carbon atoms. Yes; R ⁴ is a direct bond or a divalent group; m is 0 or 1; ] The thermosetting resin composition according to claim 1 , wherein the compound (B) is a compound represented by the formula (b1).

[In the formula (b1), R ^B1 is a divalent group, R ^B2 is independently a halogen atom or a hydrocarbon group which may have a substituent, and m and n are each independently It is an integer of 0-4. ] A resin substrate made from a thermosetting resin composition according to claim 1 or 2. A circuit board having the resin substrate according to claim 3 .

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