JP2021077786A - Printed circuit board containing polyphenylene ether - Google Patents

Abstract

To provide a substrate for a printed wiring board that improves the properties of desmear processing.SOLUTION: A substrate for a wiring board includes polyphenylene ether terminally modified with a substituent having a carbon-carbon unsaturated double bond, a cross-linked curing agent having a carbon-carbon unsaturated double bond in the molecule, an epoxy resin, a styrene-ethylene-butylene-styrene block copolymer (SEBS), a flame retardant, and silica, and the amount of resin reduction when immersed in 12% sodium hypochlorite at room temperature for 15 minutes is 1.0% or more.SELECTED DRAWING: None

Description

The present invention relates to a substrate for a printed wiring board containing polyphenylene ether, a printed wiring board containing the same, and the like.

In recent years, with the remarkable progress of information network technology or the expansion of services utilizing information networks, electronic devices are required to have a large amount of information and a high processing speed. In order to meet these demands, substrate materials such as printed wiring boards have low dielectric constant and low dielectric constant in addition to the characteristics such as flame retardancy, heat resistance, and peel strength with copper foil that have been conventionally required. Direct contact is required. For this reason, polyphenylene ether (PPE) having a relatively low dielectric constant and a relatively low dielectric loss tangent is used in a resin composition used as a material for a substrate such as a printed wiring board.

When the printed wiring board is a multi-layer type, holes such as through holes or blind vias are drilled or laser-machined for interlayer connection in the manufacture thereof. In order to remove the resin (smear) remaining inside the hole, a desmear treatment for removing the smear may be performed using a desmear solution such as potassium permanganate (Patent Document 1).

Japanese Patent No. 6215711

The resin composition described in Patent Document 1 contains known PPE and a styrene-butadiene block copolymer and is used for a substrate for a printed wiring board. However, regarding the desmear-treated physical properties, for example, solubility in a desmear solution, There was room for improvement in terms of meeting all the requirements such as surface roughness, peel strength, and smear removal property at the bottom of the via.

Therefore, an object of the present invention is to provide a substrate for a printed wiring board capable of improving the desmear-treated physical characteristics, and an electronic circuit board or a metal-clad laminate formed by using the substrate.

｛式中、
Ｘは、ａ価の任意の連結基であり、ａは２．５以上の数であり、
Ｒ⁵は、各々独立に任意の置換基であり、ｋは各々独立に１〜４の整数であり、そしてｋ個あるＲ⁵のうちの少なくとも１つは、下記式（２）：

（式中、Ｒ¹¹は、各々独立にＣ₁₋₈のアルキル基であり、Ｒ¹²は、各々独立にＣ₁₋₈のアルキレン基であり、ｂは各々独立に０又は１であり、Ｒ¹³は、水素原子、Ｃ₁₋₈のアルキル基又はフェニル基のいずれかを示し、かつ前記アルキル基、アルキレン基、及びフェニル基は、Ｃ₁₋₈の条件を満たす限度で置換基を含んでもよい）
で表される部分構造を含み、
Ｙは、各々独立に下記式（３）：

（式中、Ｒ²¹は、各々独立にＣ₁₋₆の飽和又は不飽和の炭化水素基であり、Ｒ²²は、各々独立に水素原子又はＣ₁₋₆の飽和又は不飽和の炭化水素基であり、かつ前記飽和又は不飽和の炭化水素基はＣ₁₋₆の条件を満たす限度で置換基を有していてもよい）
で表される構造を有する２価の連結基であり、ｎはＹの繰り返し数を表し、各々独立に１〜２００の整数であり、
Ｌは、任意の２価の連結基又は単結合であり、かつ
Ａは、各々独立に、炭素−炭素二重結合、及び／又はエポキシ結合を含有する置換基を示す｝
で表される構造を含むポリフェニレンエーテル成分Ａと、
主鎖末端に下記式（４Ａ）：

｛式中、ｎは０又は１の整数であり、Ｒ^１は、Ｃ_１−８の飽和アルキル基又は不飽和アルキル基であり、そしてＲ^２は水素原子又はＣ_１−８の飽和アルキル基若しくは不飽和アルキル基である｝
で表される官能基を１分子中に平均１．５〜２．５個有し、かつ、数平均分子量が１，０００以上４，５００以下であるポリフェニレンエーテル成分Ｂとを含み、
前記ポリフェニレンエーテルの総量１００質量％を基準として、前記ポリフェニレンエーテル成分Ａの含有量が２質量％以上４０質量％未満であり、かつ前記ポリフェニレンエーテル成分Ｂの含有量が６０質量％超え９８質量％未満である、項目１〜３のいずれか１項に記載のプリント配線板用基板。
（５） 前記架橋剤が、トリアリルシアヌレート、トリアリルイソシアヌレート、ポリブタジエン、及びエポキシ樹脂から成る群より選択される少なくとも１種を含む、項目４に記載のプリント配線板用基板。
（６） 前記架橋剤が、炭素−炭素不飽和二重結合を１分子中に平均２個以上有し、
前記架橋剤の数平均分子量が４，０００以下であり、かつ前記ポリフェニレンエーテル：前記架橋剤の質量比が、２５：７５〜９５：５である、項目４又は５に記載のプリント配線板用基板。
（７） 前記有機過酸化物の１分間半減期温度が１５５℃以上１８５℃以下であり、
前記ポリフェニレンエーテルと前記架橋剤の合計質量１００質量％を基準とし、前記有機過酸化物の含有量が、０．０５質量％以上０．９質量％以下である、項目４〜６のいずれか１項に記載のプリント配線板用基板。
（８） 前記樹脂組成物が、熱可塑性樹脂を更に含み、
前記熱可塑性樹脂が、ビニル芳香族化合物とオレフィン系アルケン化合物とのブロック共重合体、及びその水素添加物、並びにビニル芳香族化合物の単独重合体から成る群より選択される少なくとも１種であり、
前記ブロック共重合体又はその水素添加物における、ビニル芳香族化合物に由来する単位の含有率が２０質量％以上である、項目４〜７のいずれか１項に記載のプリント配線板用基板。
（９） 前記熱可塑性樹脂の重量平均分子量が、３０，０００〜３００，０００である、項目８に記載のプリント配線板用基板。
（１０） 前記熱可塑性樹脂の含有量が、前記ポリフェニレンエーテル及び前記架橋剤の合計１００質量％を基準とし、２質量％以上２０質量％以下である、項目８又は９に記載のプリント配線板用基板。
（１１） 前記樹脂組成物が、難燃剤を更に含み、かつ該難燃剤が、前記樹脂組成物の硬化後に前記樹脂組成物中で他の含有成分と相溶しない、項目４〜１０のいずれか１項に記載のプリント配線板用基板。
（１２） 前記樹脂組成物で形成された電子回路基板材料を含む、項目４〜１１のいずれか１項に記載のプリント配線板用基板。
（１３） 前記樹脂組成物で形成された樹脂フィルムを含む、項目４〜１１のいずれか１項に記載のプリント配線板用基板。
（１４） 前記樹脂フィルムが、硬化している、項目１３に記載のプリント配線板用基板。
（１５） 基材と前記樹脂組成物との複合体であるプリプレグを含む、項目４〜１１のいずれか１項に記載のプリント配線板用基板。
（１６） 前記基材がガラスクロスである、項目１５に記載のプリント配線板用基板。
（１７） 前記プリプレグが、硬化している、項目１５又は１６に記載のプリント配線板用基板。
（１８） 項目１４又は１７に記載のプリント配線板用基板と金属箔との積層体。 As a result of intensive studies, the present inventors have solved the above problems by specifying the amount of resin reduction when the substrate for a printed wiring board containing polyphenylene ether is immersed in a liquid different from the desmear liquid. We found what we could do and came to the completion of the present invention. That is, the present invention is as follows.
(1) A substrate for a printed wiring board containing polyphenylene ether, and the amount of resin reduction when the substrate for a printed wiring board is immersed in sodium hypochlorite having a concentration of 12% at a temperature of 25 ° C. for 15 minutes is 1. A board for a printed wiring board that is 0% or more.
(2) Polyphenylene ether terminally modified with a substituent having a carbon-carbon unsaturated double bond, a crosslinked curing agent having a carbon-carbon unsaturated double bond in the molecule, an epoxy resin, and styrene-ethylene. The substrate for a printed wiring board according to item 1, which contains a -butylene-styrene block copolymer (SEBS), a flame retardant, and silica.
(3) The substrate for a printed wiring board according to item 2, wherein the terminal-modified polyphenylene ether is an acrylate-modified polyphenylene ether having 2.5 functionality or higher.
(4) The printed wiring board substrate contains a resin composition.
The resin composition contains the polyphenylene ether, a cross-linking agent, and an organic peroxide.
The polyphenylene ether has the following formula (1):

{In the formula,
X is an arbitrary linking group of a value, and a is a number of 2.5 or more.
R ⁵ is any substituent independently, k are each independently 1 to 4 integer, and at least one of the k is R ⁵ is represented by the following formula (2):

(In the formula, R ¹¹ is an independently C _1-8 alkyl group, R ¹² is an independent C _1-8 alkylene group, b is independently 0 or 1, and R is R. _{Reference numeral} ¹³ denotes a hydrogen atom, either an alkyl group or a phenyl group of C 1-8, and the alkyl group, the alkylene group, and the phenyl group may contain a substituent to the extent that the condition of _{C 1-8 is satisfied.} Good)
Including the partial structure represented by
Y is independently expressed by the following equation (3):

(In the formula, R ²¹ is an independently saturated or unsaturated hydrocarbon group of _{C 1-6} ^{, and R 22} is an independently saturated or unsaturated hydrocarbon group of _{C 1-6.} And the saturated or unsaturated hydrocarbon group may have a substituent as long as the condition _{of C 1-6 is satisfied).}
It is a divalent linking group having a structure represented by, n represents the number of repetitions of Y, and each is an integer of 1 to 200 independently.
L is any divalent linking group or single bond, and A is a substituent containing a carbon-carbon double bond and / or an epoxy bond, respectively}.
Polyphenylene ether component A containing the structure represented by
The following formula (4A):

{Wherein, n is an integer of 0 or _1, ^{R 1} is a saturated alkyl group or unsaturated alkyl group of _{C 1-8,} and ^{R 2} is or a saturated alkyl group of a hydrogen atom or a _{C 1-8} Unsaturated alkyl group}
It contains a polyphenylene ether component B having an average of 1.5 to 2.5 functional groups represented by (1) and having a number average molecular weight of 1,000 or more and 4,500 or less.
Based on the total amount of 100% by mass of the polyphenylene ether, the content of the polyphenylene ether component A is 2% by mass or more and less than 40% by mass, and the content of the polyphenylene ether component B is more than 60% by mass and less than 98% by mass. The printed wiring board board according to any one of items 1 to 3.
(5) The substrate for a printed wiring board according to item 4, wherein the cross-linking agent contains at least one selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, polybutadiene, and epoxy resin.
(6) The cross-linking agent has an average of two or more carbon-carbon unsaturated double bonds in one molecule.
The substrate for a printed wiring board according to item 4 or 5, wherein the number average molecular weight of the cross-linking agent is 4,000 or less, and the mass ratio of the polyphenylene ether: the cross-linking agent is 25:75 to 95: 5. ..
(7) The one-minute half-life temperature of the organic peroxide is 155 ° C. or higher and 185 ° C. or lower.
Any one of items 4 to 6 in which the content of the organic peroxide is 0.05% by mass or more and 0.9% by mass or less based on the total mass of 100% by mass of the polyphenylene ether and the cross-linking agent. Substrate for printed wiring board described in the section.
(8) The resin composition further contains a thermoplastic resin, and the resin composition further contains a thermoplastic resin.
The thermoplastic resin is at least one selected from the group consisting of a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound, a hydrogenated product thereof, and a homopolymer of the vinyl aromatic compound.
The substrate for a printed wiring board according to any one of items 4 to 7, wherein the content of the unit derived from the vinyl aromatic compound in the block copolymer or its hydrogenated product is 20% by mass or more.
(9) The printed wiring board substrate according to item 8, wherein the thermoplastic resin has a weight average molecular weight of 30,000 to 300,000.
(10) The printed wiring board according to item 8 or 9, wherein the content of the thermoplastic resin is 2% by mass or more and 20% by mass or less based on a total of 100% by mass of the polyphenylene ether and the cross-linking agent. substrate.
(11) Any of items 4 to 10 in which the resin composition further contains a flame retardant, and the flame retardant is incompatible with other contained components in the resin composition after curing of the resin composition. The printed wiring board substrate according to item 1.
(12) The printed wiring board substrate according to any one of items 4 to 11, which comprises an electronic circuit board material formed of the resin composition.
(13) The printed wiring board substrate according to any one of items 4 to 11, which comprises a resin film formed of the resin composition.
(14) The printed wiring board substrate according to item 13, wherein the resin film is cured.
(15) The substrate for a printed wiring board according to any one of items 4 to 11, which comprises a prepreg which is a composite of a base material and the resin composition.
(16) The printed wiring board substrate according to item 15, wherein the substrate is a glass cloth.
(17) The printed wiring board substrate according to item 15 or 16, wherein the prepreg is cured.
(18) A laminate of the printed wiring board substrate according to item 14 or 17 and a metal foil.

According to the present invention, it is possible to improve the desmear-treated physical properties of the printed wiring board substrate, such as the solubility in the desmear solution and the smear removal property at the bottom of the via.

^{It is a 1} H-NMR measurement result of the modified polyphenylene ether 1 (modified PPE1) obtained in Production Example 1.

Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described. Since the following embodiments are aspects of the present invention, the present invention is not limited to the following embodiments. Therefore, the following embodiments can be appropriately modified and implemented within the scope of the gist of the present invention. Further, "~" in the present specification means that the numerical values at both ends thereof are included as the upper limit value and the lower limit value unless otherwise specified. In the present specification, the upper limit value and the lower limit value of the numerical range can be arbitrarily combined.

[Printed circuit board board]
The printed wiring board substrate according to the present embodiment contains polyphenylene ether (PPE) and is used for the printed wiring board. Generally, the printed wiring board refers to a substrate obtained by printing a conductor wiring pattern on the surface or inside of a board made of an insulator, and refers to a state before forming an electric component such as a capacitor. The printed wiring board substrate according to the present embodiment may have a PPE-containing resin composition or a cured product thereof, an insulator, a conductor or a wiring pattern thereof, through holes, blind vias, or the like in at least a part thereof.

The amount of resin reduction when the substrate for a printed wiring board according to the present embodiment is immersed in sodium hypochlorite having a concentration of 12% at a temperature of 25 ° C. for 15 minutes is 1.0% or more. In the art, the desmear solution is usually potassium permanganate or the like. 12% sodium hypochlorite is a different liquid from the desmear liquid used during the desmear treatment of printed wiring board substrates, and in particular 12% sodium hypochlorite accelerates smear removal more than desmear liquid. It can be regarded as a possible liquid (hereinafter, also referred to as "accelerating liquid"). According to the present invention, the composition of the substrate for a printed wiring board capable of improving the solubility in the desmear solution and the residual smear on the via bottom is 1.0% or more when immersed in an acceleration solution different from the desmear solution. Found as a resin reduction.

Immersing the printed wiring board substrate in 12% sodium hypochlorite at a temperature of 25 ° C. for 15 minutes, and the amount of resin reduction of the printed wiring board substrate measured thereby, will be described in detail in Examples. To. Sodium hypochlorite (HClONa) is a sodium salt of hypochlorous acid, which is diluted with water to be alkaline, and can form, for example, an aqueous solution having a concentration of 12% at a temperature of 25 ° C.

The amount of resin reduction when immersed in the accelerating liquid of the printed wiring board substrate described above is preferably 1.1% or more, preferably 1.2% or more, from the viewpoint of improving the desmear-treated physical characteristics. Is more preferable. The upper limit of the resin reduction amount can be, for example, 2.0% or less, or 1.6% or less from the viewpoint of peel strength or surface roughness.

The amount of resin reduction of 1.0% or more can be adjusted according to the desmear treatment conditions, for example, by controlling the structure of PPE, the type or blending ratio of the contained components other than PPE, and the like.

From the viewpoint of the amount of resin reduction of 1.0% or more, PPE preferably has a substituent having a carbon-carbon unsaturated double bond, and more preferably has a substituent having a carbon-carbon unsaturated double bond. It is terminal-modified, more preferably acrylate-terminal modified to be 2.5-functional or higher, and particularly preferably acrylate-terminal-modified to be trifunctional or trifunctional or higher. A PPE terminally modified with a substituent having a carbon-carbon unsaturated bond is immersed in an accelerator solution as compared with a PPE having a hydroxyl group at the terminal (for example, PPE product name “SA90”, Fenton's reagent for fuel cells, etc.). It tends to be easy to control the amount of resin reduction of the printed wiring board substrate to 1.0% or more. Specific examples of PPE terminal-modified with a substituent having a carbon-carbon unsaturated bond are the product name "SA9000" and the like. Specific examples of the acrylate-terminated polyphenylene ether having 2.5 functionality or more include those having a (meth) acrylate terminal group among the polyphenylene ether components A (PPE-A) described later.

From the viewpoint of resin reduction of 1.0% or more, the printed wiring board substrate is prepared by adding a crosslinked curing agent having a carbon-carbon unsaturated double bond in the molecule, an epoxy resin, and hydrogenation in addition to PPE. It preferably contains a styrene-based thermoplastic resin (SEBS), a flame retardant, and silica. A cross-linked curing agent having a carbon-carbon unsaturated double bond in the molecule will be described later as a kind of cross-linking agent. Epoxy resin, SEBS, flame retardant and silica will be described later as additional components of the resin composition constituting the substrate for the printed wiring board.

[Resin composition]
The substrate for a printed wiring board according to the present embodiment preferably contains a PPE-containing resin composition (hereinafter, also referred to as “resin composition”) or is prepared from the resin composition. The resin composition comprises PPE, a cross-linking agent, and an organic peroxide, and PPE has a polyphenylene ether component A (PPE-A) having a unique structure and another unique structure and a number average molecular weight (PPE). Mn) contains a polyphenylene ether component B (PPE-B) of 1,000 or more and 4,500 or less, and the content of PPE-A is 2% by mass or more and 40% by mass based on 100% by mass of the total amount of PPE. It is preferable that the content is less than% and the content of PPE-B is more than 60% by mass and less than 98% by mass. According to such a PPE-containing resin composition, it is possible to adjust the amount of resin reduction (≧ 1.0%) of the substrate for the printed wiring board, improve the electrical characteristics, improve the heat resistance, and improve the toughness. A cured product can be obtained, and the impregnation property into the base material can be excellent.

The number average molecular weight of PPE can be obtained in terms of standard polystyrene from the relational expression between the molecular weight of the standard polystyrene sample measured under the same conditions and the elution time by gel permeation chromatography (GPC) measurement. For example, for each of PPE-A and PPE-B, a specific method for calculating the number average molecular weight can be referred to the method described in Examples.

In addition to (a) PPE, (b) cross-linking agent, and (c) organic peroxide, the resin composition may optionally include (d) a thermoplastic resin, (e) a flame retardant, and (f) a silica filler. And (g) solvent and the like can be further contained. Hereinafter, the elements that can form the resin composition will be described.

[(A) PPE]
PPE contains a phenylene ether unit as a repeating structural unit. The phenylene group in the phenylene ether unit may or may not have a substituent. As used herein, the term "polyphenylene ether" includes dimers, trimmers, oligomers, and polymers. The PPE may also include other building blocks other than the phenylene ether unit. The amount of other structural units is typically 30% or less, 25% or less, 20% or less, 15% or less, 10% or less or 5% or less with respect to the total number of unit structures. However, the amount of other structural units may exceed 30% with respect to the total number of unit structures as long as the effects of the present invention are not impaired.

｛式中、Ｒ²¹、及びＲ²²は、各々独立して、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、及び臭素原子）、置換基を有してもよいアルキル基（例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、及びｔｅｒｔ−ブチル基等のＣ₁₋₆の、直鎖状又は分岐状のアルキル基；シクロヘキシル基等のＣ₆₋₁₀の環状アルキル基）、置換基を有してもよいアルコキシ基（例えば、メトキシ基、エトキシ基、及びブトキシ基等のＣ₁₋₆のアルコキシ基）、置換基を有してもよいアリール基（例えば、フェニル基、及びナフチル基）、置換基を有してもよいアミノ基、置換基を有してもよいニトロ基又は置換基を有してもよいカルボキシル基を表す。｝で表される、繰り返し構造単位を含む。 The PPE is preferably the following formula (3):

{In the formula, R ²¹ and R ²² each independently have a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, and a bromine atom), and an alkyl group (eg, methyl) which may have a substituent. _{C 1-6} linear or branched alkyl groups such as groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, and tert-butyl _{groups; C 6-10} cyclic groups such as cyclohexyl groups. Alkyl group), an alkoxy group which may have a substituent (for example, a C _1-6 alkoxy group such as a methoxy group, an ethoxy group, and a butoxy group), an aryl group which may have a substituent (for example, an aryl group). It represents a phenyl group and a naphthyl group), an amino group which may have a substituent, a nitro group which may have a substituent, or a carboxyl group which may have a substituent. } Includes a repeating structural unit.

More specifically, R ²¹ is an independently saturated or unsaturated hydrocarbon group of _{C 1-6} ^{, and R 22} is an independently saturated or unsaturated hydrocarbon of _{C 1-6.} The hydrocarbon group which is a group and is saturated or unsaturated thereof may contain a substituent as long as the condition _{of C 1-6 is satisfied.}

Specific examples of PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-6). -Phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), 2,6-dimethylphenol and other phenols (eg, 2,3,6-trimethylphenol, A copolymer with 2-methyl-6-butylphenol, etc.), a PPE copolymer obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols, and poly (2,6-dimethyl). -1,4-phenylene ether) or the like is heated in a toluene solvent in the presence of a phenol compound such as bisphenols or trisphenols and an organic peroxide, and redistributed, resulting in a linear structure or branching. It is a PPE having a structure.

で表される構造を含む。 [PPE-A]
PPE-A is expressed by the following formula (1):

Includes the structure represented by.

In the formula (1), X is an arbitrary linking group of a value, and a is a number of 2.5 or more, preferably an integer of 3 or more, and more preferably an integer of 3 to 6. Specific examples of X include, for example, a hydrocarbon group; a hydrocarbon group containing one or more elements selected from nitrogen, phosphorus, silicon or oxygen; or an element such as nitrogen, phosphorus, silicon or these. The group etc. can be mentioned.

で表される部分構造を含む。 Further, R ⁵ is an arbitrary substituent, k is an integer of 1 to 4, and when k is 2 or more, two R ^5s may be linked to form a ring. At least one of the k is R ⁵ is represented by the following formula (2):

Includes the partial structure represented by.

In formula (2), R ¹¹ is an independently C _1-8 alkyl group, R ¹² is an independent C _1-8 alkylene group, b is independently 0 or 1, and R is. _{Reference numeral} ¹³ indicates either a hydrogen atom, a C 1-8 alkyl group, or a phenyl group, and these alkyl group, alkylene group, and phenyl group contain a substituent to the extent that the condition of _{C 1-8 is satisfied.} May be good.

The partial structure represented by the formula (2) preferably has secondary and / or tertiary carbons, for example, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group. , 2,2-Dimethylpropyl group or a structure having a phenyl group at the terminal thereof or the like. The partial structure represented by the formula (2) is preferably directly bonded to the benzene ring to which ^{R 5 in the formula (1) is bonded.} The partial structure represented by formula (2) is attached to the formula (1) 2-position of the benzene ring to which R ⁵ is bonded in, and / or 6-position (ortho to -O-) It is preferable to do so.

の部分は、以下のいずれかの構造：

であることが好ましく、それらの具体例としては、以下の化合物から、末端のフェノール性水酸基の水素を全て取り除いたものが挙げられる：
４，６−ジｔｅｒｔ−ブチルベンゼン１，２，３−トリオール、２，６−ビス（３−ｔｅｒｔ−ブチル−２−ヒドロキシ−５−メチルベンジル）−４−メチルフェノール、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン、２，４，６−トリス（３’，５’−ジ−ｔｅｒｔ−ブチル−４’−ヒドロキシベンジル）メシチレン、ペンタエリトリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオナート］、１，３，５−トリス［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、１，３，５−トリス［［４−（１，１−ジメチルエチル）−３−ヒドロキシ−２，６−ジメチルフェニル］メチル］−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン。 The following of the structures represented by the formula (1):

The part has one of the following structures:

Specific examples thereof include the following compounds from which all the hydrogen of the terminal phenolic hydroxyl group has been removed:
4,6-ditert-butylbenzene 1,2,3-triol, 2,6-bis (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol, 1,1,3- Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,4,6-tris (3', 5'-di-tert-butyl-4'-hydroxybenzyl) mecitylene, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] Methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [[4- (1,1-dimethylethyl) -3-hydroxy- 2,6-Dimethylphenyl] Methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione.

で表される構造を含む２価の連結基（置換基を有するフェノール単位）であり、そして式（１）におけるｎは、Ｙの繰り返し数を表し、各々独立に、０〜２００の整数である。 Y in the formula (1) is independent of each other, and the following formula (3):

It is a divalent linking group (phenolic unit having a substituent) containing a structure represented by, and n in the formula (1) represents the number of repetitions of Y, each independently being an integer of 0 to 200. ..

In formula (3), R ²¹ is an independently _{saturated or unsaturated hydrocarbon group of C 1-6} , preferably a methyl, ethyl group, n-propyl group, vinyl group, allyl group, ethynyl group, propargyl. It is a group or the like, more preferably a methyl group or an ethyl group, and further preferably a methyl group. R ²² is independently a hydrogen atom or _{a saturated or unsaturated hydrocarbon group of C 1-6} , preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or the like, and more preferably a hydrogen atom. It is a methyl group, more preferably a hydrogen atom. Here, the saturated or unsaturated hydrocarbon group may have a substituent as long as the condition _{of C 1-6 is satisfied.}

表される。 A in the formula (1) is a substituent containing a carbon-carbon double bond and / or an epoxy bond. Specific examples of A are notations (4) to (8):

expressed.

In formulas (4) to (8), R ³¹ is independently a hydrogen, a hydroxyl group or a C _1-30 hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydroxyalkyl group. R ³² is an independent C _1-30 hydrocarbon group. R ³³ is independently a hydrogen, a hydroxyl group or a C _1-30 hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group or an isopropenyl group, and among ^{R 33,} At least one is a vinyl group or an isopropenyl group. s and t are integers from 0 to 5.

Specific examples of the hydrocarbon group of R ³¹ include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, and 2-methylbutyl. , 3-Methylbutyl, Amil, Cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl, Cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methyl Pentil, 3-methylpentylene, 4-methylpentylene, 1,1-dimethylbutylene, 2,2-dimethylbutylene, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2 , 3-Dimethylbutyl, n-Heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-Ethylpentyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4 -Dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,4-dimethylpentyl, 2-methyl-3,3-dimethylbutyl, 1-methyl-3,3-dimethylbutyl, 1,2 , 3-trimethylbutyl, 1,3-dimethyl-2-pentyl, 2-isopropylbutyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1-cyclohexylmethyl, 2-ethylcyclopentyl, 3-ethylcyclopentyl , 2,3-Dimethylcyclopentyl, 2,4-dimethylcyclopentyl, 2-methylcyclopentylmethyl, 2-cyclopentylethyl, 1-cyclopentylethyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methyl Heptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1,1- To dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethyl Xyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-di Methylhexyl, 2,5-dimethylhexyl, 1,1-ethylmethylpentyl, 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 4,4-ethylmethylpentyl, 1-ethyl-2- Methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 3-ethyl-1-methylpentyl, 4-ethyl-1-methylpentyl, 2- Ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-2-methylpentyl, 4-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 4-ethyl-3-methyl Pentyl, 1- (2-methylpropyl) butyl, 1- (2-methylpropyl) -2-methylbutyl, 1,1- (2-methylpropyl) ethyl, 1,1- (2-methylpropyl) ethylpropyl, 1,1-diethylpropyl, 2,2-diethylpropyl, 1,1-ethylmethyl-2,2-dimethylpropyl, 2,2-ethylmethyl-1,1-dimethylpropyl, 2-ethyl-1,1- Dimethylbutyl, 2,3-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2-methylcyclohexylmethyl, 3-methylcyclohexylmethyl, 4-Methylcyclohexylmethyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, 2-cyclohexylethyl, 1-cyclohexylethyl, 1-cyclohexyl-2-ethylene, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl , Benzyl, 2-phenylethyl and the like.

The hydrocarbon group of R ³¹ is preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-Methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl , 1-Methylhexyl, 2-Methylhexyl, 3-Methylhexyl, 4-Methylhexyl, 5-Methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 2-methylcyclohexyl , 3-Methylcyclohexyl, 4-Methylcyclohexyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methyl Heptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl and the like, more preferably methyl and ethyl. , N-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl , N-Heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethyl Xyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl and the like, more preferably methyl, ethyl, n-propyl, 2 -Propyl, n-butyl, isobutyl, t-butyl, n-pentyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2- Methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl , Decyl, Isodecyl, Undecyl, Dode Syl, benzyl, etc.

Specific examples of the hydrocarbon group of R ³² include methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,3-trimethylene, 1,1-dimethylethylene, pentamethylene and 1-ethyl. -1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1 , 2-Cyclopentylene, 1,3-Cyclopentylene, 2,2-dimethyl-1,3-propylene, 1,1-dimethyl-1,3-propylene, 3,3-dimethyl-1,3-propylene , Hexamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3-ethyl-1 , 4-Methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methylpentylene, 1,1-dimethyl-1,4 -Butylene, 2,2-dimethyl-1,4-butylene, 3,3-dimethyl-1,4-butylene, 1,2-dimethyl-1,4-butylene, 1,3-dimethyl-1,4-butylene , 2,3-Dimethyl-1,4-butylene, heptamethylene, 1-methyl-1,6-hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 4-methyl -1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1,5-pentylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 1,1 -Dimethyl-1,5-pentylene, 2,2-dimethyl-1,5-pentylene, 3,3-dimethyl-1,5-pentylene, 4,4-dimethyl-1,5-pentylene, 1,2-dimethyl -1,5-pentylene, 1,3-dimethyl-1,5-pentylene, 1,4-dimethyl-1,5-pentylene, 2,3-dimethyl-1,5-pentylene, 2,4-dimethyl-1 , 5-pentylene, 3,4-dimethyl-1,5-pentylene, 2-methyl-3,3-dimethyl-1,4-butylene, 1-methyl-3,3-dimethyl-1,4-butylene, 1 , 2,3-Trimethyl-1,4-butylene and the like.

Specific examples of the hydrocarbon group of R ³² include 1,3-dimethyl-1,4-pentylene, 2-isopropyl-1,4-butylene, 2-methyl-1,4-cyclohexylene, and 3-methyl. -1,4-Cyclohexylene, 4-methyl-1,4-cyclohexylene, 1-cyclohexylmethylene, 2-ethyl-1,3-cyclopentylene, 3-ethyl-1,3-cyclopentylene, 2, 3-Dimethyl-1,3-cyclopentylene, 2,4-dimethyl-1,3-cyclopentylene, 2-methyl-1,3-cyclopentylmethylene, 2-cyclopentylethylene, 1-cyclopentylethylene, octamethylene, 1-Methyl-1,7-Heptylene, 1-Ethyl 1,6-Hexylene, 1-propyl-1,5-Pentylene, 2-Methyl-1,7-Heptylene, 3-Methyl-1,7-Heptylene, 4-Methyl-1,7-Heptylene, 5-Methyl-1,7-Heptylene, 6-Methyl-1,7-Heptylene, 2-Ethyl-1,6-Hexylene, 3-Ethyl-1,6-Hexylene, 4-Ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, 1,1-dimethyl-1,6-hexylene, 2,2-dimethyl-1,6-hexylene, 3,3-dimethyl- 1,6-Hexylene, 4,4-dimethyl-1,6-hexylene, 5,5-dimethyl-1,6-hexylene, 1,2-dimethyl-1,6-hexylene, 1,3-dimethyl-1, 6-Hexylene, 1,4-dimethyl-1,6-hexylene, 1,5-dimethyl-1,6-hexylene, 2,3-dimethyl-1,6-hexylene, 2,4-dimethyl-1,6-- Hexylene, 2,5-dimethyl-1,6-hexylene, 1,1-ethylmethyl-1,5-pentylene, 2,2-ethylmethyl-1,5-pentylene, 3,3-ethylmethyl-1,5 -Pentylene, 4,4-ethylmethyl-1,5-pentylene, 1-ethyl-2-methyl-1,5-pentylene, 1-ethyl-3-methyl-1,5-pentylene, 1-ethyl-4- Methyl-1,5-pentylene, 2-ethyl-1-methyl-1,5-pentylene, 3-ethyl-1-methyl-1,5-pentylene, 4-ethyl-1-methyl-1,5-pentylene, 2-Ethyl-3-methyl-1,5-pentylene, 2-ethyl-4-methyl-1,5-pentylene, 3-ethyl-2-methyl-1,5-pentylene, 4-ethyl-3-methyl- 1,5-Pentylene, 3-Ethyl- Examples thereof include 4-methyl-1,5-pentylene and 4-ethyl-3-methyl-1,5-pentylene.

Further, ^{specific examples of the hydrocarbon group of R 32} include 1- (2-methylpropyl) -1,4-butylene, 1- (2-methylpropyl) -2-methyl-1,4-butylene, 1, 1- (2-methylpropyl) ethylene, 1,1- (2-methylpropyl) ethyl-1,3-propylene, 1,1-diethyl-1,3-propylene, 2,2-diethyl-1,3- Propropylene, 1,1-ethylmethyl-2,2-dimethyl-1,3-propylene, 2,2-ethylmethyl-1,1-dimethyl-1,3-propylene, 2-ethyl-1,1-dimethyl- 1,4-butylene, 2,3-dimethyl-1,4-cyclohexylene, 2,3-dimethyl-1,4-cyclohexylene, 2,5-dimethyl-1,4-cyclohexylene, 2,6-dimethyl -1,4-Cyclohexylene, 3,5-dimethyl-1,4-cyclohexylene, 2-methyl-1,4-cyclohexyl-1-methylene, 3-methyl-1,4-cyclohexyl-1-methylene, 4 -Methyl-1,4-cyclohexyl-1-methylene, 2-ethyl-1,4-cyclohexylene, 3-ethyl-1,4-cyclohexylene, 4-ethyl-1,4-cyclohexylene, 2-cyclohexylethylene , 1-cyclohexylethylene, 1-cyclohexyl-2-ethylene, nonylmethylene, 1-methyl-1,8-octylene, decylmethylene, 1-methyl-1,8-nonylene, undecylmethylene, dodecylmethylene, 1,4 -Phenylene, 1,3-phenylene, 1,2-phenylene, methylene-1,4-phenylene-methylene, ethylene-1,4-phenylene-ethylene and the like can be mentioned.

The hydrocarbon group of R ³² is preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl-. 1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1, 3-Cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3-ethyl-1,4-butylene, 1-Methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methyl-1,5-pentylene, heptamethylylene, 1-methyl-1,6- Hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 4-methyl-1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1,5- Pentylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 2-methyl-1,4-cyclohexylene, 3-methyl-1,4-cyclohexylene, 4-methyl-1, 4-Cyclohexylene, Octamethylene, 1-Methyl-1,7-Heptylene, 3-Methyl-1,7-Heptylene, 4-Methyl-1,7-Heptylene, 2-Methyl-1,7-Heptylene, 5- Methyl-1,7-Heptylene, 6-Methyl-1,7-Heptylene, 2-Ethyl-1,6-Hexylene, 3-Ethyl-1,6-Hexylene, 4-Ethyl-1,6-Hexylene, 5- Ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, dodecylmethylene and the like, more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2. -Propylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4 -Butylene, 2,2-dimethyl-1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, heptamethylylene, octamethylene, 1-methyl-1,7- Heptylene, 3-Methyl-1,7-Heptylene, 4-Methyl-1,7-Heptylene, 2-Methyl-1,7-Heptylene, 5-Methyl Chill-1,7-Heptylene, 6-Methyl-1,7-Heptylene, 2-Ethyl-1,6-Hexylene, 3-Ethyl-1,6-Hexylene, 4-Ethyl-1,6-Hexylene, 5- Ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, dodecylmethylene and the like, more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2. -Prochine, 1,1-dimethylethylene, pentamethylene, 2,2-dimethyl-1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, heptamethylene, Octamethylene, 1-Methyl-1,7-Heptylene, 3-Methyl-1,7-Heptylene, 4-Methyl-1,7-Heptylene, 2-Methyl-1,7-Heptylene, 5-Methyl-1,7 -Heptylene, 6-Methyl-1,7-Heptylene, 2-Ethyl-1,6-Hexylene, 3-Ethyl-1,6-Hexylene, 4-Ethyl-1,6-Hexylene, 5-Ethyl-1,6 -Hexylene, nonylmethylene, decylmethylene, undecylmethylene, dodecylmethylene, etc.

Regarding A in the formulas (1) and (1'), specific examples of the substituent containing a carbon-carbon double bond include a vinyl group, an allyl group, an isopropenyl group, a 1-butenyl group, and a 1-pentenyl group. Group, p-vinylphenyl group, p-isopropenylphenyl group, m-vinylphenyl group, m-isopropenylphenyl group, o-vinylphenyl group, o-isopropenylphenyl group, p-vinylbenzyl group, p-iso Propenylbenzyl group, m-vinylbenzyl group, m-isopropenylbenzyl group, o-vinylbenzyl group, o-isopropenylbenzyl group, p-vinylphenylethenyl group, p-vinylphenylpropenyl group, p-vinylphenylbu Tenyl group, m-vinylphenylethenyl group, m-vinylphenylpropenyl group, m-vinylphenylbutenyl group, o-vinylphenylethenyl group, o-vinylphenylpropenyl group, o-vinylphenylbutenyl group, methacryl Examples thereof include a group, an acrylic group, a 2-ethyl acrylic group and a 2-hydroxymethyl acrylic group.

また、Ｌが任意の２価の連結基である場合、かかるＬの具体例は、例えば、下記式：

｛式中、ａ、Ｒ⁵、ｋ、Ｘ、Ｙ、及びｎは、式（１）の説明において定義したとおりである｝
で表される構造を有する。 L in the formula (1) is an arbitrary divalent linking group or a single bond (direct bond). When L is a single bond, the equation (1) is expressed as the following equation.

Further, when L is an arbitrary divalent linking group, a specific example of such L is, for example, the following formula:

{In the equation, a, R ⁵ , k, X, Y, and n are as defined in the description of equation (1)}
It has a structure represented by.

｛式中、ｎは、Ｙの繰り返し数を表し、０〜２００の整数である｝
で表される分岐構造等が挙げられる。 The structure represented by the formula (1) can have various branched structures depending on the value of the valence a of X. For example, when a = 3 in the equation (1), the following equation:

{In the formula, n represents the number of repetitions of Y and is an integer from 0 to 200}
The branch structure represented by is mentioned.

Specific examples of the structure represented by the formula (1) include the following structures.

In the formula, Z is an arbitrary linking group corresponding to X in the formula (1). R ¹ is a substituent represented by the formula (2), and b is an integer of 1 to 4. The position of R ¹ is not limited, and R ¹ may take any position. Also, if b is 2 or more, each of the plurality of R ¹ is, take the same structure may take a different structure. Examples of R ¹ include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, a 2,2-dimethylpropyl group, or a structure having a phenyl group at the terminal thereof. A is a substituent containing a carbon-carbon double bond and / or an epoxy bond. R ² is a hydrocarbon group having a chain or cyclic structure of hydrogen or C _1-8. When ^{there are a plurality of R 2} , the substituents may be the same or different. Specific examples of R ² include, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, and an n-octyl group. Examples include a group, a phenyl group, a benzyl group, a 2-ethylhexyl group, etc., and from the viewpoint of reactivity during synthesis, hydrogen, methyl, ethyl, n-propyl group, n-butyl group, n-pentyl group, cyclopentyl group and the like. , N-hexyl group, cyclohexyl group, n-heptyl group, and n-octyl group are preferable. However, if the reactivity at the time of synthesis ^{can be controlled by appropriately setting the position of R 2} or the reaction conditions at the time of synthesis, ^{the structure of R 2} is not limited and the condition of _{C 1-8 is satisfied.} Any structure may be used within the range. Z is a hydrocarbon group; a hydrocarbon group selected from nitrogen, phosphorus, silicon, oxygen and containing one or more elements; or an element such as nitrogen, phosphorus, silicon or a group containing these.

式中、Ｒ⁴〜Ｒ¹⁰は、同じでも異なっていてもよく、水素又はＣ₁₋₈の炭化水素基を示す。また、Ｒ³¹〜Ｒ³³は、同じでも異なっていてもよく、水素又はＣ₁₋₆の炭化水素基を示す。ｊ、ｋ、ｌ、及びｍは、同じでも異なっていてもよく、０〜４の整数である。Ｒ⁴〜Ｒ¹⁰の具体例としては、水素、メチル基、エチル基、ｎ−プロピル基、イソプロピルｎ−ブチル基、イソブチル基、ｔ−ブチル基、ｎ−ペンチル基、２−ペンチル基、３−ペンチル基、シクロペンチル基、ｎ−ヘキシル基、２−ヘキシル基、３−ヘキシル基、シクロヘキシル基、ｎ−ヘプチル基、２−ヘプチル基、３−ヘプチル基、ｎ−オクチル基、２−エチルヘキシル基等が挙げられる。Ｒ³¹〜Ｒ³³の具体例としては、水素、メチル基、エチル基、ｎ−プロピル基、イソプロピルｎ−ブチル基、イソブチル基、ｎ−ペンチル基、２−ペンチル基、３−ペンチル基、シクロペンチル基、ｎ−ヘキシル基、２−ヘキシル基、３−ヘキシル基、シクロヘキシル基が挙げられる。 A specific example of the hydrocarbon group as Z is, for example, a structure represented by the following formula.

In the formula, R ^{4 to} R ¹⁰ may be the same or different and represent hydrogen or a hydrocarbon group of _{C 1-8.} Further, R ^{31 to} R ³³ may be the same or different, and represent hydrogen or a hydrocarbon group of _{C 1-6.} j, k, l, and m may be the same or different, and are integers from 0 to 4. Specific examples of R ^{4 to} R ¹⁰ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 2-pentyl group, 3-. Pentyl group, cyclopentyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, n-heptyl group, 2-heptyl group, 3-heptyl group, n-octyl group, 2-ethylhexyl group, etc. Can be mentioned. Specific examples of R ^{31 to} R ³³ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl n-butyl group, isobutyl group, n-pentyl group, 2-pentyl group, 3-pentyl group and cyclopentyl group. , N-hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group and the like.

式中、Ｒ⁴〜Ｒ¹⁰は、同じでも異なっていてもよく、水素又はＣ₁₋₈の炭化水素基を示す。ｊ、ｋ、ｌ、及びｍは、同じでも異なっていてもよく、０〜４の整数である。Ｒ⁴〜Ｒ¹⁰の具体例としては、水素、メチル基、エチル基、ｎ−プロピル基、イソプロピルｎ−ブチル基、イソブチル基、ｔ−ブチル基、ｎ−ペンチル基、２−ペンチル基、３−ペンチル基、シクロペンチル基、ｎ−ヘキシル基、２−ヘキシル基、３−ヘキシル基、シクロヘキシル基、ｎ−ヘプチル基、２−ヘプチル基、３−ヘプチル基、ｎ−オクチル基、２−エチルヘキシル基等が挙げられる。 Further, a specific example of a hydrocarbon group containing one or more elements selected from the group consisting of nitrogen, phosphorus, silicon, and oxygen as Z is represented by the following formula.

In the formula, R ^{4 to} R ¹⁰ may be the same or different and represent hydrogen or a hydrocarbon group of _{C 1-8.} j, k, l, and m may be the same or different, and are integers from 0 to 4. Specific examples of R ^{4 to} R ¹⁰ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 2-pentyl group, 3-. Pentyl group, cyclopentyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, n-heptyl group, 2-heptyl group, 3-heptyl group, n-octyl group, 2-ethylhexyl group, etc. Can be mentioned.

Specific examples of Z as an element such as nitrogen, phosphorus, silicon, or a group containing these elements are as follows.

If the structure of A is specified for the first of the above specific examples, the structure is as shown in the following formula. The same applies to the case of 4 to 6 branches, and R ³¹ , R ³² , s, and t in the following equation are as defined in the specific example of A.

The number average molecular weight of PPE-A described above is preferably 500 to 8,000 in terms of polystyrene-equivalent molecular weight using GPC.
The number average molecular weight of PPE-A is preferably 700 or more, more preferably 900 or more, still more preferably 1,100, from the viewpoint of making it easier to reduce the dielectric constant and the dielectric loss tangent in the cured form of the resin composition. That is all. On the other hand, from the viewpoint of fluidity, compatibility with other components, etc., the number average molecular weight of PPE-A is preferably 7,000 or less, more preferably 6,000 or less, still more preferably 4,500 or less. ..
The modified PPE having the structure of the formula (1) in the present embodiment can be produced, for example, by preparing PPE by a redistribution reaction method using a higher molecular weight PPE polymer and introducing A at the terminal thereof. it can. In the case of producing PPE by a redistribution reaction, it is possible to produce PPE according to the conditions defined in the known reaction conditions. In this case, since the obtained polymer has a lower molecular weight than the raw material PPE, the ratio of the raw material PPE to the polyfunctional phenol compound may be adjusted according to the target molecular weight.

Further, there is no limitation on the method of introducing the substituent A in the formula (1) or (1') into the obtained PPE polymer terminal, for example, the functional groups represented by the formulas (4) to (7). , Various known methods may be employed depending on the type of functional group. For example, the introduction of a functional group having the structure of the formula (4), (6) or (7) can generally follow the formation of an ether bond by the Williamson synthesis method. The introduction of the functional group having the structure of the formula (5) is a reaction of forming an ester bond between the hydroxyl group at the terminal of the PPE polymer and a carboxylic acid having a carbon-carbon double bond (hereinafter referred to as carboxylic acid), and is a known ester bond. A forming method can be used.

PPE-A has high curing reactivity, low dielectric properties, good fluidity and moldability, and excellent heat resistance, so that it can be suitably used as a material for various electric and electronic devices, and in particular, electricity. -It can be suitably used for manufacturing prepregs for electronic parts (printed wiring board base materials, etc.).
In the resin composition, the predetermined PPE-A may be used alone, or a plurality of different PPE-A may be used in combination.

｛式中、ｎは０又は１の整数であり、Ｒ^１は、Ｃ_１−８の飽和アルキル基又は不飽和アルキル基であり、そしてＲ^２は水素原子又はＣ_１−８の飽和アルキル基若しくは不飽和アルキル基である｝
で表される官能基を１分子中に平均１．５〜２．５個有し、かつ、数平均分子量が１，０００以上４，５００以下のＰＰＥである。本明細書では、ＰＰＥ−Ｂの主鎖末端の官能基を「末端官能基」ともいう。
このうち、ＰＰＥの数平均分子量は、本発明の作用効果を奏する観点から、１，０００以上４，５００以下である。このような低分子範囲のＰＰＥ−Ｂを、同じく低分子範囲が好ましいＰＰＥ−Ａとともに含むことで、樹脂組成物の粘度の増大を抑制できるので、樹脂組成物の基材への塗工性の向上を図ることができる。樹脂組成物の基材への塗工性の向上を図ることができることにより、樹脂組成物又はその硬化物に要求される、各種特性の向上も図ることができる。
ここでいう「低分子」とは、例えば、数平均分子量８，０００を超えるＰＰＥと比べて低分子量という趣旨である。従って、ＰＰＥ−Ｂについて「低分子」とは、ＰＰＥ−ＢがＰＰＥ−Ａより低い数平均分子量を有することを限定する趣旨ではなく、同様に、ＰＰＥ−Ａについて「低分子」とは、ＰＰＥ−ＡがＰＰＥ−Ｂより低い数平均分子量を有することを限定する趣旨ではない。ＰＰＥ−Ｂの数平均分子量は、ＰＰＥ−Ａの数平均分子量より高くてよく、また低くてよい。 [PPE-B]
PPE-B has the following formula (4A): at the end of its main chain.

{Wherein, n is an integer of 0 or _1, ^{R 1} is a saturated alkyl group or unsaturated alkyl group of _{C 1-8,} and ^{R 2} is or a saturated alkyl group of a hydrogen atom or a _{C 1-8} Unsaturated alkyl group}
A PPE having an average of 1.5 to 2.5 functional groups represented by (1) and a number average molecular weight of 1,000 or more and 4,500 or less. In the present specification, the functional group at the end of the main chain of PPE-B is also referred to as "terminal functional group".
Of these, the number average molecular weight of PPE is 1,000 or more and 4,500 or less from the viewpoint of exerting the action and effect of the present invention. By including PPE-B having such a low molecular weight range together with PPE-A, which also has a preferable low molecular weight range, an increase in the viscosity of the resin composition can be suppressed, so that the coating property of the resin composition on the substrate can be improved. It can be improved. By improving the coatability of the resin composition on the base material, it is possible to improve various properties required for the resin composition or a cured product thereof.
The term "low molecular weight" as used herein means, for example, that the molecular weight is lower than that of PPE having a number average molecular weight of more than 8,000. Therefore, "small molecule" for PPE-B does not mean to limit that PPE-B has a lower number average molecular weight than PPE-A, and similarly, "small molecule" for PPE-A means PPE. It is not intended to limit -A to having a lower number average molecular weight than PPE-B. The number average molecular weight of PPE-B may be higher or lower than the number average molecular weight of PPE-A.

The number average molecular weight of PPE-B is preferably 1,000 or more, more preferably 1,200 or more, from the viewpoint of making it easier to improve the resin fluidity and various properties required for the cured product of the resin composition. , More preferably 1,500 or more. From the same viewpoint, the number average molecular weight of PPE-B is preferably 4,500 or less, more preferably 4,000 or less, still more preferably 3,500 or less.

In addition, PPE-B can be distinguished from PPE-A.
In the resin composition, the predetermined PPE-B may be used alone, or a plurality of different PPE-Bs may be used in combination.

Then, PPE-B has an average of 1.5 to 2.5 terminal functional groups represented by the formula (4A) in one molecule at the end of the main chain. As a result, it becomes easy to suppress a large increase in the molecular weight, and an increase in the viscosity of the resin composition can be suppressed, so that the coatability of the resin composition to the base material can be improved.

From the viewpoint of further excellent resin fluidity during heat molding, the terminal functional group represented by the formula (4A) is more preferably a methacrylic group and / or an acrylic group.
However, the terminal functional group is a functional group other than a methacryl group or an acrylic group, for example, a benzyl group, an allyl group, a propagyl group, a glycidyl group, an epoxy group, and a vinyl, as long as it does not interfere with the action and effect of the present invention. It may be a functional group such as a benzene group.

[Combination of PPE-A and PPE-B]
In the present embodiment, it is preferable to use the above PPE-A and the above PPE-B in combination from the viewpoint of exerting the effects of the present invention. Rather than simply using multiple PPEs that are different from each other, PPE-A having a unique structure and PPE-B having a unique molecular weight and another unique structure are identified, and then both are identified. The present embodiment pays attention to improving the desmear-treated physical properties by determining the content of each in the resin composition together with the combined use.

In the resin composition, the predetermined PPE-A may be used alone, a plurality of different PPE-A may be used in combination, or the predetermined PPE-B may be used alone. , A plurality of different PPE-Bs may be used in combination, as described above.

Further, the resin composition may contain other PPEs other than PPE-A and PPE-B as long as the effects of the present invention are not impaired. Other PPEs include PPE having a number average molecular weight included in a preferable number average molecular weight range in PPE-A, PPE having a number average molecular weight included in a number average molecular weight range in PPE-B, and a number average molecular weight of 8,000. High molecular weight PPE exceeding the above. Among these, examples of high molecular weight PPE include PPE having an average number of phenolic hydroxyl groups per molecule of 1.2 or more and a number average molecular weight of more than 8,000. However, as described above, the resin composition of the present embodiment does not have to contain other PPE.

When only PPE-A and PPE-B are used as PPE, 100% by mass or 100 parts by mass of PPE in the resin composition corresponds to 100% by mass or 100 parts by mass of PPE-A and PPE-B in total. .. On the other hand, when the resin composition contains PPE-A and PPE other than PPE-B, 100% by mass of PPE or 100 parts by mass of PPE is 100% by mass of PPE-A, PPE-B, and other PPE in total. It corresponds to 100 parts by mass in total.

The resin composition may contain a resin other than PPE as long as it does not interfere with the action and effect of the present invention.

From the viewpoint of exerting the effects of the present invention, the content of PPE-A is 2% by mass or more and less than 40% by mass, and the content of PPE-B exceeds 60% by mass, based on 100% by mass of the total amount of PPE. It is less than 98% by mass.
First, when the lower limit of the content of PPE-A is the above value, the ratio of PPE-A to the resin composition can be secured. On the other hand, if the upper limit of the content of PPE-A is the above value, the ratio of PPE-B to the resin composition can be secured. Similarly, when the lower limit of the content of PPE-B is the above value, the ratio of PPE-B to the resin composition can be secured. On the other hand, if the upper limit of the content of PPE-B is the above value, the ratio of PPE-A to the resin composition can be secured.
Then, by combining PPE-A and PPE-B in the above-mentioned specific ratio, various properties required for the resin composition or the cured product thereof can be improved, and in particular, the cured product of the resin composition can be improved. It is possible to balance the securing of an excellent glass transition temperature (Tg), the improvement of the desmear-treated physical properties, and the improvement of the electrical characteristics (for example, reduction of dielectric loss tangent (Df)).

Therefore, from the viewpoint of exerting the effects of the present invention, the content of PPE-A preferably exceeds 2% by mass, more preferably 3% by mass or more, still more preferably 5% by mass, based on the total amount of PPE of 100% by mass. % Or more. From the same viewpoint, the content of PPE-A is preferably 39% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less.
Further, from the viewpoint of exerting the action and effect of the present invention, the content of PPE-B is preferably 61% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass, based on the total amount of PPE of 100% by mass. % Or more. From the same viewpoint, the content of PPE-B is preferably 97% by mass or less, more preferably less than 97% by mass, and further preferably less than 95% by mass.

When PPE-A and PPE-B are used in combination, PPE-B may be added to PPE-A, or PPE-A may be added to PPE-B. Thus, for example, the equipment may be designed to add PPE-B in the PPE-A or similar PPE production line, or in the PPE-B or similar PPE production line, PPE-A. The equipment may be designed to add. Further, for example, at the stage of preparing a varnish by adding a solvent (organic solvent) to the resin composition, PPE-A and PPE-B may be added at the same time or in the presence of one of them. In any case, when PPE-A and PPE-B are used in combination, it is possible to effectively utilize the PPE-A and PPE-B without major changes from the known production line.

[(B) Crosslinking agent]
In this embodiment, any cross-linking agent capable of causing or promoting a cross-linking reaction can be used. The cross-linking agent preferably has a number average molecular weight of 4,000 or less. When the number average molecular weight of the cross-linking agent is 4,000 or less, an increase in the viscosity of the resin composition can be suppressed, and good resin fluidity during heat molding can be obtained. The number average molecular weight may be any one measured by a general molecular weight measuring method, and specific examples thereof include a value measured by using GPC.

From the viewpoint of the cross-linking reaction, the cross-linking agent is preferably a cross-linking type curing agent having a carbon-carbon unsaturated double bond in one molecule, and an average of two carbon-carbon unsaturated double bonds in one molecule. It is more preferable to have the above, and from the viewpoint of improving the desmear-treated physical properties, a cross-linking agent having an average of two or more carbon-carbon unsaturated double bonds in one molecule (hereinafter, also referred to as (b-1) first cross-linking agent). It is more preferable to use a cross-linking agent having at least two epoxy groups (hereinafter, also referred to as (b-2) second cross-linking agent) in combination. The cross-linking agent may be composed of one kind of compound or two or more kinds of compounds. The "carbon-carbon unsaturated double bond" as used herein means a double bond located at the end branched from the main chain when the cross-linking agent is a polymer or an oligomer. Examples of carbon-carbon unsaturated double bonds include 1,2-vinyl bonds in polybutadiene.

When the number average molecular weight of the cross-linking agent is less than 600, the number of carbon-carbon unsaturated double bonds (average value) per molecule of the cross-linking agent is preferably 2 to 4. When the number average molecular weight of the cross-linking agent is 600 to 1500, the number of carbon-carbon unsaturated double bonds (average value) per molecule of the cross-linking agent is preferably 4 to 26. When the number average molecular weight of the cross-linking agent is 1,500 to 4,000, the number of carbon-carbon unsaturated double bonds (average value) per molecule of the cross-linking agent is preferably 26 to 60. .. When the number average molecular weight of the cross-linking agent is within the above range, the number of carbon-carbon unsaturated double bonds is equal to or more than a specific value, so that the resin composition according to the present embodiment has the reactivity of the cross-linking agent. Further, the crosslink density of the cured product of the resin composition is further improved, and as a result, more excellent heat resistance can be imparted. On the other hand, when the number average molecular weight of the cross-linking agent is within the above range, the number of carbon-carbon unsaturated double bonds is not more than a specific value, so that more excellent resin fluidity can be imparted during heat molding. ..

(B-1) First Cross-linking Agent Examples of the first cross-linking agent include a trialkenyl isocyanurate compound such as triallyl isocyanurate (TAIC), a trialkenyl cyanurate compound such as triallyl cyanurate (TAC), and a molecule. Polyfunctional methacrylate compound having two or more methacryl groups, a polyfunctional acrylate compound having two or more acrylic groups in the molecule, a polyfunctional vinyl compound having two or more vinyl groups in the molecule such as polybutadiene, vinyl in the molecule. Examples thereof include vinylbenzyl compounds such as divinylbenzene having a benzyl group, and polyfunctional maleimide compounds having two or more maleimide groups in molecules such as 4,4'-bismaleimide diphenylmethane. These cross-linking agents may be used alone or in combination of two or more. The first cross-linking agent preferably contains at least one compound selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, and polybutadiene. When the first cross-linking agent contains at least one compound described above, the cross-linking density is further increased during the curing reaction (cross-linking reaction), whereby the heat resistance of the cured product of the resin composition is further increased. It tends to improve.

The mass ratio of PPE: first cross-linking agent is preferably 25:75 to 95: 5 from the viewpoint of balancing the low dielectric constant at the time of curing and the low dielectric loss tangent and the cross-linking density of the cross-linked structure. More preferably, it is 32:68 to 85:15.

(B-2) Second Crosslinking Agent The resin composition preferably contains a second crosslinking agent in addition to the first crosslinking agent from the viewpoint of accelerating the desmear treatment of the substrate for the printed wiring board. As the second cross-linking agent, an epoxy resin is preferable from the viewpoint of a cross-linking network by functional groups remaining in the molecule and from the viewpoint of promoting desmear treatment. Although it is not desired to be bound by the theory, since the benzene ring or the crosslinked portion of the epoxy resin is more easily decomposed by the desmear solution than the benzene ring of PPE, the epoxy resin is used as the second crosslinked agent in addition to the first crosslinked agent. It is considered that the PPE resin composition containing the PPE resin composition can balance the crosslinked structure and the desmear-treated physical properties.

Examples of the epoxy resin include novolak phenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, naphthol aralkyl type epoxy resin and the like. Among these, aromatic type is preferable from the viewpoint of desmear-treated physical properties, and novolak phenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, DGEBA type and the like are more preferable. It can be used alone or in combination of two or more.

The content of the second cross-linking agent is preferably 1 part by mass to 20 parts by mass, and more preferably 2 parts by mass to 18 parts by mass, based on a total of 100 parts by mass of PPE and the second cross-linking agent. .. When the content is 1 part by mass or more, the resin composition of the present embodiment tends to be more excellent in low dielectric constant, low dielectric loss tangent property, and adhesion to the metal leaf when cured. Since the content of the second cross-linking agent is 20 parts by mass or less, the resin composition of the present embodiment tends to have more excellent resin fluidity at the time of heat molding.

[(C) Organic peroxide]
In this embodiment, PPE and any organic peroxide having an ability to accelerate the polymerization reaction of the resin composition containing a cross-linking agent can be used. Examples of the organic peroxide include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 2,5-dimethyl-2,5-di (t-butylper). Oxy) Hexin-3, di-t-butyl peroxide, t-butyl cumyl peroxide, di (2-t-butyl peroxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butyl peroxy) ) Hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) ) Octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, trimethylsilyltriphenylsilyl peroxide and other peroxides. A radical generator such as 2,3-dimethyl-2,3-diphenylbutane can also be used as a reaction initiator for the resin composition. Above all, from the viewpoint of being able to provide a cured product having excellent heat resistance and mechanical properties, a lower dielectric constant, and a dielectric loss tangent, 2,5-dimethyl-2,5-di (t-butyl). Peroxy) hexin-3, di (2-t-butylperoxyisopropyl) benzene, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane are preferred.

The 1-minute half-life temperature of the organic peroxide is preferably 155 ° C. or higher and 185 ° C. or lower, and more preferably 160 ° C. to 180 ° C. or 165 ° C. to 175 ° C. In the present specification, the 1-minute half-life temperature is a temperature at which the time during which the organic peroxide is decomposed and the amount of active oxygen thereof is halved is 1 minute. For the 1-minute half-life temperature, the organic peroxide solution is dissolved in a radical-inactive solvent such as benzene so as to have a concentration of 0.05 mol / L to 0.1 mol / L. It is a value confirmed by the method of thermally decomposing the material in a nitrogen atmosphere.

When the 1-minute half-life temperature of the organic peroxide is 155 ° C. or higher, when the PPE-containing resin composition is subjected to heat-pressurization molding, the reaction with the cross-linking agent is started after the PPE is sufficiently melted. Therefore, it tends to be excellent in moldability. On the other hand, since the one-minute half-life temperature of the organic peroxide is 185 ° C. or lower, the decomposition rate of the organic peroxide under normal heat and pressure molding conditions (for example, the maximum ultimate temperature of 200 ° C.) is sufficient. Since the cross-linking reaction with the cross-linking agent can proceed efficiently and slowly, it is possible to form a cured product having good electrical characteristics (particularly dielectric positive contact).

Examples of organic peroxides having a 1-minute half-life temperature in the range of 155 ° C to 185 ° C include t-hexylperoxyisopropyl monocarbonate (155.0 ° C) and t-butylperoxy-3,5,5. -Trimethylhexanoate (166.0 ° C), t-butylperoxylaurate (159.4 ° C), t-butylperoxyisopropylmonocarbonate (158.8 ° C), t-butylperoxy2-ethylhexylmonocarbonate (161.4 ° C.), t-hexylperoxybenzoate (160.3 ° C.), 2,5-dimethyl-2,5-di (benzoylperoxy) hexane (158.2 ° C.), t-butylperoxyacetate (159.9 ° C), 2,2-di- (t-butylperoxy) butane (159.9 ° C), t-butylperoxybenzoate (166.8 ° C), n-butyl 4,4-di- (T-Butylperoxy) Valerate (172.5 ° C), Di (2-t-Butylperoxyisopropyl) benzene (175.4 ° C), Dicumyl peroxide (175.2 ° C), Di-t-hexylper Oxide (176.7 ° C.), 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (179.8 ° C.), t-butylcumyl peroxide (173.3 ° C.) and the like. Be done.

The content of the organic peroxide is preferably 0.05% by mass or more, more preferably 0.5, from the viewpoint that the reaction rate can be increased based on the total mass of PPE and the cross-linking agent of 100% by mass. It is preferably 5% by mass or more, more preferably 1.5% by mass or more, and more preferably 5% by mass or less, from the viewpoint of being able to keep the dielectric constant and the dielectric tangent of the obtained cured product low. It is preferably 4.5% by mass or less, more preferably 0.9% by mass or less.

[(D) Thermoplastic resin]
The resin composition preferably contains a thermoplastic resin from the viewpoint of the amount of resin reduction in the substrate for the printed wiring board impregnated with the accelerating liquid and the physical characteristics of the desmear treatment.

The thermoplastic resin is water obtained by hydrogenating a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound and a hydrogenated product thereof (a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound). It is preferably at least one selected from the group consisting of hydrogenated block copolymers) and homopolymers of vinyl aromatic compounds. The content of the unit derived from the vinyl aromatic compound of the block copolymer or its hydrogenated product is preferably 20% by mass or more, and can be 99% by mass or less. When the content of the unit derived from the vinyl aromatic compound of the block copolymer or its hydrogenated product is 20% by mass or more, the compatibility with PPE is further improved and the adhesion strength with the metal leaf is further improved. Tend to do.

The vinyl aromatic compound may have an aromatic ring and a vinyl group in the molecule, and examples thereof include styrene. The olefin-based alkene compound may be an alkene having a linear or branched structure in the molecule, and examples thereof include ethylene, propylene, butylene, isobutylene, butadiene, and isoprene. Among these, the thermoplastic resin is a styrene-butadiene block copolymer, a styrene-ethylene-butadiene block copolymer, a styrene-ethylene-butylene block copolymer, and a styrene-from the viewpoint of further excellent compatibility with PPE. Ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene-butylene block copolymer, styrene-isoprene block copolymer, styrene-ethylene-propylene block copolymer, styrene-isobutylene block copolymer; styrene Hydrogen additive of -butadiene block copolymer, hydrogen additive of styrene-ethylene-butadiene block copolymer, hydrogen additive of SEBS, hydrogen additive of styrene-butadiene-butylene block copolymer, styrene-isoprene block It is preferably at least one selected from the group consisting of hydrogenated styrene-based thermoplastic resins such as hydrogenated polymers; and styrene homopolymers (polystyrene: PS), and is a styrene-butadiene block copolymer. , SEBS, hydrogenated SEBS, and PS, more preferably one or more selected from the group.

The hydrogenation rate of the hydrogenated product is not particularly limited, and a carbon-carbon unsaturated double bond derived from an olefin-based alkene compound may partially remain.

The weight average molecular weight of the thermoplastic resin is preferably 30,000 to 300,000, more preferably 31,000 to 290,000. When the weight average molecular weight is 30,000 or more, the resin composition of the present embodiment tends to be more excellent in heat resistance when cured. Since the weight average molecular weight is 300,000 or less, the resin composition of the present embodiment tends to have better resin fluidity at the time of heat molding. The weight average molecular weight is determined by the method described in Examples described later.

The content of the thermoplastic resin is preferably 2 parts by mass to 20 parts by mass based on a total of 100 parts by mass of PPE and the cross-linking agent. When the content is 2 parts by mass or more, the resin composition of the present embodiment tends to be more excellent in low dielectric constant, low dielectric loss tangent property, and adhesion to the metal leaf when cured. When the content is 20 parts by mass or less, the resin composition of the present embodiment tends to have more excellent resin fluidity at the time of heat molding.

[(E) Flame Retardant]
The resin composition preferably contains a flame retardant. From the viewpoint of improving heat resistance, the flame retardant is preferably one that is incompatible with other components in the resin composition after curing. Preferably, the flame retardant is incompatible with the PPE and / or the cross-linking agent in the resin composition after curing of the resin composition. Examples of the flame retardant include inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide and zinc borate; hexabromobenzene, decabromodiphenylethane, 4,4-dibromobiphenyl, ethylenebistetrabromophthalimide and the like. Aromatic bromine compounds of the above; phosphorus-based flame retardants such as resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate and the like can be mentioned. These flame retardants may be used alone or in combination of two or more. Among these, the flame retardant is preferably decabromodiphenylethane from the viewpoint of further excellent low dielectric constant and low dielectric loss tangent when the resin composition is cured.

The content of the flame retardant is not particularly limited, but from the viewpoint of maintaining the flame retardancy of UL standard 94V-0 level, it is preferably 5 parts by mass or more with respect to 100 parts by mass of the total of PPE and the cross-linking agent. It is more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more. Further, from the viewpoint that the dielectric constant of the obtained cured product and the dielectric loss tangent can be kept low, the content of the flame retardant is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and further preferably 40 parts by mass or less. is there.

[(F) Silica filler]
The resin composition may contain a silica filler. Examples of the silica filler include natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, and hollow silica. The content of the silica filler can be 10 to 100 parts by mass with respect to 100 parts by mass of the total of PPE and the cross-linking agent. Further, the silica filler may have its surface treated with a silane coupling agent or the like.

In addition to the above additives, the resin composition may further contain additives such as heat stabilizers, antioxidants, UV absorbers, surfactants and lubricants, solvents and the like. When the resin composition contains a solvent, the resin composition can be in the form of a varnish in which the solid components in the resin composition are dissolved or dispersed in the solvent.

[(G) solvent]
From the viewpoint of solubility, the solvent is preferably an aromatic compound such as toluene or xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, and chloroform. These solvents may be used alone or in combination of two or more.
From the viewpoint of suitably dissolving PPE in the solvent and facilitating the securing of suitable fluidity of the resin composition even at about room temperature, the solvent is preferably a solvent of an aromatic compound such as toluene, for example. , Toluene / methyl ethyl ketone mixed solvent, toluene / cyclohexane mixed solvent, toluene / cyclopentanone mixed solvent and the like are preferable. Further, in the case of the resin composition of the present embodiment, even if the solvent is toluene alone, it dissolves suitably in such a solvent, and by extension, the substrate is excellent in impregnation property. Therefore, a solvent using toluene alone is also preferable.

[Electronic circuit board material]
The printed wiring board substrate according to the present embodiment includes or can be made of an electronic circuit board material formed of the resin composition described above. The electronic circuit board material is preferably formed using the varnish described above. Specifically, the electronic circuit board material is a resin film, an impregnated composite of a base material and a resin (hereinafter, also referred to as "prepreg"), a metal foil with a resin, or a laminate containing at least one of these. ..

[Resin film]
The resin film can be obtained by applying the varnish alone or on a support such as a support film, and then drying and removing the organic solvent in the resin varnish to form a film.

Examples of the support include polyolefins such as polyethylene, polypropylene and polyvinyl chloride; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate; polyimide; metal foils such as copper foil and aluminum foil; and release paper. The support may be subjected to chemical or physical treatment such as matting treatment, corona treatment, and mold release treatment.

The resin film according to this embodiment can be suitably used as an interlayer insulating sheet, an adhesive film, or the like of a laminated body such as a multilayer printed wiring board.

[Prepreg]
The prepreg according to the present embodiment includes a base material and the resin composition of the present embodiment impregnated or coated on the base material. The prepreg can be obtained, for example, by impregnating the varnish with a base material such as glass cloth and then drying and removing the solvent component with a hot air dryer or the like.

As the base material, various glass cloths such as roving cloth, cloth, chopped mat, and surface mat; asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloth; total aromatic polyamide fiber, total aromatic polyester. Woven or non-woven fabrics obtained from liquid crystal fibers such as fibers and polybenzoxazole fibers; natural fiber cloths such as cotton cloth, linen cloth and felt; cloths obtained from carbon fiber cloth, kraft paper, cotton paper, paper-glass mixed fiber yarn, etc. Natural cellulose-based base material; polytetrafluoroethylene porous film and the like can be mentioned. These base materials may be used alone or in combination of two or more.

The proportion of the solid content of the resin composition of the present embodiment in the prepreg is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. When the above ratio is 30% by mass or more, the insulation reliability tends to be further improved when the prepreg is used for an electronic substrate or the like. When the above ratio is 80% by mass or less, mechanical properties such as flexural modulus tend to be further excellent in applications such as electronic substrates.

[Metal-clad laminate (laminate)]
The metal-clad laminate (laminate) according to the present embodiment is obtained by laminating and curing the resin composition of the present embodiment or the prepreg of the present embodiment and a metal foil. The metal-clad laminate preferably has a form in which a cured product of a prepreg (also referred to as a "cured product composite") and a metal foil are laminated and adhered to each other, and is preferably used as a material for an electronic circuit board. .. Examples of the metal foil include aluminum foil and copper foil. Among these, copper foil is preferable because it has low electrical resistance. The cured product composite to be combined with the metal foil may be one sheet or a plurality of sheets, and depending on the application, the metal foil is laminated on one side or both sides of the composite and processed into a laminated plate.

As a method for producing a laminated board, for example, a PPE-containing resin composition and a base material form a composite (for example, the above-mentioned prepreg), which is laminated with a metal leaf, and then the resin composition is cured. , A method of obtaining a laminated board in which a cured product laminated body and a metal foil are laminated can be mentioned. One of the particularly preferable uses of the laminated board is a printed wiring board. In the printed wiring board, it is preferable that at least a part of the metal foil is removed from the metal-clad laminate.

[Printed circuit board]
In the printed wiring board according to the present embodiment, a part of the metal foil is removed from the metal-clad laminate. The printed wiring board of the present embodiment can typically be formed by a method of pressure heating molding using the prepreg of the present embodiment described above. Examples of the base material include the same materials as those described above for the prepreg. In the printed wiring board of the present embodiment, the amount of resin reduction when the substrate is immersed in the accelerating liquid is controlled within the numerical range of the characteristics, so that smears are removed from the holes, and the electrical characteristics (for example, low) are obtained. Excellent dielectric constant and low dielectric loss tangent) and insulation reliability.

Hereinafter, the present embodiment will be described in detail with reference to Examples, but the present invention is not limited to the Examples.

(PPE synthesis reaction)
The following reaction was carried out in an atmosphere of an inert gas. The solvent used in the reaction is a commercially available reagent. The raw materials and reagents used are as follows.

1. 1. Solvent Toluene: A special grade reagent manufactured by Wako Pure Chemical Industries was used as it was.
Methyl ethyl ketone: A special grade reagent manufactured by Wako Pure Chemical Industries was used as it was.
Methanol: A special grade reagent manufactured by Wako Pure Chemical Industries was used as it was.
2. Initiator NOF BMT: NOF products were used as they were.
3. 3. Raw material PPE
S202A (polystyrene equivalent number average molecular weight 16,000): A product manufactured by Asahi Kasei Corporation was used as it was.
Each of S202A has the following structure.

4. Raw material phenol (polyfunctional / bifunctional phenol)
4-1. Phenols 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane having a valence of a (a = 3 to 6) containing a partial structure of the formula (2): ADEKA CORPORATION The product (ADEKA STAB AO-30) was used as it was.

4-2. Phenols of valence 2 not including the partial structure of the formula (2) Bisphenol A: Aldrich reagent product was used as it was.

5. Denatured group raw material Methacrylic anhydride: Aldrich reagent product was used as it was.
Dimethylaminopyridine: The Aldrich reagent product was used as it was.

(Identification and analysis of PPE)
1. 1. Number average molecular weight measurement The number average molecular weight was measured by GPC under chloroform solvent. The number average molecular weight was determined by the polystyrene conversion method based on the calibration curve using standard polystyrene.
2. NMR measurement A sample was dissolved in deuterated chloroform to a concentration of 5% by mass, and NMR measurement was performed. The progress of the reaction was confirmed by the decrease of the hydroxyl group peak from the ratio of the aromatic peak of the polyfunctional phenol unit to the proton peak of the hydroxyl group.
3. 3. Melt Viscosity 200 ml of a 20 mass% methyl ethyl ketone solution of a sample was placed in a beaker, and the viscosity was measured at 25 ° C. and a rotation speed of 30 rpm using a B-type rotational viscometer.

4. Average number of terminal functional groups The average number of terminal functional groups per molecule of PPE was determined by the following method. That is, a sample obtained by adding a tetramethylammonium hydroxide solution to a methylene chloride solution of PPE in accordance with the method described in "Polymer Papers, vol.51, No. 7 (1994), p. 480". The change in absorbance at a wavelength of 318 nm was measured with an ultraviolet-visible absorptiometer. From this measured value, the number of phenolic hydroxyl groups before and after terminal denaturation of PPE was determined. Further, the number of molecules of PPE (number average number of molecules) was determined by using the number average molecular weight of PPE obtained by the above method 1 and the mass of PPE.
From these values, the average number of phenolic hydroxyl groups per molecule of PPE before and after denaturation was determined according to the following mathematical formula (1). :
Average number of phenolic hydroxyl groups per molecule = number of phenolic hydroxyl groups / number average number of molecules ... (1)
For the average number of terminal functional groups after modification, the average number of terminal functional groups after modification was determined according to the following mathematical formula (2). :
Average number of terminal functional groups per molecule = average number of phenolic hydroxyl groups before modification-average number of phenolic hydroxyl groups after modification ... (2)

｛式中、ｌ、ｍ、及びｎは、下記数平均分子量を満たすように任意に選択される数である｝
で表されるような構造を有するＰＰＥ（以下、ＰＰＥ１という）であると確認できた。ＧＰＣ測定の結果、得られたＰＰＥ１のポリスチレン換算での分子量はＭｎ＝１，５００であった。また、ＰＰＥ１の２０％メチルエチルケトン溶媒中での溶液粘度は１２５ｃＰｏｉｓｅであった。 (Manufacturing Example 1)
Synthesis of PPE1 A 500 ml three-necked flask was provided with a three-way cock, and a Dimroth condenser and an isobaric dropping funnel were further installed. After replacing the inside of the flask with nitrogen, 100 g of the raw material PPE S202A, 200 g of toluene, and 12.8 g of 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane as a polyfunctional phenol were added. .. A thermometer was installed in the flask, and the flask was heated to 90 ° C. in an oil bath while stirring with a magnetic stirrer to dissolve the raw material PPE. As an initiator, 37.5 g of a 40% metaxylene solution (Nippon Oil Co., Ltd .: Niper BMT) of a mixture of benzoyl peroxide, benzoyl m-methylbenzoyl peroxide, and m-toluyl peroxide was diluted to 87.5 g of toluene and added dropwise at isobaric pressure. I put it in the funnel. After the temperature in the flask was lowered to 80 ° C., the initiator solution was started dropping into the flask to start the reaction. The initiator was added dropwise over 2 hours, and after the addition, the temperature was raised to 90 ° C. again, and stirring was continued for 4 hours. After the reaction, the polymer solution was added dropwise to methanol, reprecipitated, and then filtered off from the solution to recover the polymer. Then, this was dried under vacuum at 100 ° C. for 3 hours. ¹ It was confirmed by 1 H-NMR that low molecular weight phenol was incorporated into the polymer and the peak of the hydroxyl group disappeared. The ^{polymer obtained from this 1 1} H-NMR measurement result has the following formula:

{In the formula, l, m, and n are numbers arbitrarily selected to satisfy the following number average molecular weights}
It was confirmed that the PPE has a structure as represented by (hereinafter referred to as PPE1). As a result of GPC measurement, the molecular weight of the obtained PPE1 in terms of polystyrene was Mn = 1,500. The solution viscosity of PPE1 in a 20% methyl ethyl ketone solvent was 125 cPoise.

｛式中、ｌ、ｍ、及びｎは、下記数平均分子量を満たすように任意に選択される数である｝
で表されるような構造を有する変性ＰＰＥ（以下、変性ＰＰＥ１という）であると確認できた。
また、ＧＰＣ測定の結果、得られた変性ＰＰＥ１のポリスチレン換算での分子量はＭｎ＝１，６００であった。また、変性ＰＰＥ１の平均末端官能基数は、上記数式（２）に従って、２．５以上であることが算出された。更に、変性ＰＰＥ１の２０％メチルエチルケトン溶媒中での溶液粘度は１３１ｃＰｏｉｓｅであった。 (Synthesis of modified PPE1)
80 g of toluene and 26 g of PPE1 synthesized above were mixed and heated to about 85 ° C. 0.55 g of dimethylaminopyridine was added to the heated mixture. When all the solids seemed to be dissolved, 4.9 g of methacrylic anhydride was gradually added to the lysate. The resulting solution was maintained at 85 ° C. for 3 hours with continuous mixing. The solution was then cooled to room temperature to give a toluene solution of methacrylate-modified PPE.
A part of the solution was collected, dried, and then ¹ H-NMR measurement was carried out. Since the peak derived from the hydroxyl group of PPE had disappeared, it was judged that the reaction was proceeding, and the purification operation was started. 120 g of the toluene solution of the methacrylate-modified PPE was added dropwise to 360 g of methanol vigorously stirred with a magnetic stirrer in a 1 L beaker over 30 minutes. The obtained precipitate was filtered under reduced pressure with a membrane filter and then dried to obtain 38 g of a polymer. ^{The 1} H-NMR measurement result of the dried polymer is shown in FIG. It was confirmed that the peak derived from the hydroxyl group of PPE around 4.5 ppm disappeared and the peak derived from the olefin of the methacrylic group was expressed around 5.75 ppm. In addition, since the peaks derived from dimethylaminopyridine, methacrylic anhydride, and methacrylic acid have almost disappeared by GC measurement, it is judged that the peaks derived from the methacrylic group of NMR are those of the methacrylic group bonded to the PPE terminal. did. From this result, the obtained polymer has the following formula:

{In the formula, l, m, and n are numbers arbitrarily selected to satisfy the following number average molecular weights}
It was confirmed that the modified PPE having the structure represented by (hereinafter referred to as modified PPE1).
Moreover, as a result of GPC measurement, the molecular weight of the obtained modified PPE1 in terms of polystyrene was Mn = 1,600. Further, the average number of terminal functional groups of the modified PPE1 was calculated to be 2.5 or more according to the above formula (2). Further, the solution viscosity of the modified PPE1 in a 20% methyl ethyl ketone solvent was 131 cPoise.

Material PPE used to form the resin composition and its cured product
-Modified polyphenylene ether 1 (modified PPE1) obtained above.
-Terminal methacrylic acid modified PPE "Product name SA9000" (manufactured by Sabic Innovative Plastics, Mn: 2756, number of terminal functional groups: 2.0)
・ "PPE S202A" (manufactured by Asahi Kasei Corporation, Mn: 16,000)

First cross-linking agent-Polybutadiene "Product name B-1000"
(Made by Nippon Soda, Mn: 1200, Tg: -44 ° C)
・ Divinylbenzene

Organic peroxide ・ Bis (1-tert-butylperoxy-1-methylethyl) benzene "Product name Perbutyl P" (manufactured by NOF CORPORATION)

Second cross-linking agent-Epoxy resin (DGEBA type epoxy group equivalent 184-194 Mw370)

Thermoplastic Resin-Hydrogenated Styrene-based Thermoplastic Resin (SEBS) "Product Name Tough Tech N525" (Mw 400,000, Styrene Content 67% by Mass)

Flame Retardant ・ Decabromodiphenylethane "Product name SAYTEX8010" (manufactured by Albemarle)

Silica "CRS1077-EXR4""Fused spherical silica EXR-4" manufactured by Ryumori Co., Ltd. processed by Hosokawa Micron's crushing classifier "CRS1077"

Base material ・ L glass cloth (manufactured by Asahi Schebel, style: 2116)

Evaluation method 1. Number average molecular weight of PPE, weight average molecular weight of thermoplastic resin Using GPC analysis, the number average molecular weight of PPE and the weight average molecular weight of thermoplastic resin were determined by comparison with the elution time of standard polystyrene with known molecular weight. Specifically, after preparing a measurement sample having a sample concentration of 0.2 w / vol% (solvent: chloroform), HLC-8220 GPC (manufactured by Toso Co., Ltd.) is used as a measuring device, and a column: Shodex GPC KF-405L HQ × Measurement was performed under the conditions of 3 (manufactured by Showa Denko Co., Ltd.), eluent: chloroform, injection amount: 20 μL, flow rate: 0.3 mL / min, column temperature: 40 ° C., detector: RI.

2. Accelerated liquid evaluation (resin reduction amount)
Three samples for evaluating desmear solution resistance prepared in Examples or Comparative Examples were immersed in sodium hypochlorite at a temperature of 25 ° C. and a concentration of 12% for 15 minutes before performing the following desmear treatment (3). The weight of each sample before and after being subjected to this series of dipping treatments was measured, the weight reduction rate (%) before and after the dipping treatment was determined, and the average value was determined as the resin reduction amount in the acceleration liquid evaluation.

3. 3. Desmia treatment and its evaluation (3-1) Evaluation of Desmia liquid resistance (resin reduction rate) Three Desmia liquid resistance evaluation samples prepared in Examples or Comparative Examples were used, and each Desmia liquid resistance evaluation sample was used as 45. Immerse in swelling liquid MacDermid 9204 (manufactured by MacDermid Performance Solutions Japan Co., Ltd.) at ℃ for 5 minutes, and then soak in MacDermid 9275 and MacDermid 9276 (manufactured by MacDermid Performance Solutions Japan Co., Ltd.) at 70 ℃ for 10 minutes. Soaked for minutes. Then, the sample was immersed in a neutralizing solution MacDizer 9279 (manufactured by MacDermid Performance Solutions Japan Co., Ltd.) and sulfuric acid (98%) at 45 ° C. for 5 minutes and washed with water. The weight of each desmear liquid resistance evaluation sample before and after the series of desmear treatments was measured, the weight loss rate (%) before and after the desmear treatment was determined, and the average value was determined as the resin reduction amount of the desmear treatment.

(3-2) Measurement of Surface Roughness The surface roughness of the desmear-treated sample was measured according to JIS B0031 or by using "VR-3000" manufactured by KEYENCE CORPORATION.

(3-3) Peel strength The peel strength of the peel strength measuring sample prepared in Example or Comparative Example was measured according to JIS C-6488.

(3-4) Evaluation of Via Bottom Smear The via bottom after desmear treatment was observed by an SEM secondary electron image (× 1,000), and the presence or absence of smear was visually evaluated according to the following criteria.
◎ (Good) Smear remains or is completely removed at a position of 0 to 2 μm inward from the via edge of the bottom.
〇 (Allowable) Smear remains at a position of 2 μm to 5 μm or less inside from the via edge of the bottom.
× (impossible) Smear remains inward from the via edge at the bottom to a position exceeding 5 μm.

<Examples 1 and 2, Comparative Examples 1 and 2>
Preparation of varnish According to the composition shown in Table 1, a thermoplastic resin or a desmear accelerator is optionally added to toluene as a solvent, stirred and dissolved, and then PPE, a flame retardant and silica are added, respectively, and PPE is added. Stirring was continued until the solution was dissolved. Next, a cross-linking agent and an organic peroxide were added to the lysate, and the mixture was sufficiently stirred to obtain a varnish.

Preparation of prepreg After impregnating the obtained varnish with L glass cloth, the excess varnish is scraped off by passing it through a predetermined slit, and dried in a drying oven at 105 ° C. for a predetermined time to remove toluene. I got a prepreg. This prepreg was cut out to a predetermined size.

Preparation of Copper-clad Laminated Plate A predetermined number of obtained prepregs are stacked, and copper foil (manufactured by Furukawa Denki Kogyo Co., Ltd., thickness 35 μm, GTS-MP foil) is laminated on both sides of the stacked prepregs in a vacuum. By pressing, a copper-clad laminate was obtained. ^{In this vacuum press process, first, the condition of a pressure of 10 kg / cm 2} is adopted while heating from room temperature at a heating rate of 3 ° C./min, and then after reaching 130 ° C., the heating rate is 3 ° C./min. The condition of pressure 40 kg / cm ^{2 was adopted while heating.} After the temperature reached 200 ° C., ^{the conditions of a pressure of 40 kg / cm 2} and a time of 60 minutes were adopted while maintaining the temperature at 200 ° C.

Preparation of Copper Foilless Laminated Plate A laminated plate was obtained by removing the copper foil from the copper-clad laminate obtained above by etching.

Preparation of sample for measuring peel strength After peeling off the carrier from the copper foil layer of the copper-clad laminate manufactured as described above, the surface is plated with electrolytic copper plating to a thickness of 10 μm, and a dry film is laminated. The etching resist layer was formed. Then, a circuit pattern for measuring the peeling strength having a width of 0.4 mm was exposed and developed on the etching resist layer to form an etching pattern. Then, the circuit was etched with a copper etching solution and the etching resist was peeled off to prepare a sample for measuring peel strength having a circuit thickness of 10 μm.

Preparation of Sample for Desmia Liquid Resistance Evaluation Two sheets of the varnish prepared above were coated and dried on the surface of a heat-resistant film so as to have a thickness of 100 μm to prepare a resin layer. Then, after the resin layers were bonded to each other by hot working, the heat-resistant film was peeled off and cut into 5 cm × 5 cm squares to prepare a sample for evaluating desmear liquid resistance.

The evaluation and measurement results of each sample are shown in Table 1 below.

Claims (18)

A substrate for a printed wiring board containing polyphenylene ether, and the amount of resin reduction when the substrate for a printed wiring board is immersed in sodium hypochlorite having a concentration of 12% at a temperature of 25 ° C. for 15 minutes is 1.0% or more. A printed wiring board board. Polyphenylene ether terminally modified with a substituent having a carbon-carbon unsaturated double bond, a crosslinked curing agent having a carbon-carbon unsaturated double bond in the molecule, an epoxy resin, and styrene-ethylene-butylene- The substrate for a printed wiring board according to claim 1, which contains a styrene block copolymer (SEBS), a flame retardant, and silica. The substrate for a printed wiring board according to claim 2, wherein the terminal-modified polyphenylene ether is an acrylate-modified polyphenylene ether having 2.5 functionality or higher. The printed wiring board substrate contains a resin composition.
The resin composition contains the polyphenylene ether, a cross-linking agent, and an organic peroxide.
The polyphenylene ether has the following formula (1):

{In the formula,
X is an arbitrary linking group of a value, and a is a number of 2.5 or more.
R ⁵ is any substituent independently, k are each independently 1 to 4 integer, and at least one of the k is R ⁵ is represented by the following formula (2):

(In the formula, R ¹¹ is an independently C _1-8 alkyl group, R ¹² is an independent C _1-8 alkylene group, b is independently 0 or 1, and R is R. _{Reference numeral} ¹³ denotes a hydrogen atom, either an alkyl group or a phenyl group of C 1-8, and the alkyl group, the alkylene group, and the phenyl group may contain a substituent to the extent that the condition of _{C 1-8 is satisfied.} Good)
Including the partial structure represented by
Y is independently expressed by the following equation (3):

(In the formula, R ²¹ is an independently saturated or unsaturated hydrocarbon group of _{C 1-6} ^{, and R 22} is an independently saturated or unsaturated hydrocarbon group of _{C 1-6.} And the saturated or unsaturated hydrocarbon group may have a substituent as long as the condition _{of C 1-6 is satisfied).}
It is a divalent linking group having a structure represented by, n represents the number of repetitions of Y, and each is an integer of 1 to 200 independently.
L is any divalent linking group or single bond, and A is a substituent containing a carbon-carbon double bond and / or an epoxy bond, respectively}.
Polyphenylene ether component A containing the structure represented by
The following formula (4A):

{Wherein, n is an integer of 0 or _1, ^{R 1} is a saturated alkyl group or unsaturated alkyl group of _{C 1-8,} and ^{R 2} is or a saturated alkyl group of a hydrogen atom or a _{C 1-8} Unsaturated alkyl group}
It contains a polyphenylene ether component B having an average of 1.5 to 2.5 functional groups represented by (1) and having a number average molecular weight of 1,000 or more and 4,500 or less.
Based on the total amount of 100% by mass of the polyphenylene ether, the content of the polyphenylene ether component A is 2% by mass or more and less than 40% by mass, and the content of the polyphenylene ether component B is more than 60% by mass and less than 98% by mass. The printed wiring board for the printed wiring board according to any one of claims 1 to 3. The substrate for a printed wiring board according to claim 4, wherein the cross-linking agent contains at least one selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, polybutadiene, and epoxy resin. The cross-linking agent has an average of two or more carbon-carbon unsaturated double bonds in one molecule.
The printed wiring board according to claim 4 or 5, wherein the number average molecular weight of the cross-linking agent is 4,000 or less, and the mass ratio of the polyphenylene ether: the cross-linking agent is 25:75 to 95: 5. substrate. The one-minute half-life temperature of the organic peroxide is 155 ° C or higher and 185 ° C or lower.
Any of claims 4 to 6, wherein the content of the organic peroxide is 0.05% by mass or more and 0.9% by mass or less based on the total mass of 100% by mass of the polyphenylene ether and the cross-linking agent. The printed wiring board substrate according to item 1. The resin composition further comprises a thermoplastic resin.
The thermoplastic resin is at least one selected from the group consisting of a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound, a hydrogenated product thereof, and a homopolymer of the vinyl aromatic compound.
The substrate for a printed wiring board according to any one of claims 4 to 7, wherein the content of the unit derived from the vinyl aromatic compound in the block copolymer or its hydrogenated product is 20% by mass or more. The printed wiring board substrate according to claim 8, wherein the thermoplastic resin has a weight average molecular weight of 30,000 to 300,000. The content of the thermoplastic resin is
The substrate for a printed wiring board according to claim 8 or 9, wherein the total amount of the polyphenylene ether and the cross-linking agent is 100% by mass or more and 2% by mass or more and 20% by mass or less. Any one of claims 4 to 10, wherein the resin composition further contains a flame retardant, and the flame retardant is incompatible with other contained components in the resin composition after curing of the resin composition. Substrate for printed wiring board described in. The substrate for a printed wiring board according to any one of claims 4 to 11, which comprises an electronic circuit board material formed of the resin composition. The substrate for a printed wiring board according to any one of claims 4 to 11, which comprises a resin film formed of the resin composition. The printed circuit board for a printed wiring board according to claim 13, wherein the resin film is cured. The substrate for a printed wiring board according to any one of claims 4 to 11, which comprises a prepreg which is a composite of a base material and the resin composition. The printed circuit board for a printed wiring board according to claim 15, wherein the base material is a glass cloth. The printed wiring board substrate according to claim 15 or 16, wherein the prepreg is cured. A laminate of a printed wiring board substrate according to claim 14 or 17 and a metal foil.

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