JP5539706B2 - Prepreg, metal foil-clad laminate, and printed wiring board - Google Patents

Description

  The present invention relates to a prepreg, a metal-clad foil laminate, and a printed wiring board.

  Printed wiring board materials for electronic devices are required to have excellent chemical and physical characteristics in addition to thermal and electrical characteristics, and epoxy resins have been widely used as such printed wiring board materials. Furthermore, fire safety is also required for printed wiring boards. Therefore, for example, an epoxy resin subjected to a halogenation treatment has been used as the epoxy resin. However, since there is a risk of generating harmful gases during a fire or recycling heating process, there is a growing demand for epoxy resins that do not contain halogen elements for the purpose of reducing environmental impact.

  Furthermore, the use of lead-free solder is rapidly spreading as solder used when soldering to a printed wiring board. However, when using lead-free solder, it is necessary to make it higher than the conventional soldering temperature. For this reason, the printed wiring board material is softened, the expansion rate is increased, and a phenomenon that causes blistering, and a phenomenon that gas is generated due to thermal decomposition of the printed wiring board material, causing blistering. There arises a problem that the circuit of the board is disconnected.

  On the other hand, with rapid development in the field of electrical and electronic materials in recent years, electronic devices are required to be downsized and highly functional, and printed circuit boards are required to be highly integrated. However, the high integration increases the amount of heat generated per unit area, and the temperature applied to the printed wiring board during energization is further increased. Therefore, the temperature difference between energization and de-energization becomes large, and for example, a problem that peeling or cracking occurs occurs.

  In order to solve these problems, a method of improving an epoxy resin which is one of materials constituting a printed wiring board has been proposed. As an example, there is a method of using an epoxy resin and a silicone resin in combination. For example, Patent Documents 1 to 3 propose a method of using an alkoxy group-containing silane-modified epoxy resin obtained by subjecting an epoxy resin and an alkoxysilane partial condensate to a dealcoholization condensation reaction. Patent Document 4 proposes a method of using a varnish containing an epoxy resin and a tetrafunctional alkoxysilane compound.

JP 2002-212262 A JP 2003-037368 A JP 2003-048955 A JP 2004-335661 A

  However, when a laminated board is produced without adding an alkoxyl group-containing epoxy resin described in Patent Documents 1, 2, and 4 without adding a compound that binds the alkoxyl group and the epoxy resin, the epoxy resin and the alkoxysilane The bond formation between the layers becomes insufficient, and the flame retardancy tends to decrease.

  Moreover, when using the alkoxyl group-containing epoxy resin described in Patent Documents 1 and 3, for example, in soldering using lead-free solder, the alkoxyl group contained in the resin causes a dealcoholization reaction, The volatile gas generated by this causes the substrate to swell, the circuit is cut off, and often an electrical short circuit may occur.

  When the alkoxyl group-containing epoxy resin described in Patent Documents 2 and 4 is used, for example, the alkoxyl group contained in the resin undergoes a dealcoholization reaction in the curing step to generate a volatile gas, resulting in voids (bubbles) ). Therefore, when a printed wiring board is used, the voids straddle between a hole for forming a through hole for conducting conduction between layers and a wiring pattern to be insulated, and copper plating deposited on the wall surface of the hole Precipitating into the void tends to cause an electrical short defect between the through hole and the wiring pattern.

  When the mixture of the epoxy resin and the tetrafunctional alkoxysilane described in Patent Document 4 is used, the bond formation between the epoxy resin and the tetrafunctional alkoxysilane can be achieved only by mixing the epoxy resin and the alkoxysilane before the curing step. It tends to be insufficient and cause cracks. As described above, conventionally known techniques do not generate voids during curing, and a printed wiring board material that satisfies all of heat resistance, flame retardancy, and crack resistance has not been obtained.

  The present invention has been made in view of the above circumstances, and provides a prepreg, a metal foil-clad laminate, and a printed wiring board that do not generate voids during curing and have excellent heat resistance, flame retardancy, and crack resistance. The main purpose.

  The present inventor has prepared a prepreg containing a resin composition obtained by mixing a specific alkoxysilane compound at a specific ratio and co-hydrolyzing with an epoxy resin, a curing agent, and a base material. As a result, the present inventors have found that the above problems can be solved, and have made the present invention.

（式中、ｎは０〜３の整数を表し、Ｒ¹は、同一又は異なっていてもよく、水素原子又は有機基を表す。また、Ｒ²は、同一又は異なっていてもよく、水素原子又は炭素数１〜８のアルキル基を表す。）
前記アルコキシシラン化合物は、
（Ｂ）前記式（１）において、ｎは１〜２の整数であり、Ｒ¹として、少なくとも１つの環状エーテル基を有する、少なくとも１種のアルコキシシラン化合物と、
（Ｃ）前記式（１）において、ｎは１〜２の整数であり、Ｒ¹として、少なくとも１つのアリール基を有する、少なくとも１種のアルコキシシラン化合物と、
を含み、かつ、下記式（２）で表される（Ｂ）及び（Ｃ）の混合指標αが、０．００１〜１９である樹脂組成物と、
硬化剤と、
基材と、
を含有するプリプレグ；
混合指標α＝（αｃ）／（αｂ） （２）
（式中、αｂ：（Ｂ）成分の含有量（ｍｏｌ％）、αｃ：（Ｃ）成分の含有量（ｍｏｌ％））。
〔２〕
前記（Ａ）エポキシ樹脂のエポキシ当量は、１００〜６００ｇ／ｅｑであり、かつ、前記（Ａ）エポキシ樹脂の２５℃における粘度は、１０００Ｐａ・ｓ以下である、〔１〕に記載のプリプレグ。
〔３〕
前記（Ａ）エポキシ樹脂は、ポリフェノール化合物のグリシジルエーテル化物である多官能エポキシ樹脂である、〔１〕又は〔２〕に記載のプリプレグ。
〔４〕
前記アルコキシシラン化合物として、
（Ｄ）前記式（１）において、ｎが０である、少なくとも１種のアルコキシシラン化合物を、更に含む〔１〕〜〔３〕のいずれか一項に記載のプリプレグ。
〔５〕
下記式（３）で表される前記アルコキシシラン化合物の混合指標β１が、０．０１〜１．４である、〔１〕〜〔４〕のいずれか一項に記載のプリプレグ；
混合指標β１＝｛（βⁿ²）／（βⁿ⁰＋βⁿ¹）｝ （３）
（式中、
βⁿ²：前記式（１）において、ｎが２であるアルコキシシラン化合物の含有量（ｍｏｌ％）、
βⁿ⁰：前記式（１）において、ｎが０であるアルコキシシラン化合物の含有量（ｍｏｌ％）、
βⁿ¹：前記式（１）において、ｎが１であるアルコキシシラン化合物の含有量（ｍｏｌ％）、
ここで、０≦｛β２＝（βⁿ⁰）／（βⁿ⁰＋βⁿ¹＋βⁿ²）｝≦０．１である）。
〔６〕
下記式（４）で表される、前記（Ａ）エポキシ樹脂と前記アルコキシシラン化合物との混合指標γが、０．０２〜１５である、〔１〕〜〔５〕のいずれか一項に記載のプリプレグ；
混合指標γ＝（γａ）／（γｓ） （４）
（式中、
γａ：エポキシ樹脂の質量（ｇ）、
γｓ：前記式（１）において、ｎが０〜２の整数であるアルコキシシラン化合物の質量（ｇ））
〔７〕
〔１〕〜〔６〕のいずれか一項に記載のプリプレグと、
前記プレプリグに積層された金属箔と、
を少なくとも備える、金属箔張積層板。
〔８〕
〔７〕記載の金属箔張積層板の前記金属箔がエッチング処理された、プリント配線板。 That is, the present invention is as follows.
[1]
(A) A resin composition obtained by cohydrolyzing and condensing an epoxy resin and an alkoxysilane compound represented by the following formula (1),

(In the formula, n represents an integer of 0 to 3, R ¹ may be the same or different and represents a hydrogen atom or an organic group. R ² may be the same or different, and represents a hydrogen atom. Or represents a C1-C8 alkyl group.)
The alkoxysilane compound is
(B) In the formula (1), n is an integer of 1 to 2, and R ¹ has at least one kind of alkoxysilane compound having at least one cyclic ether group;
(C) In the formula (1), n is an integer of 1 to 2, and R ¹ has at least one aryl group having at least one aryl group;
A blending index α of (B) and (C) represented by the following formula (2) is 0.001 to 19, and a resin composition:
A curing agent;
A substrate;
A prepreg containing
Mixing index α = (αc) / (αb) (2)
(Wherein, αb: content of component (B) (mol%), αc: content of component (C) (mol%)).
[2]
The epoxy equivalent of the (A) epoxy resin is 100 to 600 g / eq, and the viscosity of the (A) epoxy resin at 25 ° C. is 1000 Pa · s or less, according to [1].
[3]
The prepreg according to [1] or [2], wherein the (A) epoxy resin is a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound.
[4]
As the alkoxysilane compound,
(D) The prepreg according to any one of [1] to [3], further including at least one alkoxysilane compound in which n is 0 in the formula (1).
[5]
The prepreg according to any one of [1] to [4], wherein a mixing index β1 of the alkoxysilane compound represented by the following formula (3) is 0.01 to 1.4;
Mixing index β1 = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
(Where
β ⁿ² : the content (mol%) of the alkoxysilane compound in which n is 2 in the formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n is 0 in the formula (1),
β ⁿ¹ : the content (mol%) of the alkoxysilane compound in which n is 1 in the formula (1),
Here, 0 ≦ {β2 = (β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1).
[6]
The mixing index γ of the (A) epoxy resin and the alkoxysilane compound represented by the following formula (4) is 0.02 to 15; [1] to [5] Prepregs;
Mixing index γ = (γa) / (γs) (4)
(Where
γa: mass of epoxy resin (g),
γs: the mass (g) of the alkoxysilane compound in which n is an integer of 0 to 2 in the formula (1)
[7]
The prepreg according to any one of [1] to [6],
A metal foil laminated on the prepreg;
A metal foil-clad laminate.
[8]
[7] A printed wiring board obtained by etching the metal foil of the metal foil-clad laminate.

  ADVANTAGE OF THE INVENTION According to this invention, the void at the time of hardening does not generate | occur | produce and can provide the prepreg, the metal foil tension laminated board, and printed wiring board which were excellent in heat resistance, a flame retardance, and crack resistance.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

（式中、ｎは０〜３の整数を表し、Ｒ¹は、同一又は異なっていてもよく、水素原子又は有機基を表す。また、Ｒ²は、同一又は異なっていてもよく、水素原子又は炭素数１〜８のアルキル基を表す。）
前記アルコキシシラン化合物は、
（Ｂ）ｎは１〜２の整数を表し、Ｒ¹として、少なくとも１つの環状エーテル基を有する、少なくとも１種のアルコキシシラン化合物と、
（Ｃ）ｎは１〜２の整数を表し、Ｒ¹として、少なくとも１つのアリール基を有する、少なくとも１種のアルコキシシラン化合物と、
を含み、かつ、下記式（２）で表される（Ｂ）及び（Ｃ）の混合指標αが、０．００１〜１９である樹脂組成物と、
硬化剤と
基材と
を含有するプレプリグ；
混合指標α＝（αｃ）／（αｂ） （２）
（式（２）中、αｂ：前記（Ｂ）成分の含有量（ｍｏｌ％）、αｃ：前記（Ｃ）成分の含有量（ｍｏｌ％））、である。 (Prepreg)
The prepreg of this embodiment is
(A) A resin composition obtained by cohydrolyzing and condensing an epoxy resin and an alkoxysilane compound represented by the following formula (1),

(In the formula, n represents an integer of 0 to 3, R ¹ may be the same or different and represents a hydrogen atom or an organic group. R ² may be the same or different, and represents a hydrogen atom. Or represents a C1-C8 alkyl group.)
The alkoxysilane compound is
(B) n represents an integer of 1 to 2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) n represents an integer of 1 to 2, and as R ¹ , at least one alkoxysilane compound having at least one aryl group;
A blending index α of (B) and (C) represented by the following formula (2) is 0.001 to 19, and a resin composition:
A prepreg containing a curing agent and a substrate;
Mixing index α = (αc) / (αb) (2)
(In the formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)).

  The present inventor has disclosed a prepreg containing a resin composition obtained by cohydrolytic condensation of an epoxy resin and a specific alkoxysilane compound, a curing agent, and a base material, and a metal foil molded thereby. Stretched laminates and printed wiring boards have excellent reliability that does not cause short-circuit failure due to voids, and are further superior in heat resistance, flame retardancy, and crack resistance. I found that I can achieve.

((A) Epoxy resin)
The (A) epoxy resin in the present embodiment refers to a compound having an oxirane ring, usually two or more oxirane rings in the molecule, excluding an alkoxysilane compound and a condensate thereof described later, and satisfying the above requirements. If it is, it will not be specifically limited. These may be used alone or in combination.

The epoxy equivalent (WPE) of the epoxy resin is preferably 100 to 600 g / eq, more preferably 100 to 500 g / eq, and still more preferably 100 to 300 g / eq. Depending on the compositional balance of the epoxy resin and the alkoxysilane compound represented by the formula (1), the epoxy equivalent (WPE) may be 100 g / eq or more to leave unreacted cyclic ether groups. Since it can suppress, a flame retardance may be further excellent and it exists in the tendency for the fluidity | liquidity of a resin composition to improve and to improve productivity by making 600 g / eq below.
Furthermore, the epoxy equivalent of the epoxy resin is particularly preferably from 100 to 300 g / eq, since the heat resistance when the metal foil-clad laminate and the printed wiring board are further improved.

  The epoxy resin preferably has a viscosity at 25 ° C. of 1000 Pa · s or less, more preferably 500 Pa · s or less, and still more preferably 100 Pa · s or less. When the viscosity of the epoxy resin at 25 ° C. is 1000 Pa · s or less, the fluidity as a liquid is improved and the compatibility with the alkoxysilane compound described later tends to be improved. Further, when the viscosity at 25 ° C. is 500 Pa · s or less, the efficiency of impregnation into the base material is improved, so that the productivity tends to be improved, and more preferably 100 Pa · s or less.

  The type of the epoxy resin is not particularly limited. For example, a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound, an alicyclic epoxy resin, a polyfunctional epoxy resin that is a glycidyl etherified product of various novolak resins, or an aromatic epoxy resin. Nuclei hydrides, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, and the like. Among them, a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound is preferable from the viewpoint of easy availability and good crack resistance of the target metal-clad laminate of the present embodiment and printed wiring board. Of these, a type having a bisphenol A skeleton is more preferable. Moreover, these epoxy resins may be used alone or in combination.

(Polyfunctional epoxy resin)
The polyfunctional epoxy resin which is a glycidyl etherified product of a polyphenol compound is not particularly limited, and specifically, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethyl Bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl)- 2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene -Bis (3-methyl-6-tert-butyl) Ruphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, 2,6-di (t-butyl) hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1-di (4-hydroxyphenyl) fluorene, etc. Examples thereof include phenols having a fluorene skeleton, polyfunctional epoxy resins which are glycidyl etherified products of polyphenol compounds of phenolized polybutadiene.

  Among the above, bisphenol has many types that are excellent in fluidity and are commercially available and can be obtained at low cost, and the metal foil-clad laminate of the present embodiment and the printed wiring board tend to be excellent in heat resistance. A polyfunctional epoxy resin which is a glycidyl etherified product of a phenol having an A skeleton or a bisphenol F skeleton is preferable. Among these, a polyfunctional epoxy resin which is a glycidyl etherified product of phenols having a bisphenol A skeleton is particularly preferable.

  A typical example of a polyfunctional epoxy resin which is a glycidyl etherified product of phenols having a bisphenol skeleton is shown below.

  When a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound is used as the epoxy resin, these repeating units (n in the chemical formula showing the above representative examples) are not particularly limited, but preferably Is less than 20, more preferably 0.001 to 10, and still more preferably 0.01 to 2. When the repeating unit is 0.001 or more, the epoxy resin and the alkoxysilane compound react with each other and the heat resistance tends to be improved. By setting the number to 20 or less, the fluidity of the epoxy resin is improved, and the alkoxysilane. The compatibility with the compound tends to be improved. From the viewpoint of the balance between heat resistance and fluidity described above, the repeating unit is particularly preferably from 0.01 to 2.

(Alicyclic epoxy resin)
The alicyclic epoxy resin is not particularly limited as long as it is an epoxy resin having an alicyclic epoxy group, and examples thereof include an epoxy resin having a cyclohexene oxide group, a tricyclodecene oxide group, a cyclopentene oxide group, and the like. Can be mentioned.

  Specific examples of the alicyclic epoxy resin include 4-vinyl epoxycyclohexane, dioctyl epoxyhexahydrophthalate, and di-2-ethylhexyl epoxyhexahydrophthalate as monofunctional alicyclic epoxy compounds. Examples of the bifunctional alicyclic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4 -Epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) Methyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate , Methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), 1,2,8, 9-diepoxy limonene. Examples of the polyfunctional alicyclic epoxy compound include 1,2-epoxy-4- (2-oxiranyl) cyclohexene adduct of 2,2-bis (hydroxymethyl) -1-butanol. Examples of the polyfunctional alicyclic epoxy compound include Epolide GT401 and EHPE3150 (manufactured by Daicel Chemical Industries). Among these, a bifunctional alicyclic epoxy compound is preferable from the viewpoint of availability and reactivity. Specifically, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate is particularly preferable.

  Typical examples of the alicyclic epoxy resin are shown below.

(Polyfunctional epoxy resin that is glycidyl etherified product of novolak resin)
The polyfunctional epoxy resin that is a glycidyl etherified product of novolak resin is not particularly limited, and examples thereof include phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthol. Glycidyl etherification products of various novolac resins such as novolak resins made from various phenols such as phenols, xylylene skeleton-containing phenol novolak resins, dicyclopentadiene skeleton-containing phenol novolak resins, biphenyl skeleton-containing phenol novolak resins, and fluorene skeleton-containing phenol novolak resins. Etc. Among these, from the viewpoint of easy availability, a novolak resin using phenol or cresols as a raw material is preferable.

  A typical example of a polyfunctional epoxy resin which is a glycidyl etherified product of a novolak resin is shown below.

(Nuclear hydride of aromatic epoxy resin)
The nuclear hydride of the aromatic epoxy resin is not particularly limited. For example, a glycidyl etherified product of a phenol compound (bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, etc.) or various phenols ( Phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.) or hydrogenated glycidyl ethers of novolac resins Is mentioned.

(Heterocyclic epoxy resin)
The heterocyclic epoxy resin is not particularly limited, and examples thereof include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.

(Glycidyl ester epoxy resin)
The glycidyl ester-based epoxy resin is not particularly limited, and examples thereof include epoxy resins composed of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.

(Glycidylamine epoxy resin)
The glycidylamine epoxy resin is not particularly limited. For example, an epoxy resin obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivative, and diaminomethylbenzene derivative. Etc.

(Epoxy resin obtained by glycidylation of halogenated phenols)
Epoxy resins obtained by glycidylation of halogenated phenols are not particularly limited. For example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated Examples thereof include epoxy resins obtained by glycidyl etherification of halogenated phenols such as bisphenol S and chlorinated bisphenol A.

  The epoxy resin mentioned above can use a polyol together. The polyol is not particularly limited as long as it is a compound having 2 or more hydroxyl groups in the molecule. For example, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,2-hexanediol, 1,6- Examples include hexanediol.

(Alkoxysilane compound)
The alkoxysilane compound in this embodiment is a silicon compound having 1 to 4 alkoxyl groups, and is represented by the following formula (1).

In formula (1), n represents an integer of 0 to 3, and R ¹ may be the same or different and each represents a hydrogen atom or an organic group. R ² may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

R ¹ in the formula (1) may be the same or different in a plurality of cases and represents a hydrogen atom or an organic group, and is not particularly limited, but examples of the organic group include an organic group having a cyclic ether group described later, aryl In addition to the organic group having a group, examples include an organic group having an alkyl group, a vinyl group, a methacryl group, a mercapto group, and an isocyanate group. Among them, an alkyl group is preferable because it can be obtained at a low cost.

  Here, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group (n-butyl, i-butyl, t-butyl, sec-butyl), and a pentyl group (n -Pentyl, i-pentyl, neopentyl, etc.), hexyl group (n-hexyl, i-hexyl, etc.), heptyl (n-heptyl, i-heptyl, etc.), octyl group (n-octyl, i-octyl, t-octyl) Etc.), nonyl (n-nonyl, i-nonyl etc.), decyl group (n-decyl, i-decyl etc.), dodecyl group (n-dodecyl, i-dodecyl etc.). These may be either linear or branched alkyl groups.

  Among these, since it is easily available, an alkyl group having 10 or less carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group. Is more preferable. In addition, hydrogen atoms or a part or all of the main chain skeleton of these alkyl groups are ether groups, ester groups, carbonyl groups, siloxane groups, halogen atoms such as fluorine, methacryl groups, acrylic groups, mercapto groups, amino groups, It may be substituted with at least one group selected from the group consisting of hydroxyl groups.

Also, R ² in the formula (1) described above, if a plurality, may be identical or different, represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ² is not particularly limited as long as it satisfies the above requirements, but is preferably a methyl group or an ethyl group because alcohols generated by the hydrolysis reaction can be easily removed.

((B) component)
The component (B) of the alkoxysilane compound represented by the formula (1), in the formula (1), n is an integer of 1 to 2, and R ¹ has at least one cyclic ether group. It is a kind of alkoxysilane compound.

  The cyclic ether group refers to an organic group having an ether in which carbon of a cyclic hydrocarbon is substituted with oxygen, and usually means a cyclic ether group having a 3- to 6-membered ring structure. Among them, a 3-membered or 4-membered cyclic ether group having a large ring strain energy and high reactivity is preferable, and a 3-membered ether group is particularly preferable.

  Specific examples of the cyclic ether group include, for example, a glycidoxyalkyl group having oxyglycidyl groups having 4 or less carbon atoms such as β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl, and the like, glycidyl Group, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4 epoxyepoxycyclohexyl) ) Alkyl substituted with a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group such as propyl group, β- (3,4-epoxycyclohexyl) butyl group, β- (3,4-epoxycyclohexyl) pentyl group Groups and the like.

  Among the above, from the viewpoint of reactivity, oxyglycidyl group to C1-C3 alkyl group such as β-glycidoxyethyl group, γ-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, etc. A glycidoxyalkyl group to which is bonded, or an alkyl group having 3 or less carbon atoms substituted with a C5-C8 cycloalkyl group having an oxirane group is preferred.

  Specific examples of the component (B) include, for example, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2,3 -Epoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 2- (3,4-epoxy Hexyl) ethyl triethoxysilane, 2,3-epoxypropyl trimethoxysilane, 2,3-epoxy propyl triethoxy silane, and the like. Among these, from the viewpoint of easy availability and compatibility with epoxy resin, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane is preferred. These may be used alone or in combination.

((C) component)
The component (C) of the alkoxysilane compound represented by the formula (1) is at least one kind in which n is an integer of 1 to 2 and R ¹ has at least one aryl group in the formula (1). This is an alkoxysilane compound.

  An aryl group refers to a functional group or substituent derived from an aromatic hydrocarbon (simple aromatic ring or polycyclic aromatic hydrocarbon). The aryl group is not particularly limited as long as it matches this, but in consideration of steric hindrance in the higher order structure, a phenyl group, a benzyl group, and the like are preferable.

  Specific examples of the component (C) include, for example, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, phenyltriethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, dimethoxydiphenylsilane, diphenyldiethoxysilane, phenyl Examples include trimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane. Among these, phenyltriethoxysilane and phenyltrimethoxysilane are preferable from the viewpoint of availability and fluidity. These may be used alone or in combination.

“(B) at least one alkoxysilane compound in which n is an integer of 1 to 2 and R ¹ has at least one cyclic ether group in formula (1)”, and “(C) formula In (1), the mixing ratio of “at least one alkoxysilane compound having n as an integer of 1 to 2 and having at least one aryl group as R ¹ ” is calculated by the following formula (2). It is represented by a mixing index α.
Mixing index α = (αc) / (αb) (2)
In formula (2),
αb: content of component (B) (mol%),
αc: represents the content (mol%) of the component (C).

  In the present embodiment, the mixing index α is set in the range of 0.001 to 19. When the mixing index α is less than 0.001, the heat resistance and flame retardancy tend to deteriorate when a metal foil-clad laminate and a printed wiring board are used. If it exceeds 19, the fluidity of the resin composition decreases and the compatibility with the epoxy resin tends to deteriorate, and the heat resistance and crack resistance when used as a metal foil-clad wiring board and a printed wiring board are It tends to get worse. In particular, when high heat resistance, flame retardancy, and crack resistance are required, the mixing index α is more preferably 0.2 to 5, and further preferably 0.3 to 2.

((D) component)
In addition to the components (A) to (C) described above, the resin composition in the present embodiment includes n as the component (D), where n represents the number of R ¹ in the above formula (1), that is, ( An alkoxysilane compound having four OR ² ) may be further cohydrolyzed and condensed. Examples of the component (D) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and tetraphenoxysilane. Among these, tetramethoxysilane and tetraethoxysilane are preferable because they are relatively inexpensive. These may be used alone or in combination.

(Other alkoxysilane compounds)
In the resin composition in the present embodiment, the alkoxysilane compound represented by the formula (1) other than the components (B) to (D) described above may be further cohydrolyzed and condensed. Examples of such compounds include dimethyldimethoxysilane, dimethylethoxysilane, hydroxymethyltrimethylsilane, methoxytrimethylsilane, methyltrimethoxysilane, mercaptomethyltrimethoxysilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, bis (2-chloro Ethoxy) methylsilane, ethoxytrimethylsilane, diethoxymethylsilane, ethyltriethoxysilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, ethoxydimethylvinylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxymethylsilane , Methyltris (ethylmethylketoxime) silane, trimethylpropoxysilane, trimethoxyisopropoxysilane, diethoxydi Tilsilane, 3- [dimethoxy (methyl) silyl] propane-1-thiol, trimethoxy (propyl) silane, (3-mercaptopropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, diethoxymethylvinylsilane, butoxytrimethylsilane, Butyltrimethoxysilane, methyltriethoxysilane, methoxyltriethoxysilane, triethoxyvinylsilane, diethoxydiethylsilane, dimethoxyldipropoxysilane, ethyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane Allyltriethoxysilane, 3-bromopropyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, hexyloxytrimethylsilane, propyltriethoxysilane, Xyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3-ureidopropyltriethoxysilane, Methoxytripropylsilane, dibutoxydimethylsilane, methyltripropoxysilane, methyltriisopropoxysilane, octyloxytrimethylsilane, pentyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, hexyltriethoxysilane, Examples include 3-methacryloxypropyltriethoxysilane, octyltriethoxysilane, dodecyloxytrimethylsilane, and diethoxydodecylmethylsilane.

In this embodiment, the mixing ratio of the “alkoxysilane compound in which n is 2”, the “alkoxysilane compound in which n is 1”, and the “alkoxysilane compound in which n is 0” of the alkoxysilane compound is represented by the following formula ( It is represented by the mixture index β1 calculated in 3).
Mixing index β1 = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
In the above formula (3),
β ⁿ² : the content (mol%) of the alkoxysilane compound in which n is 2 in formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n is 0 in formula (1),
β ⁿ¹ : content (mol%) of an alkoxysilane compound in which n is 1 in formula (1),
And 0 ≦ {β2 = (β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1.

  In the resin composition in the present embodiment, the mixing index β1 is preferably 0.01 to 1.4, more preferably 0.03 to 1.2, and still more preferably 0.05 to 1.0. By setting the mixing index β1 to 0.01 or more, the fluidity of the resin composition is improved, and the substrate can be more efficiently impregnated with the mixture of the resin composition and the curing agent. Tend to be. Moreover, when the mixture index β1 is set to 1.4 or less, the heat resistance and crack resistance tend to be improved when the metal foil-clad laminate and the printed wiring board are obtained. In particular, in order to improve the balance of fluidity, heat resistance, and crack resistance of the resin composition, the mixing index β1 is more preferably 0.03 to 1.2, and 0.05 to 1.0. More preferably it is. In addition, it can suppress that the viscosity of a resin composition raises extremely by making (beta) 2 0 or more and 0.1 or less, and can improve the handleability of a resin composition. As the β2 value is smaller, the viscosity of the resin composition tends to decrease.

The mixing ratio of (A) epoxy resin and alkoxysilane compound “alkoxysilane compound in which n is an integer of 0 to 2” in the present embodiment is represented by a mixing index γ calculated by the following formula (4). .
Mixing index γ = (γa) / (γs) (4)
In the above formula (4),
γa: mass of epoxy resin (g),
γs: the mass (g) of the alkoxysilane compound in which n is an integer of 0 to 2 in formula (1).

  The mixing index γ is preferably 0.02 to 15, more preferably 0.04 to 7, and still more preferably 0.08 to 5. When the mixing index γ is 0.02 or more, crack resistance tends to be improved when the metal foil-clad laminate and the printed wiring board are set, and by being 15 or less, the metal foil-clad laminate, And when it is set as a printed wiring board, it exists in the tendency for heat resistance and a flame retardance to improve. In particular, in order to improve the balance of heat resistance, flame retardancy, and crack resistance, the mixing index γ is more preferably 0.04 to 7, and further preferably 0.08 to 5.

  The epoxy equivalent (WPE) of the resin composition in the present embodiment obtained by cohydrolyzing and condensing the above-described (A) epoxy resin and the alkoxysilane compound represented by the above formula (1) is 100 to 100. It is preferable that it is 700 g / eq, More preferably, it is 120-500 g / eq, More preferably, it is 150-400 g / eq. By setting the epoxy equivalent (WPE) to 100 g / eq or more, it is possible to suppress the remaining unreacted cyclic ether group, so that the flame retardancy tends to be excellent, and by setting it to 700 g / eq or less, Since the crosslinked structure of the cured product can be formed densely, it tends to be excellent in crack resistance. Moreover, it exists in the tendency for the heat resistance at the time of setting it as a metal foil tension laminated board and a printed wiring board because epoxy equivalent shall be 120-500 g / eq, More preferably, it is 150-400 g / eq.

  In this embodiment, the viscosity at 25 ° C. of the resin composition obtained by cohydrolyzing and condensing the above-described (A) epoxy resin and the above-described alkoxysilane compound represented by the formula (1) is 1000 Pa · s or less. The liquid is preferably 500 Pa · s or less, more preferably 100 Pa · s or less. When the viscosity at 25 ° C. is 1000 Pa · s or less, the fluidity as a liquid is improved, and the miscibility with other substances such as curing agents and additives described later tends to be improved. Further, when the viscosity at 25 ° C. is 500 Pa · s or less, the efficiency of impregnation into the base material is improved, so that the productivity tends to be improved, and more preferably 100 Pa · s or less.

(Cohydrolysis condensation process)
In the present embodiment, first, the resin composition can be obtained by cohydrolyzing and condensing the above-described (A) epoxy resin and the above-described alkoxysilane compound represented by the formula (1). The “cohydrolytic condensation” in the present embodiment means a hydrolysis condensation reaction performed in the presence of an epoxy resin, and is clearly distinguished from a reaction in the absence of an epoxy resin.

  The “cohydrolytic condensation” in the present embodiment is composed of at least two steps of a reflux step without dehydration and a subsequent dehydration condensation step. The “refluxing process without dehydration” is a process in which water and a solvent blended for cohydrolysis and water and a solvent derived from an alkoxysilane compound generated during the reaction are reacted while being returned to the reaction solution. is there. Although the method is not particularly limited, the reaction is usually carried out while attaching a cooling pipe to the upper part of the reaction vessel and refluxing the generated water or solvent. The “dehydration condensation step” is a step in which the condensation reaction is performed while removing the blended water and solvent and the water and solvent generated in the “refluxing step without dehydration”. The method is not particularly limited, but usually the reaction is carried out by distillation under reduced pressure using a rotary evaporator or the like.

  The heating temperature during the cohydrolysis condensation reaction is preferably 130 ° C. or lower, more preferably 0 to 120 ° C., and still more preferably 0 to 100 ° C. By setting the temperature to 130 ° C. or lower, there is a tendency that deterioration of the resin composition can be suppressed. The reaction time for cohydrolysis condensation is appropriately selected depending on the heating temperature, but in order to reduce the residual amount of unreacted substances, it is preferably 0.5 hours or more, more preferably 1 hour or more. It is. Moreover, in order to suppress modification | denaturation of a resin composition, it is preferable that it is 24 hours or less, More preferably, it is 12 hours or less.

  The resin composition of this embodiment may be performed by adding a hydrolysis-condensation catalyst during the co-hydrolysis condensation of the above-described (A) epoxy resin and alkoxysilane compound. The hydrolysis condensation catalyst is not particularly limited as long as it promotes a conventionally known hydrolysis condensation reaction. For example, a metal (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth, etc., organic metals (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium) Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth and other organic oxides, organic acid salts, organic halides, alkoxides, etc.), inorganic bases Magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.), organic base (Ammonia, tetramethylammonium hydroxide, etc.). Among these, from the viewpoint of the balance between the reaction promoting effect and the storage stability of the resin, an organic metal of titanium or tin is preferable. Among the above organic metals, organic tin is preferable.

  Organotin refers to those in which at least one organic group is bonded to a tin atom, and examples of the structure include monoorganotin, diorganotin, triorganotin, tetraorganotin, etc. Among them, Diorganotin is preferred.

  Examples of organic tin include monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra n-octyltin, tetra n-butyltin, dibutyltin oxide, dibutyltin diacetate, dibutyltin dioctate, dibutyltin diversate, dibutyl Tin dilaurate, dibutyltin oxylaurate, dibutyltin stearate, dibutyltin dioleate, dibutyltin / silicon ethyl reactant, dibutyltin salt and silicate compound, dioctyltin salt and silicate compound, dibutyltin bis (acetylacetonate) , Dibutyltin bis (ethyl malate), dibutyltin bis (butylmalate), dibutyltin bis (2-ethylhexylmalate), dibutyltin bis (benzylmalate), dibutyltin bis (stearylmalate) ), Dibutyltin bis (oleyl malate), dibutyltin malate, dibutyltin bis (O-phenylphenoxide), dibutyltin bis (2-ethylhexyl mercaptoacetate), dibutyltin bis (2-ethylhexyl mercaptopropionate) ), Dibutyltin bis (isononyl 3-mercaptopropionate), dibutyltin bis (isooctylthioglycolate), dibutyltin bis (3-mercaptopropionate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate , Dioctyltin dioctate, dioctyltin didodecyl mercapto, dioctyltin versatate, dioctyltin distearate, dioctyltin bis (ethyl maleate), dioctyltin bis (octylmalate), dioctyltin maleate Dioctyl tin bis (isooctyl thioglycolate), dioctyl tin bis (2-ethylhexyl mercaptoacetate), dibutyl tin dimethoxide, dibutyl tin diethoxide, dibutyl tin dibutoxide, dioctyl tin dimethoxide, dioctyl tin diethoxide, dioctyl tin dibutoxide, octyl acid Examples thereof include tin and tin stearate. Among these, from the viewpoint of the reaction promotion effect, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diacetate, dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin dietoxide, dioctyl Tin dibutoxide is preferred.

  These hydrolytic condensation catalysts may be used alone or in combination. For example, organic acid tin and alkaline organic tin can be used in combination, or after reacting with an organic acid salt such as tin, it can be treated with an inorganic base. As an inorganic base in this case, water of polyvalent cation such as magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide and the like can be easily removed from the resin composition by solid-liquid separation if necessary. Oxides are preferred.

The addition amount of the hydrolysis-condensation catalyst is not particularly limited, but the preferable addition amount can be obtained from the mixing index δ which is a ratio to (OR ² ) in the above formula (1). Here, the mixing index δ is expressed by the following formula (5).
Mixing index δ = (δe) / (δs) (5)
In formula (5),
δe: addition amount of hydrolytic condensation catalyst (mol number),
δs: represents the amount (number of moles) of (OR ² ) in formula (1).

  The mixing index δ is preferably 0.0005 to 5, more preferably 0.001 to 1, and still more preferably 0.005 to 0.5. Depending on the composition of the resin composition, when the mixing index δ is 0.0005 or more, an effect of promoting hydrolysis condensation can be obtained, and when it is 5 or less, the ring opening of the cyclic ether group tends to be suppressed. It is in.

In the step of obtaining the resin composition of the present embodiment by cohydrolysis condensation, the amount of water added is not particularly limited, but the preferred amount added is a ratio to (OR ² ) in the above formula (1). It can be obtained from a certain mixing index ε.
Here, the mixing index ε is expressed by the following formula (6).
Mixing index ε = (εw) / (εs) (6)
In formula (6),
εw: amount of water added (in mol),
εs: represents the amount (mol number) of (OR ² ) in formula (1).

  The mixing index ε is preferably 0.1 to 5, more preferably 0.2 to 3, and still more preferably 0.3 to 1.5. When the mixing index ε is 0.1 or more, a phenomenon in which the hydrolysis reaction does not proceed can be suppressed, and when the mixing index ε is 5 or less, the ring opening of the cyclic ether group tends to be suppressed. . The addition of water in the co-hydrolysis condensation described above is mainly performed by hydrolysis of the alkoxysilane compound, and therefore needs to be performed in the “refluxing process without dehydration”. The timing of the addition is not particularly limited, and may be added first or gradually during the reaction using a feed pump or the like.

  The cohydrolysis condensation reaction of the present embodiment can be performed without a solvent or in a solvent. The solvent is not particularly limited as long as it is an organic solvent that can dissolve an epoxy resin and an alkoxysilane compound and is inactive to them, and examples thereof include dimethyl ether, diethyl ether, diisopropyl ether, and 1,4-dioxane. 1,3-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, ether solvents such as anisole; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; hexane, Aliphatic hydrocarbon solvents such as cyclohexane, heptane, octane, isooctane; toluene, o-xylene, m-xylene, p-xylene, ethylbenzene Ethyl acetate, ester solvents such as butyl acetate; aromatic hydrocarbon-based solvent such as methanol, ethanol, butanol, isopropanol, n- butanol, butyl cellosolve, alcohol-based solvents such as butyl carbitol. These solvents can also be used as one kind or a mixture of two or more kinds.

  Among these, from the viewpoint of suppressing the ring opening of the epoxy group during the reaction, ether solvents, ketone solvents, aliphatic hydrocarbon solvents, and aromatic hydrocarbon solvents are preferable, and the ether solvent is 50% by mass or more. More preferable is a solvent containing, at least one or more mixed solvents selected from the group consisting of 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and propylene glycol dimethyl ether are more preferable, and 1,4-dioxane and tetrahydrofuran are particularly preferable. preferable. Also, alcohol solvents such as methanol, ethanol, butanol, isopropanol, and n-butanol are preferable because they are easily available.

  The amount of the solvent added is preferably 0.01 to 20 times, more preferably 0.02 to 15 times, and more preferably 0.02 to 15 times the total mass of the epoxy resin and alkoxysilane compound subjected to the cohydrolysis condensation reaction. The amount is preferably 0.03 to 10 times. Since the molecular weight of the resin composition can be controlled by the addition amount of the solvent, a resin composition having an appropriate molecular weight and, therefore, an appropriate viscosity can be obtained by setting the range of the addition amount described above.

(Curing agent)
As the curing agent of the present embodiment, for example, synthesized from a novolak type phenol resin, an amine curing agent, imidazoles, dicyandiamide and its derivatives, an acid and acid anhydride curing agent, a dimer of linolenic acid, and ethylenediamine. Polyamide resins, bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes, polymers of phenols and various diene compounds, phenols Use of polycondensates of dimethylol with aromatic dimethylol, condensates of bismethoxymethylbiphenyl with naphthols or phenols, biphenols and their modified products, boron trifluoride-amine complexes, guanidine derivatives, etc. Can . These may be used alone or in combination. Among these curing agents, there are many combinations that exhibit a synergistic effect with respect to the curing speed, curing conditions, and the like, and it is preferable to use a plurality in combination in order to accelerate curing and reduce the blending amount. Among these, from the viewpoint that those having active hydrogen in the molecule are suitable, novolak-type phenol resins, amine-based curing agents, imidazoles, dicyandiamide and derivatives thereof are more preferable, and novolak-type phenol resins are particularly preferable. Further, when a novolac type phenol resin is used, organic compounds such as 1,8-diazabicyclo (5.4.0) undecene-7, 1,5-diazabicyclo (4.3.0) nonene-5, triphenylphosphine, etc. When used in combination with phosphine or the like, a further excellent effect may be obtained.

  The novolak type phenol resin preferably has a softening point of 100 to 150 ° C. and a hydroxyl group equivalent of 95 to 110 g / eq. By setting the softening point to 150 ° C. or less, the substrate can be efficiently impregnated with the mixed liquid of the resin composition and the curing agent. By setting the softening point to 100 ° C. or more, the metal foil-clad laminate and the printed wiring board Excellent heat resistance and flame retardancy can be imparted. Moreover, the heat resistance excellent in the metal foil tension laminated board and the printed wiring board can be provided by making a hydroxyl group equivalent into this range.

  Further, the addition amount of the novolac type phenol resin is preferably 0.2 to 2 equivalents, more preferably 0.5 to 1.5 equivalents, and still more preferably with respect to 1 equivalent of the cyclic ether group contained in the resin composition. 0.7 to 1.3 equivalents. Since it can suppress that an unreacted cyclic ether group remains by making addition amount into 0.2 equivalent or more, heat resistance can be improved, and unreacted novolak type can be made into 2 equivalent or less. Since it can suppress that a phenol resin remains, heat resistance can be improved.

  Specific examples of the amine curing agent include, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, bis (hexamethylene) triamine, 1,3,6-trisaminomethylhexane, trimethylhexamethylenediamine, Polyetherdiamine, diethylaminopropylamine, mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine, metaxylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone , Aromatic diamine eutectic mixture, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5] undecane, polyamine epoxy resin adduct, Liamine-ethylene oxide-propylene oxide adduct, cyanoethylated polyamine, ketimine compound, linear diamine, linear tertiary amine, tetramethylguanidine, alkyl-tert-monoamine, triethanolamine, piperidine, N, N'-dimethylpiperazine , Triethylenediamine, pyridine, picoline, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5, benzyldimethylamine, 2- (dimethylaminomethyl) ) Phenol, 2,4,6-tris (dimethylaminomethyl) phenol, tri-2-ethylhexylate of 2,4,6-tris (dimethylaminomethyl) phenol, dimethylcyclohexylamine, dimethylbenzylamine, dimethylhexyl Amine, dimethylaminomethyl phenol, dimethylamino p- cresol. Among these, from the viewpoint of a synergistic effect with other curing agents, 1,8-diazabicyclo [5.4.0] undecene-7,1,5-diazabicyclo [4.3.0] nonene-5, 2- (Dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol are preferred.

  Specific examples of imidazoles include 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole. 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n -Undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2 -Phenyl-4,5-di (hydroxymethyl) imidazole, -(2-cyanoethyl) -2-phenyl-4,5-di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl] -(1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl- 4'-methylimidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid addition of 2-phenylimidazole , 2,4-diamino-6- [2'-methylimidazolyl- - (1 ')] isocyanuric acid adduct of ethyl -s- triazine. Among them, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 1- (2-cyanoethyl) -2-n-undecylimidazole are preferable because they are easily available.

  Specific examples of derivatives of dicyandiamide include, for example, o-tolylbiguanide, α-2,5-dimethylbiguanide, α, ω-diphenylbiguanide, 5-hydroxynaphthyl-1-biguanide, α, α'-bisguanylguanidino. Diphenyl ether, phenyl biguanide, p-chlorophenyl biguanide, α-benzyl biguanide, α, ω-dimethyl biguanide, α, α'-hexamethylenebis [ω- (p-chlorophenyl)] biguanide, o-tolyl biguanide zinc salt, Examples include diphenyl biguanide iron salt, phenyl biguanide copper salt, biguanide nickel salt, ethylene bis biguanide hydrochloride, lauryl biguanide hydrochloride, phenyl biguanide oxalate and the like.

  Examples of acid and acid anhydride curing agents include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride , Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, “4-methylhexahydro Phthalic anhydride / hexahydrophthalic anhydride = 70/30 (mass ratio) ”, 4-methylhexahydrophthalic anhydride,“ methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride / bicyclo [ 2.2.1] Heptane-2,3-dicarboxylic anhydride ", tetrapropenyl succinic anhydride, octenyl Haq anhydride, 2,5-di-keto tetrahydrofuran. Among them, alicyclic acid anhydrides are preferred because of their long pot life and little heat generation. Specific examples of the alicyclic acid anhydride include, for example, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, and the like.

(Base material)
The base material of this embodiment can use the well-known thing used for various printed wiring board materials. For example, glass fibers such as F glass, D glass, S glass, NE glass, T glass, E glass, and Q glass, inorganic fibers such as alumina, asbestos, boron, silica alumina glass, Tyranno, silicon carbide, silicon nitride, and zirconia Polyamide fiber such as polyamide, aromatic polyamide, wholly aromatic polyamide, polyester fiber such as polyester, aromatic polyester, wholly aromatic polyester, polyether ether ketone, polyether imide, polyether sulfone, carbon, cellulose, tetra Examples thereof include organic fibers such as fluoroethylene, kraft paper, cotton linter paper, mixed paper of linter and kraft pulp, and mixtures thereof. Among these, glass fiber is preferable from the viewpoint of strength, water absorption, and availability.

  The shape of the substrate is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat. Moreover, the said material and shape are selected by the use and performance of the target molding, and if necessary, it can be used alone or from two or more types of materials and shapes. Although there is no limitation in particular in the thickness of a base material, Usually, the thing about 0.01-0.5 mm can be used according to the thickness of the target laminated board. In addition, from the viewpoint of heat resistance, moisture resistance, and workability, the base material should be surface-treated with a silane coupling agent, a silicone compound, etc., or mechanically opened to improve the affinity with the resin component. Is preferred.

(Additive)
In the resin composition of the present embodiment, the mixture of the resin composition and the curing agent, and the cured product thereof, various organic resins, inorganic fillers, and colorants are used in accordance with the purpose within a range not impairing the effects of the present embodiment. Leveling agents, lubricants, surfactants, silicone compounds, diluents (reactive diluents, non-reactive diluents, etc.), antioxidants, light stabilizers, and the like can be added as appropriate. In addition, as additives for plastics (plasticizers, flame retardants, stabilizers, antistatic agents, impact resistance enhancers, foaming agents, antibacterial / antifungal agents, conductive fillers, antifogging agents, crosslinking agents, etc.) The provided material may be blended.

  Here, the organic resin is not particularly limited, and examples thereof include an epoxy resin, an acrylic resin, a polyester resin, and a polyimide resin. Among them, those having a highly reactive organic group such as an epoxy resin are preferable.

  Examples of inorganic fillers include silicas (melted crushed silica, crystal crushed silica, spherical silica, fumed silica, colloidal silica, precipitated silica, etc.) silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, sulfuric acid Barium, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber And molybdenum disulfide. Among them, silicas, calcium carbonate, aluminum oxide, aluminum hydroxide, calcium silicate and the like are preferable, and silicas are more preferable in consideration of the physical properties of the cured product. These inorganic fillers may be used alone or in combination.

  The colorant is not particularly limited as long as it is a substance used for the purpose of coloring. For example, phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, azomethine-based various organic materials Inorganic pigments such as system dyes, titanium oxide, lead sulfate, chrome yellow, zinc yellow, chrome vermilion, valve shell, cobalt violet, bitumen, ultramarine, carbon black, chrome green, chrome oxide, cobalt green and the like. These colorants may be used alone or in combination.

  The leveling agent is not particularly limited. For example, oligomers having a molecular weight of 4000 to 12000 made of acrylates such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, hydrogenated castor oil And titanium-based coupling agents. These leveling agents may be used alone or in combination.

  The lubricant is not particularly limited, and hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax, higher fatty acid lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid, stearylamide Higher fatty acid amide lubricants such as palmitylamide, oleylamide, methylenebisstearamide, ethylenebisstearamide, hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, di-, tri -, Or tetra-) higher fatty acid ester lubricants such as stearate, alcohol lubricants such as cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol, lauric acid, myristic acid, palmitic acid, stearic acid, Examples include metal soaps that are metal salts such as magnesium, calcium, cadmium, barium, zinc, and lead such as rachidic acid, behenic acid, ricinoleic acid, and naphthenic acid, and natural waxes such as carnauba wax, candelilla wax, beeswax, and montan wax. . These lubricants may be used alone or in combination.

  The surfactant refers to an amphiphilic substance having a hydrophobic group having no affinity for the solvent in the molecule and an amphiphilic group (usually a hydrophilic group) having an affinity for the solvent. Moreover, the kind is not specifically limited, For example, a silicone type surfactant, a fluorine type surfactant, etc. are mentioned. Surfactants may be used alone or in combination.

  Examples of the silicone compound include, but are not limited to, silicone resin, silicone condensate, silicone partial condensate, silicone oil, silane coupling agent, silicone oil, polysiloxane, and the like. Or what modified | denatured by introduce | transducing an organic group into a side chain is also contained. The modification method is not particularly limited. For example, amino modification, epoxy modification, alicyclic epoxy modification, carbinol modification, methacryl modification, polyether modification, mercapto modification, carboxyl modification, phenol modification, silanol modification, polyether modification. , Polyether / methoxy modification, diol modification and the like.

  The reactive diluent is not particularly limited. For example, alkyl glycidyl ether (alkyl monoglycidyl ether, alkylcoglycidyl ether, etc.), phenyl glycidyl ether, monoglycidyl ether of alkylphenol, trimethylolpropane triglycidyl ether, orthocresyl Glycidyl ether, metaparacresyl glycidyl ether, glycidyl methacrylate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexahydrophthalic acid diglycidyl ester, alkanoic acid glycidyl ester, Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol Glycidyl ether, polypropylene glycol diglycidyl ether, fatty acid-modified epoxy, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyglycol diglycidyl ether, 1,2: 8,9 diepoxylimonene, and the like.

  The non-reactive diluent is not particularly limited, and examples thereof include high-boiling solvents such as benzyl alcohol, butyl diglycol, and propylene glycol monomethyl ether.

  Other diluents are not particularly limited. For example, any organic solvent, glycerin, polyol, water, propylene glycol diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol poly A glycidyl ether etc. are mentioned.

  The antioxidant is not particularly limited, and examples thereof include organic phosphorus antioxidants such as triphenyl phosphate and phenylisodecyl phosphite, and organic sulfurs such as distearyl-3,3′-thiodipropinate. Examples of the antioxidant include phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol.

  The light stabilizer is not particularly limited, and examples thereof include benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, and triazine-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.

  You may add the following substance further to the resin composition of this embodiment, the mixture of a resin composition and a hardening | curing agent, and its hardened | cured material. For example, solvents, oils and fats, processed oils, natural resins, synthetic resins, pigments, dyes, pigments, release agents, preservatives, adhesives, deodorants, flocculants, cleaning agents, deodorants, pH adjusters, photosensitive materials, Ink, electrode, plating solution, catalyst, resin modifier, plasticizer, softener, agrochemical, insecticide, fungicide, pharmaceutical raw material, emulsifier / surfactant, rust inhibitor, metal compound, filler, cosmetic / pharmaceutical raw material , Dehydrating agent, drying agent, antifreeze, adsorbent, colorant, rubber, foaming agent, colorant, abrasive, mold release agent, flocculant, antifoaming agent, curing agent, reducing agent, flux agent, film treatment agent, Casting raw materials, minerals, acids / alkalis, shot agents, antioxidants, surface coating agents, additives, oxidants, explosives, fuels, bleaches, light emitting elements, fragrances, concrete, fibers (carbon fibers, aramid fibers, glass) Fiber), glass, metal, excipient, disintegrant, Mixture, fluidizing agents, gelling agents, stabilizers, preservatives, buffering agents, suspending agents, thickeners, and the like.

(Prepreg)
A prepreg can be produced by impregnating a base material with a mixture of the resin composition of the present embodiment and a curing agent and drying the mixture. For the impregnation of the mixture into the substrate, a method of applying and immersing a varnish whose viscosity has been lowered by diluting with a solvent can be used, and if the mixture has a high viscosity, it is impregnated efficiently. Therefore, it is preferable to use a varnish.

  The solvent for producing the varnish is not particularly limited as long as it is compatible with the resin. For example, alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol, cyclohexanol, ether solvents such as tetrahydrofuran, 1,4-dioxane, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, Ketone solvents such as cyclohexanone and acetophenone, amide solvents such as N-methylpyrrolidone, N, N'-dimethylformamide and N, N'-diethylacetamide, aromatic carbonization such as benzene, toluene, xylene, trimethylbenzene and chlorobenzene Hydrogen solvent, ester solvents such as ethyl acetate and methyl cellosolve acetate, nitrile solvents such as acetonitrile and butyl nitrile, dichlorometa , There is a halide solvent such as chloroform, These may be used singly or may be used in combination.

  As a method of applying and immersing, a method using a roll coater, a die coater, a gravure coater, etc., a method of scraping off an excess mixture with a slit or a mangle after passing the substrate through a bath in which the mixture is stored, etc. Is mentioned.

  The proportion of the base material in the prepreg is preferably 20 to 80% by mass. By making the proportion 20% by mass or more, excellent dimensional stability and strength can be imparted, and by making the proportion 80% by mass or less, excellent heat resistance, flame retardancy, and crack resistance can be imparted. it can.

  As a method for drying the substrate impregnated with the varnish, a known method such as hot air or electromagnetic waves can be used. The temperature during heat drying is preferably 100 to 250 ° C. By setting the temperature to 250 ° C. or lower, the thermal decomposition and thermal deterioration of the composition tend to be suppressed. By setting the temperature to 100 ° C. or higher, the solvent can be efficiently evaporated, which tends to improve productivity. is there. The heating and drying time is appropriately selected depending on the temperature during drying, but is preferably 20 seconds or longer in order to reduce the residual amount of the solvent, and 60 minutes or less in order to suppress thermal decomposition and thermal deterioration of the composition. It is preferable that

(Metal foil-clad laminate)
A metal foil tension plate can be produced by laminating at least one prepreg and a metal foil, followed by heating and pressure molding. That is, the metal foil-clad laminate according to this embodiment can be a metal foil-clad laminate including at least the prepreg and the metal foil laminated on the prepreg. When there is one prepreg, metal foil is laminated on both upper and lower surfaces or one side, and when there are two or more prepregs, metal foil is laminated on the outermost upper and lower surfaces or one surface of the laminated prepreg. As a method of heating and pressure molding, various known methods may be selected as appropriate, and the temperature is preferably 100 to 250 ° C., the time 1 minute to 10 hours, the pressure 0.01 to 100 MPa, more preferably the temperature 120. ~ 200 ° C, 1 minute to 5 hours, pressure 0.1 to 50 MPa. By setting it as this temperature and time range, it can be set as a completely hardened state, suppressing the thermal decomposition and thermal deterioration of a composition. Moreover, by setting it as this pressure range, desired thickness can be achieved, although a base material is the state which is not exposed from the cured resin surface.

  As the metal foil, various known materials can be appropriately selected and used. For example, copper and copper alloys, aluminum and aluminum alloys, silver and silver alloys, gold and gold alloys, zinc and zinc alloys. , Nickel and nickel-based alloys, tin and tin-based alloys, iron and iron-based alloys, etc. Among them, copper and copper-based alloys are preferred from the viewpoint of excellent electrical conductivity and excellent adhesion to resin. .

  Moreover, an ultrathin metal foil with a carrier foil can also be used as the metal foil. Since the ultrathin metal foil with carrier foil is a metal foil obtained by bonding a peelable carrier foil and an ultrathin metal foil, an ultrathin metal foil layer can be formed on both sides or one side of a laminate. For example, when a circuit is formed by a semi-additive method or the like, flash etching can be performed after the circuit is formed by performing electroplating using an ultrathin metal foil as a power feeding layer directly without performing electroless plating.

  As the carrier foil of the ultrathin metal foil with the carrier foil, various known ones can be appropriately selected and used. For example, copper and copper-based alloy, aluminum and aluminum-based alloy, silver and silver-based alloy, gold and gold Alloy, zinc and zinc alloy, nickel and nickel alloy, tin and tin alloy, iron and iron alloy, and the like. Moreover, as metal foil, various well-known things can be selected suitably and can be used, for example, copper and copper alloy, aluminum and aluminum alloy, silver and silver alloy, gold and gold alloy, zinc and zinc -Based alloys, nickel and nickel-based alloys, tin and tin-based alloys, iron and iron-based alloys, etc. Among them, copper and copper-based alloys from the viewpoint of excellent electrical conductivity and excellent adhesion to resin Is preferred.

(Printed wiring board)
A printed wiring board can be produced by appropriately selecting various known methods for the laminated board. That is, the printed wiring board according to the present embodiment can be a printed wiring board in which the metal foil of the metal foil-clad laminate is etched. The method for the etching process is not particularly limited, and a known method may be adopted. For example, it can be manufactured by forming a wiring pattern by a subtractive method and forming a through hole or the like as necessary.

Examples that specifically describe the present embodiment are illustrated below, but the present embodiment is not limited to the following examples.
The physical properties in Examples and Comparative Examples were evaluated as follows.

<Epoxy equivalent (WPE)>
It was measured according to “JIS K7236: 2001 (How to determine epoxy equivalent of epoxy resin)”.

<Viscosity>
Measurement was performed under the following conditions.
Rotary E-type viscometer: “TV-22” manufactured by Toki Sangyo Co., Ltd.
Rotor: 3 ° × R14 (Other rotors may be selected as necessary.)
Measurement temperature: 25 ° C
Sample volume: 0.4mL

<Calculation of mixing index α>
The mixing index α was calculated from the following formula (2).
Mixing index α = (αc) / (αb) (2)
here,
αb: (B) In the formula (1), n is 1 to 2, and R ¹ is an alkoxysilane compound content (mol%) having at least one cyclic ether group,
αc: (C) In Formula (1), n is 1 to 2, and the content (mol%) of an alkoxysilane compound having at least one aryl group as R ¹ .

<Calculation of mixing index β1>
The mixing index β1 was calculated from the following equation (3).
Mixing index β1 = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
here,
β ⁿ² : the content (mol%) of the alkoxysilane compound in which n is 2 in formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n is 0 in formula (1),
β ⁿ¹ : content (mol%) of an alkoxysilane compound in which n is 1 in formula (1),
Note that the value of β2 = {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} was also calculated.

<Calculation of mixing index γ>
The mixing index γ was calculated from the following equation (4).
Mixing index γ = (γa) / (γs) (4)
here,
γa: mass of epoxy resin (g),
γs: Mass (g) of the alkoxysilane compound in which n is 0 to 2 in the formula (1).

<Calculation of mixing index δ>
The mixing index δ was calculated from the following equation (5).
Mixing index δ = (δe) / (δs) (5)
here,
δe: addition amount of hydrolytic condensation catalyst (mol number),
δs: the amount (mol number) of (OR ² ) in the formula (1).

<Calculation of mixing index ε>
The mixing index ε was calculated from the following equation (6).
Mixing index ε = (εw) / (εs) (6)
here,
εw: amount of water added (in mol),
εs: the amount (mol number) of (OR ² ) in the formula (1).

<Measurement of softening point of novolac type phenolic resin>
The measurement was performed according to Section 5.8 of “JIS K6910: 2007 (Phenolic resin test method)”.

<Measurement of hydroxyl group equivalent of novolac-type phenolic resin>
The hydroxyl value was measured in accordance with “JIS K0070: 1002 (Test method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical product)” and converted into a hydroxyl equivalent.

<Void evaluation>
The composition stirred and mixed with the formulation shown in Table 2 was poured into a fluorine-coated container (diameter × height = 7 cmφ × 5 mm) and heated at 100 ° C. for 1 hour. The obtained semi-cured sample was visually checked for the presence or absence of voids under a magnifying glass. When no voids were confirmed, the void evaluation was judged to be good.

<Heat resistance evaluation>
10 double-sided copper clad laminates of each example and each comparative example were used, heated in an autoclave at 121 ° C. for 2 hours, and then impregnated in a solder bath set at 288 ° C. for 20 seconds to swell the plate. saw. It was judged that heat resistance was good when 6-8 sheets out of 10 sheets did not swell, and heat resistance was judged particularly good when 9 sheets or more did not swell.

<Flame retardance evaluation>
Samples for flame retardancy measurement were prepared by etching both surfaces of the double-sided copper-clad laminates of each example and each comparative example, and using the obtained samples, the UL94 standard (Test for Flammability of Plastic Materials for Parts in Based on Devices and Applications, UL94, Fifth Edition), it was evaluated by the vertical method. When V-0, it was judged that the flame retardancy was good.

<Crack resistance>
The test piece was produced by cut | disconnecting the double-sided copper clad laminated board of each Example and each comparative example to length 50mm and width 25mm. Using 10 of these test pieces, a vapor-phase thermal shock test (treatment at −40 ° C. and 120 ° C. for 10 minutes each is regarded as one cycle, 1000 cycles in total) was evaluated visually for the presence or absence of cracks. When cracks did not occur in the -8 test pieces, it was judged that the crack resistance was good, and when no cracks were produced more than 9 test pieces, the crack resistance was judged to be particularly good.

  About the resin composition of an Example and a comparative example, when there was no generation | occurrence | production of a void and heat resistance, a flame retardance, and crack resistance were favorable or it was especially favorable, it was judged as a pass "(circle)" as comprehensive determination. Among them, a case where two or more items among voids, heat resistance, flame retardancy, and crack resistance were particularly good was judged as “◎” as a comprehensive judgment.

About the raw material used by the Example and the comparative example, it shows to the following (1)-(10).
(1) Epoxy resin A: bisphenol A type epoxy resin (hereinafter referred to as “Bis-A epoxy resin”)
・ Product name: “AER2600”, manufactured by Asahi Kasei Epoxy Corporation
Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
Epoxy equivalent (WPE): 187 g / eq
Viscosity (25 ° C.): 14.3 Pa · s

(2) Alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as “GPTMS”)
・ Product name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.
(3) Alkoxysilane Compound I: Phenyltrimethoxysilane (hereinafter referred to as “PTMS”)
・ Product name: “KBM-103” manufactured by Shin-Etsu Chemical Co., Ltd.
(4) Alkoxysilane compound J: Dimethyldimethoxysilane (hereinafter referred to as “DMDMS”)
・ Product name: “KBM-22” manufactured by Shin-Etsu Chemical Co., Ltd.
(5) Alkoxysilane compound K: tetraethoxysilane (hereinafter referred to as “TES”)
・ Product name: “KBE-04”, manufactured by Shin-Etsu Chemical Co., Ltd.
(6) Alkoxysilane compound L: polymethoxysiloxane (hereinafter referred to as “P-MS”)
・ Product name: “Methyl silicate 51” manufactured by Fuso Chemical Industry Co., Ltd.

(7) Solvent (7-1) Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., stabilizer-free type, hereinafter referred to as “THF”)
(7-2) 2-butanone (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as “MEK”)

(8) Hydrolysis condensation catalyst: dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as “DBTDL”)
(9) Curing agent (9-1) Curing agent A: Novolac type phenolic resin (manufactured by DIC, trade name “PHENOLITE”; hydroxyl group equivalent 104 g / eq, softening point 100 ° C.) (hereinafter referred to as “NP resin”),
(9-2) Curing agent B: 1,8-diazabicyclo [5.4.0] undecene-7 (manufactured by Sun Apro, trade name “DBU”) (hereinafter referred to as “DBU”),
(10) Substrate: Glass cloth (Asahi Shovel Co., Ltd., trade name “2116”)

(Synthesis Example 1)
Resin composition A: Resin composition A was produced and evaluated by the following procedure.
(1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer.
(2) According to the composition ratio in Table 1, in an atmosphere of 25 ° C., the epoxy resin, alkoxysilane compound and THF are placed in a flask containing a stirrer, mixed and stirred, and then water and a hydrolysis condensation catalyst are added. The mixture was stirred.
(3) Subsequently, a cooling tube was set in the flask, and the flask was immediately immersed in an oil bath at 80 ° C. to start stirring, and reacted for 10 hours while refluxing.
(4) After completion of the reaction, after cooling to 25 ° C., the cooling tube was removed from the flask, and a sample solution was collected after completion of the refluxing process.
(5) The solution after completion of the refluxing process was distilled off at 400 Pa and 50 ° C. for 1 hour using an evaporator, and then further dehydrated and condensed while being distilled off at 80 ° C. for 5 hours.
(6) After completion of the reaction, the mixture was cooled to 25 ° C. to obtain a resin composition A.
(7) Table 3 shows the mixing indices α to ε in this resin composition.
(8) Further, according to the above method, the epoxy equivalent (WPE) of the resin composition A obtained in the above (6) was measured. The resin composition had an epoxy equivalent (WPE) of 275 g / eq and showed an appropriate value. The viscosity was 80.1 Pa · s and a fluid liquid.

(Synthesis Example 2)
Resin composition B: According to the composition ratio in Table 1, resin composition B was synthesized and evaluated in the same manner as in Synthesis Example 1. The resin composition was epoxy equivalent (WPE) = 231 g / eq, and showed an appropriate value. The viscosity was 13.2 Pa · s and a fluid liquid.

(Synthesis Example 3)
Resin composition C: Resin composition C was synthesized and evaluated in the same manner as in Synthesis Example 1 in accordance with the composition ratio in Table 1. The resin composition was epoxy equivalent (WPE) = 210 g / eq, and showed an appropriate value. The viscosity was 15.3 Pa · s and a fluid liquid.

(Synthesis Example 4)
Resin composition D: Resin composition D was synthesized and evaluated in the same manner as in Synthesis Example 1 according to the composition ratio in Table 1. The resin composition had an epoxy equivalent (WPE) = 204 g / eq and showed an appropriate value. The viscosity was 9.8 Pa · s, and it was a fluid liquid.

(Synthesis Example 5)
Resin composition E: Resin composition E was synthesized and evaluated in the same manner as in Synthesis Example 1 according to the composition ratio in Table 1. The resin composition was epoxy equivalent (WPE) = 191 g / eq, and showed an appropriate value. The viscosity was 10.1 Pa · s, and it was a fluid liquid.

(Synthesis Example 6)
Resin composition F: Resin composition F was synthesized and evaluated in the same manner as in Synthesis Example 1 according to the composition ratios in Table 1. The resin composition had an epoxy equivalent (WPE) = 311 g / eq and showed an appropriate value. The viscosity was 200 Pa · s, and it was a fluid liquid.

(Synthesis Example 7)
Resin composition G: Resin composition G was synthesized and evaluated in the same manner as in Synthesis Example 1 in accordance with the composition ratio in Table 1. The resin composition had an epoxy equivalent (WPE) = 361 g / eq, and showed an appropriate value. The viscosity was 380 Pa · s, and it was a fluid liquid.

(Synthesis Example 8)
Resin composition H: Resin composition G was synthesized and evaluated in the same manner as in Synthesis Example 1 according to the composition ratio in Table 1. The resin composition was epoxy equivalent (WPE) = 221 g / eq, and showed an appropriate value. The viscosity was 99.3 Pa · s, and it was a fluid liquid.

(Comparative Synthesis Example 1)
Resin composition I: According to the composition ratio in Table 1, resin composition H was synthesized and evaluated in the same manner as in Synthesis Example 1. The resin composition had an epoxy equivalent (WPE) of 183 g / eq and showed an appropriate value. The viscosity was 9.2 Pa · s, and it was a fluid liquid.

(Comparative Synthesis Example 2)
Resin composition J: Resin composition I was synthesized and evaluated in the same manner as in Synthesis Example 1 in accordance with the composition ratio in Table 1. The resin composition was epoxy equivalent (WPE) = 389 g / eq, and showed an appropriate value. The viscosity was 1000 Pa · s or more, exceeding the upper limit of measurement, and was not fluid.

(Comparative Synthesis Example 3)
Resin composition K: According to the composition ratio in Table 1, it was added to the reaction vessel, immersed in an oil bath at 85 ° C., and stirred and dissolved. Further, while purging with nitrogen, the temperature of the oil bath was raised to 105 ° C., and the dealcoholization reaction was performed for 8 hours. Next, after cooling to 60 ° C., the pressure was reduced to 12000 Pa, the dissolved alcohol was removed, and the resin composition H was synthesized and evaluated. The resin composition was epoxy equivalent (WPE) = 250 g / eq, and showed an appropriate value. The viscosity was 3.2 Pa · s, and it was a fluid liquid.

Example 1
Using the resin composition A of Synthesis Example 1, the raw materials were blended according to the composition shown in Table 2, and the stirred and mixed composition was poured into a fluorine-coated container (diameter × height = 7 cmφ × 5 mm), 100 Heated at 0 ° C. for 1 hour. When the obtained semi-cured sample was visually checked for the presence or absence of voids under a magnifying glass, voids were not generated and the void evaluation was judged to be good.
Resin varnish A was prepared by using the resin composition A of Synthesis Example 1, blending raw materials according to the composition of Table 2, and blending MEK as an organic solvent so that the solid content was 50%.
A glass cloth was impregnated with the resin varnish A so as to have a resin content of about 40%, and then dried at 120 ° C. for 30 minutes to prepare prepreg A. Four prepregs A were stacked, and a copper foil having a thickness of 35 μm was stacked on the top and bottom, and heated and pressed at a temperature of 180 ° C. and 3 MPa for 150 minutes to prepare a double-sided copper-clad laminate A.

Since 10 laminates A were used and heated in an autoclave at 121 ° C. for 2 hours and then impregnated in a solder bath set at 288 ° C. for 20 seconds, no swelling occurred at 10/10 sheets. The heat resistance was judged to be particularly good. A sample for flame retardancy measurement is prepared by etching both surfaces of the laminate A, and the obtained sample is used to test the UL 94 standard (Test for Flammability of Plastics for Devices in Devices and Applications, UL94, Fifth E). Based on the evaluation by the vertical method, it was determined that the flame retardancy was good because it was V-0.
A test piece is prepared by cutting the laminate A into a length of 50 mm and a width of 25 mm, and 10 test pieces are used to perform a gas-phase thermal shock test (treatment at −40 ° C. and 120 ° C. for 30 minutes is 1 The total number of cycles was 500), and the presence or absence of cracks was visually evaluated. Since no cracks were generated at 9/10 pieces, it was judged that the crack resistance was particularly good.
From the above results, it was determined that the resin composition A was acceptable as a comprehensive judgment because no void was generated and the heat resistance, flame retardancy, and crack resistance were particularly good or good.

(Example 2)
Using the resin composition B of Synthesis Example 2, it was produced and evaluated in the same manner as in Example 1. Table 3 shows the evaluation results and mixing indexes α to ε. Except that the resin composition B of Synthesis Example 2 was used, voids were evaluated in the same manner as in Example 1. As a result, voids were not generated and the void evaluation was judged to be good. A laminate B was produced in the same manner as in Example 1 except that the resin composition B of Synthesis Example 2 was used.
When heat resistance was evaluated in the same manner as in Example 1 using the laminate B, it was judged that the heat resistance was particularly good because no swelling occurred at 10/10 sheets.
When the flame retardance was evaluated by the same method as in Example 1 using the laminate B, it was determined that the flame retardancy was good because it was V-0.
When the crack resistance was evaluated by the same method as in Example 1 using the laminate B, no cracks were generated at 9/10 pieces, so that the crack resistance was judged to be particularly good.
From the above results, it was determined that the resin composition B was acceptable as a comprehensive judgment because no void was generated and the heat resistance, flame retardancy, and crack resistance were particularly good or good.

(Example 3)
Using the resin composition C of Synthesis Example 3, it was produced and evaluated in the same manner as in Example 1. Table 3 shows the evaluation results and mixing indexes α to ε.
Except that the resin composition C of Synthesis Example 3 was used, voids were evaluated in the same manner as in Example 1. As a result, voids were not generated and the void evaluation was judged to be good.
A laminate C was produced in the same manner as in Example 1 except that the resin composition C of Synthesis Example 3 was used.
When the heat resistance was evaluated by the same method as in Example 1 using the laminate C, it was judged that the heat resistance was good because 10/10 sheets were not swollen.
When the flame retardance was evaluated in the same manner as in Example 1 using the laminate C, it was determined that the flame retardancy was good because it was V-0.
When the crack resistance was evaluated by the same method as in Example 1 using the laminate C, no cracks were generated at 9/10 pieces, so it was judged that the crack resistance was good.
From the above results, it was determined that the resin composition C was acceptable as a comprehensive judgment because no void was generated and the heat resistance, flame retardancy, and crack resistance were particularly good or good.

Example 4
Using the resin composition D of Synthesis Example 4, it was produced and evaluated in the same manner as in Example 1. Table 3 shows the evaluation results and mixing indexes α to ε. Except that the resin composition D of Synthesis Example 4 was used, voids were evaluated in the same manner as in Example 1. As a result, voids were not generated and the void evaluation was judged to be good.
A laminate D was produced in the same manner as in Example 1 except that the resin composition D of Synthesis Example 4 was used.
When heat resistance was evaluated in the same manner as in Example 1 using the laminate D, it was judged that heat resistance was good because no swelling occurred at 8/10 sheets.
When the flame retardance was evaluated by the same method as in Example 1 using the laminate D, it was determined that the flame retardancy was good because it was V-0.
When the crack resistance was evaluated by the same method as in Example 1 using the laminate D, no cracks were generated at 9/10 pieces, so it was judged that the crack resistance was particularly good.
From the above results, it was determined that the resin composition D was acceptable as a comprehensive judgment because no void was generated and the heat resistance, flame retardancy, and crack resistance were particularly good or good.

(Example 5)
Using the resin composition E of Synthesis Example 5, it was produced and evaluated in the same manner as in Example 1. Table 3 shows the evaluation results and mixing indexes α to ε.
Except that the resin composition E of Synthesis Example 5 was used, voids were evaluated in the same manner as in Example 1. As a result, voids were not generated and the void evaluation was judged to be good.
A laminate E was produced in the same manner as in Example 1 except that the resin composition E of Synthesis Example 5 was used.
When heat resistance was evaluated in the same manner as in Example 1 using the laminate E, it was judged that heat resistance was good because 6/10 sheets were not swollen.
When the flame retardance was evaluated by the same method as in Example 1 using the laminate E, it was determined that the flame retardancy was good because it was V-0.
When the crack resistance was evaluated in the same manner as in Example 1 using the laminate E, no cracks were generated at 10/10 pieces, so that the crack resistance was judged to be particularly good.
From the above results, by using the resin composition E, no void was generated, and the heat resistance, flame retardancy, and crack resistance were particularly good or good, so that it was judged as acceptable as a comprehensive judgment.

(Example 6)
Using the resin composition F of Synthesis Example 6, it was produced and evaluated in the same manner as in Example 1. Table 3 shows the evaluation results and mixing indexes α to ε.
Except that the resin composition F of Synthesis Example 6 was used, voids were evaluated in the same manner as in Example 1. As a result, voids were not generated and the void evaluation was judged to be good.
A laminate F was produced in the same manner as in Example 1 except that the resin composition F of Synthesis Example 6 was used.
When heat resistance was evaluated in the same manner as in Example 1 using the laminate F, no swelling occurred at 7/10 sheets, and it was judged that heat resistance was good.
When the flame retardance was evaluated by the same method as in Example 1 using the laminate F, it was determined that the flame retardancy was good because it was V-0.
When the crack resistance was evaluated by the same method as in Example 1 using the laminate F, no cracks were generated at 8/10 pieces, so it was judged that the crack resistance was good.
From the above results, it was determined that the resin composition F was acceptable as a comprehensive judgment because no void was generated and the heat resistance, flame retardancy, and crack resistance were all good.

(Example 7)
Using the resin composition G of Synthesis Example 7, it was produced and evaluated in the same manner as in Example 1. Table 3 shows the evaluation results and mixing indexes α to ε.
Except that the resin composition G of Synthesis Example 7 was used, voids were evaluated in the same manner as in Example 1. As a result, voids were not generated and the void evaluation was judged to be good.
A laminate G was produced in the same manner as in Example 1 except that the resin composition G of Synthesis Example 7 was used.
When heat resistance was evaluated in the same manner as in Example 1 using the laminate G, it was judged that heat resistance was good because 7/10 sheets were not swollen.
When the flame retardance was evaluated by the same method as in Example 1 using the laminate G, it was determined that the flame retardancy was good because it was V-0.
When the crack resistance was evaluated by the same method as in Example 1 using the laminate G, no cracks were generated at 6/10 pieces, so it was judged that the crack resistance was good.
From the above results, by using the resin composition G, no void was generated, and heat resistance, flame retardancy, and crack resistance were all good.

(Example 8)
Using the resin composition H of Synthesis Example 8, it was produced and evaluated in the same manner as in Example 1. Table 3 shows the evaluation results and mixing indexes α to ε.
Except that the resin composition H of Synthesis Example 8 was used, voids were evaluated in the same manner as in Example 1. As a result, voids were not generated and the void evaluation was judged to be good.
A laminate H was produced in the same manner as in Example 1 except that the resin composition H of Synthesis Example 8 was used.
When the heat resistance was evaluated in the same manner as in Example 1 using the laminate H, it was judged that the heat resistance was good because 10/10 sheets were not swollen.
When the flame retardance was evaluated by the same method as in Example 1 using the laminate H, it was determined that the flame retardancy was good because it was V-0.
When the crack resistance was evaluated by the same method as in Example 1 using the laminate H, no cracks were generated at 9/10 pieces, so it was judged that the crack resistance was good.
From the above results, it was determined that the resin composition H was acceptable as a comprehensive judgment because no void was generated and the heat resistance, flame retardancy, and crack resistance were particularly good or good.

(Comparative Example 1)
Using the resin composition I of Comparative Synthesis Example 1, it was produced and evaluated in the same manner as in Example 1. Table 3 shows the evaluation results and mixing indexes α to ε.
Except that the resin composition I of Comparative Synthesis Example 1 was used, voids were evaluated in the same manner as in Example 1. As a result, voids were not generated and the void evaluation was judged to be good.
A laminate I was prepared in the same manner as in Example 1 except that the resin composition I of Comparative Synthesis Example 1 was used.
When the heat resistance was evaluated by the same method as in Example 1 using the laminate I, swelling was generated at 5/10 sheets, and the heat resistance was judged to be poor.
When the flame retardance was evaluated by the same method as in Example 1 using the laminate I, the flame retardancy was judged to be poor because it was not V-0.
When the crack resistance was evaluated in the same manner as in Example 1 using the laminate I, no cracks were generated at 10/10 pieces, and therefore the crack resistance was judged to be particularly good.
From the above results, by using the resin composition I, there is no generation of voids, and crack resistance is particularly good, but heat resistance and flame retardancy are poor, so that it is rejected as a comprehensive judgment. It was judged.

(Comparative Example 2)
Using the resin composition J of Comparative Synthesis Example 2, it was produced and evaluated in the same manner as in Example 1. Table 3 shows the evaluation results and mixing indexes α to ε.
Voids were evaluated in the same manner as in Example 1 except that the resin composition J of Comparative Synthesis Example 2 was used. As a result, no voids were generated, and it was determined that the void evaluation was good.
A laminate J was produced in the same manner as in Example 1 except that the resin composition J of Comparative Synthesis Example 2 was used.
When the heat resistance was evaluated in the same manner as in Example 1 using the laminate J, swelling was caused at 4/10 sheets, and the heat resistance was judged to be poor.
When the flame retardance was evaluated in the same manner as in Example 1 using the laminate J, it was determined that the flame retardancy was good because it was V-0.
When the crack resistance was evaluated in the same manner as in Example 1 using the laminate J, no cracks were generated at 2/10 pieces, so the crack resistance was judged to be poor.
From the above results, by using the resin composition I, there is no generation of voids and the flame retardancy is good, but the heat resistance and crack resistance are poor. did.

(Comparative Example 3)
Using the resin composition K of Comparative Synthesis Example 3, it was produced and evaluated in the same manner as in Example 1.
Voids were evaluated in the same manner as in Example 1 except that the resin composition K of Comparative Synthesis Example 3 was used. As a result, no voids were generated, and the void evaluation was judged to be good.
A laminate K was produced in the same manner as in Example 1 except that the resin composition K of Comparative Synthesis Example 3 was used.
When the heat resistance was evaluated in the same manner as in Example 1 using the laminate plate K, swelling occurred at 4/10 sheets, and the heat resistance was judged to be poor.
When the flame retardance was evaluated by the same method as in Example 1 using the laminate K, the flame retardancy was judged to be poor because it was not V-0.
When the crack resistance was evaluated by the same method as in Example 1 using the laminate K, no cracks were generated at 0/10 pieces, so the crack resistance was judged to be poor.
From the above results, it was determined that the resin composition K was rejected as a comprehensive judgment because no void was generated but the heat resistance, flame retardancy, and crack resistance were poor.

(Comparative Example 4)
According to the composition of Table 2, it manufactured and evaluated by the method similar to Example 1 using Bis-A epoxy resin, GPTMS, and PTMS instead of the resin composition A. The results are shown in Table 3.
Voids were evaluated in the same manner as in Example 1 except that Bis-A epoxy resin, GPTMS, and PTMS were used in place of the resin composition A. As a result, voids were confirmed and the void evaluation was judged to be poor. did.
Moreover, since the void generate | occur | produced, it was difficult to manufacture the laminated board for evaluating heat resistance, a flame retardance, and crack tolerance.

(Comparative Example 5)
According to the composition of Table 2, it manufactured and evaluated by the method similar to Example 1 using the Bis-A epoxy resin instead of the resin composition A. The results are shown in Table 3.
A void was evaluated in the same manner as in Example 1 except that a Bis-A epoxy resin was used instead of the resin composition A. As a result, no void was generated and the void evaluation was judged to be good.
A laminate L was produced in the same manner as in Example 1 except that a Bis-A epoxy resin was used instead of the resin composition A.
When the heat resistance was evaluated in the same manner as in Example 1 using the laminate L, it was determined that the heat resistance was poor because 1/10 sheets were swollen.
When the flame retardance was evaluated by the same method as in Example 1 using the laminate L, the flame retardancy was judged to be poor because it was not V-0.
When the crack resistance was evaluated by the same method as in Example 1 using the laminate L, no cracks were generated at 10/10 pieces, so that the crack resistance was judged to be particularly good.
From the above results, by using a Bis-A epoxy resin instead of the resin composition A, no voids are generated and crack resistance is particularly good, but heat resistance and flame retardancy are poor. , It was judged as unacceptable as a comprehensive judgment.

  As shown in Tables 1 to 3, in each Example, no void was generated during curing, and the heat resistance, flame retardancy, and crack resistance were excellent, and it was confirmed to have high reliability. On the other hand, in each comparative example, at least one of void, heat resistance, flame retardancy, and crack resistance was unacceptable.

  The prepreg, the metal-clad foil-clad laminate, and the printed wiring board according to the present invention can be suitably used as a substrate material in the electric material field. For example, a television, a digital camera, a personal computer, a printer, an audio device, an electronic device It has industrial applicability as a substrate material for household appliances such as a range and a refrigerator, and a substrate material for observation equipment, electromagnetic wave generators, oscillators, solar cells, and the like.

Claims (8)

(A) A resin composition obtained by cohydrolyzing and condensing an epoxy resin and an alkoxysilane compound represented by the following formula (1),

(In the formula, n represents an integer of 0 to 3, R ¹ may be the same or different and represents a hydrogen atom or an organic group. R ² may be the same or different, and represents a hydrogen atom. Or represents a C1-C8 alkyl group.)
The alkoxysilane compound is
(B) In the formula (1), n is an integer of 1 to 2, and as R ¹ , at least one alkoxysilane compound having at least one 3-membered ether group;
(C) In the formula (1), n is an integer of 1 to 2, and R ¹ has at least one aryl group having at least one aryl group;
A blending index α of (B) and (C) represented by the following formula (2) is 0.001 to 19, and a resin composition:
A curing agent;
A substrate;
A prepreg containing
Mixing index α = (αc) / (αb) (2)
(Wherein, αb: content of component (B) (mol%), αc: content of component (C) (mol%)).   2. The prepreg according to claim 1, wherein the epoxy equivalent of the (A) epoxy resin is 100 to 600 g / eq, and the viscosity of the (A) epoxy resin at 25 ° C. is 1000 Pa · s or less.   The prepreg according to claim 1 or 2, wherein the (A) epoxy resin is a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound. As the alkoxysilane compound,
(D) The prepreg as described in any one of Claims 1-3 which further contains the at least 1 sort (s) of alkoxysilane compound whose n is 0 in the said Formula (1). The prepreg according to any one of claims 1 to 4, wherein a mixing index β1 of the alkoxysilane compound represented by the following formula (3) is 0.01 to 1.4;
Mixing index β1 = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
(Where
β ⁿ² : the content (mol%) of the alkoxysilane compound in which n is 2 in the formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n is 0 in the formula (1),
β ⁿ¹ : the content (mol%) of the alkoxysilane compound in which n is 1 in the formula (1),
Here, 0 ≦ {β2 = (β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1). The prepreg according to any one of claims 1 to 5, wherein a mixing index γ of the (A) epoxy resin and the alkoxysilane compound represented by the following formula (4) is 0.02 to 15. ;
Mixing index γ = (γa) / (γs) (4)
(Where
γa: mass of epoxy resin (g),
γs: the mass (g) of the alkoxysilane compound in which n is an integer of 0 to 2 in the formula (1) The prepreg according to any one of claims 1 to 6,
A metal foil laminated on the prepreg;
A metal foil-clad laminate.   A printed wiring board in which the metal foil of the metal foil-clad laminate according to claim 7 is etched.