JP2011032389A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition suitable for forming an insulating layer of a circuit board, such as a multilayer circuit board, wherein flame retardancy is improved, dielectric loss tangent and a coefficient of thermal expansion of the insulating layer are low, and adhesion between a conductor layer and an insulating resin can be more stably maintained. <P>SOLUTION: The problem is solved when a specific acrylate compound, an epoxy resin, and a cyanate ester resin are contained. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition containing a specific acrylate compound, an epoxy resin, and a cyanate ester resin.

  Conventionally, as a resin composition used for an insulating layer of a multilayer printed wiring board, it has been known that a resin composition containing a cyanate ester resin can form an insulating layer having excellent heat resistance and dielectric properties (Patent Document 1, 2) However, the flame retardancy was not always satisfactory.

  Therefore, various efforts have been made to improve the flame retardancy of the resin composition. For example, Non-Patent Document 1 discloses a method for improving flame retardancy by adding a phosphorus-based flame retardant. However, when the environmental test is performed under high temperature and high humidity, the heat resistance decreases, the relative permittivity, the dielectric loss tangent decreases, and the coefficient of thermal expansion increases. The peel strength between the insulating layers and the circuit conductor layer decreases significantly. There was a problem that the characteristics possessed before the addition were significantly reduced.

  On the other hand, Patent Document 3 discloses a phosphorus-containing (meth) acrylic compound as a flame retardant for a radical polymerizable flame retardant resin composition. However, since most of the resin compositions have radical polymerizability, their application range has been considered to be limited.

International Publication 2003/099952 Pamphlet International Publication No. 2008/044766 Pamphlet JP 2007-238738 A

Hitachi Chemical Technical Report No. 45 (2005-7)

  The problem to be solved by the present invention is to provide a resin composition having improved flame retardancy while keeping the dielectric tangent and thermal expansion coefficient of the insulating layer low and maintaining more stable adhesion between the conductor layer and the insulating resin. That is.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by containing a specific acrylate compound, epoxy resin, and cyanate ester resin, and have completed the present invention.

That is, the present invention includes the following aspects.
(1) A resin composition comprising (A) a (meth) acrylate compound having a phosphaphenanthrene skeleton, (B) an epoxy resin, and (C) a cyanate ester resin.
(2) The resin composition as described in (1) above, further comprising (D) an organic peroxide.
(3) The resin composition as described in (1) or (2) above, further comprising (E) a metal-based curing accelerator.
(4) When the nonvolatile content of the resin composition is 100% by mass, the content of the component (B) is 5 to 60% by mass, the content of the component (C) is 5 to 50% by mass, and the component (A) The content is 2 to 20% by mass, the content of the component (E) is 25 to 500 ppm, and the content of the component (D) is 0.05 to 3% by mass, and the ratio between the cyanate ester group and the epoxy group is The resin composition as described in said (3) which is 1: 0.4-1: 2.
(5) (E) The metal-based curing accelerator is an organometallic complex or organometallic salt of one or more metals selected from cobalt, copper, zinc, iron, nickel, manganese, and tin. The resin composition as described in said (3) or (4).
(6) The resin composition as described in any one of (1) to (5) above, further comprising (F) a vinylbenzyl compound.
(7) The resin composition according to any one of (1) to (6), further comprising (G) a polymer compound.
(8) The resin composition as described in any one of (1) to (7) above, further comprising (H) an inorganic filler.
(9) The resin composition as described in any one of (1) to (8) above, which further comprises (I) rubber particles.
(10) The resin composition according to any one of (1) to (9) above, further comprising (J) a flame retardant (excluding a (meth) acrylate compound having a phosphaphenanthrene skeleton). .
(11) The resin composition as described in any one of (1) to (10) above, further comprising (K) a curing accelerator (excluding metal-based curing accelerators and organic peroxides). .
(12) The dielectric loss tangent characteristic is 0.001 to 0.018, and the adhesion strength reduction rate before and after the environmental test is 0.1% to 70%. The resin composition in any one.
(13) A sheet-like material comprising the resin composition according to any one of (1) to (12) above.
(14) A multilayer printed wiring board comprising the sheet-like material according to (13).

By containing a specific acrylate compound, epoxy resin, cyanate ester resin, the dielectric loss tangent and thermal expansion coefficient of the formed insulating layer is low, and the flame resistance is maintained while keeping the adhesion between the conductor layer and the insulating resin more stable. It has become possible to provide a resin composition with improved

  The present invention is a resin composition comprising (A) a (meth) acrylate compound having a phosphaphenanthrene skeleton, (B) an epoxy resin, and (C) a cyanate ester resin.

[(A) (Meth) acrylate compound having phosphaphenanthrene skeleton]
The (meth) acrylate compound having (A) phosphaphenanthrene skeleton used in the present invention can stably maintain other physical properties while improving the flame retardancy of the resin composition. The component (A) is not particularly limited, and can be obtained by Michael addition reaction between a compound having a phosphaphenanthrene skeleton and a (meth) acrylate compound, and a radical polymerizable property such as a (meth) acryloyl group. It has a group and a phosphorus atom is taken in during curing by radical polymerization. In particular, a phosphorus-containing (meth) acrylate compound comprising a 9,10-dihydro-9oxa-10-phosphaphenanthrene-10 oxide compound and a polyfunctional acrylate compound having three or more (meth) acryloyl groups in one molecule preferable. The (meth) acrylate compound having such a phosphaphenanthrene skeleton includes 9,10-dihydro-9oxa-10-phosphaphenanthrene-10 oxide, HCA (manufactured by Sanko Co., Ltd.) and trimethylolpropane tri (meth). It can be produced by a method of Michael addition of acrylate, pentaerythritol tetra (meth) acrylate, or tris (2-acryloyloxyethyl) isocyanurate. Specifically, a (meth) acrylate compound having a phosphaphenanthrene skeleton described in JP-A-2007-238738 can be used. You may use these 1 type or in combination of 2 or more types.

  Examples of commercially available (meth) acrylate compounds having a phosphaphenanthrene skeleton include HFA-6007M (manufactured by Showa Polymer Co., Ltd., phosphorus content 8.6%), HFA-6065P (manufactured by Showa Polymer Co., Ltd.). , Phosphorus content 4.9%), HFM-9B (Showa High Polymer Co., Ltd., phosphorus content 7.2%), and the like. Of these, HFA-6007M (Showa High Polymer Co., Ltd., phosphorus content 8.6%) and HFM-9B (Showa High Polymer Co., Ltd., phosphorus content 7.2%) are preferable.

  The content of the (meth) acrylate compound having a phosphaphenanthrene skeleton in the resin composition is not particularly limited. The upper limit of the content of the (meth) acrylate compound having a phosphaphenanthrene skeleton in the resin composition is 20% with respect to 100% by mass of the nonvolatile content in the resin composition from the viewpoint of preventing an increase in the coefficient of thermal expansion. % By mass is preferable, 15% by mass is more preferable, and 10% by mass is still more preferable. On the other hand, the lower limit of the content of the (meth) acrylate compound having a phosphaphenanthrene skeleton in the resin composition is 100% by mass with respect to the nonvolatile content in the resin composition from the viewpoint of obtaining sufficient flame retardancy. 1 mass% is preferable, 2 mass% is more preferable, and 3 mass% is still more preferable.

[(B) Epoxy resin]
Component (B) is not particularly limited, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, biphenyl type epoxy resin, Aralkyl-type epoxy resin, naphthol-type epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene-type epoxy resin, epoxidized product of condensation products of phenols and aromatic aldehydes having phenolic hydroxyl groups, biphenyl aralkyl-type epoxy resin, fluorene-type Examples thereof include an epoxy resin, a xanthene type epoxy resin, and triglycidyl isocyanurate. Two or more epoxy resins may be used in combination. Epoxy resins include bisphenol A type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, and epoxy resins having a butadiene structure from the viewpoint of heat resistance, insulation reliability, and adhesion to metal films. preferable. As the epoxy resin, a naphthol type epoxy resin represented by the following general formula (1) is particularly preferable.

(In Formula (1), n shows the number of 1-6 as an average value, X shows a glycidyl group or a C1-C8 hydrocarbon group, and the ratio of hydrocarbon group / glycidyl group is 0.05- 2.0.)
The ratio of the hydrocarbon group and glycidyl group as an average value in the epoxy resin is in the range of hydrocarbon group / glycidyl group = 0.05 to 2.0, preferably in the range of 0.1 to 1.0. . Examples of the hydrocarbon group when X represents a hydrocarbon group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, propargyl group, butyl group, n-pentyl group, sec -Pentyl group, tert-pentyl group, cyclohexyl group, phenyl group, benzyl group and the like can be mentioned, and a methyl group is particularly preferable. The naphthol epoxy resin represented by the formula (1) is a known resin described in JP-A-2006-160868, and can be produced according to the production method described in the publication.

  Commercially available epoxy resins include “jER828EL” (liquid bisphenol A type epoxy resin) manufactured by Japan Epoxy Resin Co., Ltd., “HP4032”, “HP4032D” (naphthalene type bifunctional epoxy resin) manufactured by DIC Corporation, and DIC. "HP4700" (naphthalene type tetrafunctional epoxy resin) manufactured by Co., Ltd. "ESN-475V" and "ESN-185V" (naphthol type epoxy resin) manufactured by Toto Kasei Co., Ltd., "PB-3600" manufactured by Daicel Chemical Industries, Ltd. ”(Epoxy resin having a butadiene structure),“ NC3000H ”,“ NC3000L ”,“ NC3100 ”,“ NC3000 ”,“ NC3000FH-75M ”(biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., Japan Epoxy Resin Co., Ltd. ) "YX4000" (biphenyl type epoxy tree) ), Manufactured by Japan Epoxy Resins Co., Ltd. "YX8800" (anthracene skeleton-containing epoxy resin) and the like. You may use these 1 type or in combination of 2 or more types.

  There is no restriction | limiting in particular in content of the epoxy resin in a resin composition. The upper limit of the content of the epoxy resin in the resin composition is relatively low in the resin composition from the viewpoint of preventing the coefficient of thermal expansion and the dielectric loss tangent from increasing due to the relatively decreased content of the cyanate ester resin. 60 mass% is preferable with respect to 100 mass% of non volatile matter of 50, 50 mass% is more preferable, 40 mass% is still more preferable. On the other hand, the lower limit of the content of the epoxy resin in the resin composition is preferably 5% by mass with respect to 100% by mass of the nonvolatile content in the resin composition, from the viewpoint of preventing a decrease in adhesion with the conductor layer. 10 mass% is more preferable and 15 mass% is still more preferable.

[(C) Cyanate ester resin]
The (C) cyanate ester resin used in the present invention can impart high heat resistance, low dielectric loss tangent, low coefficient of thermal expansion, and the like of the resin composition. The component (C) is not particularly limited, and is a novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol type (bisphenol A type, bisphenol F type, Examples thereof include cyanate ester resins (such as bisphenol S type) and prepolymers in which these are partially triazine. You may use these 1 type or in combination of 2 or more types. Although the weight average molecular weight of cyanate ester resin is not specifically limited, Preferably it is 500-4500, More preferably, it is 600-3000.

  Specific examples of the cyanate ester resin include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4 ′. -Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) ) Bifunctional cyanate resins such as methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, phenol novolac, Cresolno Examples thereof include polyfunctional cyanate resins derived from racks, dicyclopentadiene structure-containing phenol resins, prepolymers in which these cyanate resins are partly triazines, etc. These may be used alone or in combination of two or more. .

  As a commercially available cyanate ester resin, a phenol novolak type polyfunctional cyanate ester resin represented by the following formula (2) (manufactured by Lonza Japan Co., Ltd., PT30, cyanate equivalent 124), represented by the following formula (3): Prepolymer (part Lona Japan Co., Ltd., BA230, cyanate equivalent 232), containing a dicyclopentadiene structure represented by the following formula (4) Examples include cyanate ester resins (Lonza Japan Co., Ltd., DT-4000, DT-7000).

［式（２）中、ｎは平均値として任意の数（好ましくは０〜２０）を示す。］

[In Formula (2), n shows arbitrary numbers (preferably 0-20) as an average value. ]

（式（４）中、ｎは平均値として０〜５の数を表す。）

(In Formula (4), n represents the number of 0-5 as an average value.)

  There is no restriction | limiting in particular in content of the cyanate ester resin in a resin composition. The upper limit of the content of the cyanate ester resin in the resin composition is preferably 50% by mass with respect to 100% by mass of the non-volatile content in the resin composition from the viewpoint of preventing a decrease in adhesion with the conductor layer. % By mass is more preferable, and 30% by mass is even more preferable. On the other hand, the lower limit of the content of the cyanate ester resin in the resin composition is from the viewpoint of preventing a decrease in heat resistance, an increase in thermal expansion coefficient, and an increase in dielectric loss tangent, with respect to 100% by mass of the nonvolatile content in the resin composition, 5 mass% is preferable, 8 mass% is more preferable, and 10 mass% is still more preferable.

  The ratio of the cyanate equivalent of the cyanate ester resin to the epoxy equivalent of the epoxy resin is preferably 1: 0.4 to 1: 2, and more preferably 1: 0.5 to 1: 1.5. When the equivalence ratio is less than 1: 0.4, the adhesion between the underlying conductor layer and the insulating layer tends to decrease, and when the equivalence ratio is more than 1: 2, the coefficient of thermal expansion and the dielectric loss tangent increase. Tend to.

  The resin composition of the present invention contains the component (A), the component (B), and the component (C), the dielectric loss tangent and thermal expansion coefficient of the insulating layer are low, and the adhesion between the conductor layer and the insulating resin is more stably maintained. However, flame retardancy can be imparted.

  The dielectric loss tangent characteristic of the resin composition containing the component (A), the component (B), and the component (C) of the present invention can be grasped by the measurement method described in <Measurement of dielectric loss tangent> described later.

  The upper limit value of the dielectric loss tangent characteristic of the resin composition of the present invention is preferably 0.018, more preferably 0.017, still more preferably 0.016, and still more preferably 0.015. The lower limit of the dielectric loss tangent characteristic of the resin composition of the present invention is preferably 0.004, more preferably 0.003, still more preferably 0.002, and still more preferably 0.001.

  The flame retardancy characteristics of the resin composition containing the component (A), the component (B), and the component (C) of the present invention can be grasped by an evaluation method described in <Flame retardance evaluation> described later.

  The flame retardant properties of the resin composition of the present invention all showed V-0.

  The adhesion strength before and after the environmental test of the resin composition containing the components (A), (B), and (C) of the present invention is described later <Measurement of adhesion strength between CZ-treated copper foil and resin composition> Can be grasped by the measuring method described in 1.

  The upper limit of the adhesion strength reduction rate before and after the environmental test of the resin composition of the present invention is preferably 70%, more preferably 65%, still more preferably 60%, and even more preferably 55%. The lower limit value of the adhesiveness reduction rate characteristic of the resin composition of the present invention is preferably 15%, more preferably 10%, still more preferably 8%, still more preferably 5%, even more preferably 1%, 0.1% % Is particularly preferred.

[(D) Organic peroxide]
By further containing (D) an organic peroxide in the resin composition of the present invention, the acrylate can be efficiently cured. There are no particular restrictions on the type of organic peroxide, but cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, diisopropyl Organic peroxides such as benzene hydroperoxide, cumene hydroperoxide, and tert-butyl hydroperoxide are listed. You may use these 1 type or in combination of 2 or more types.

  The content of the organic peroxide is not particularly limited as long as the acrylate can be efficiently cured. The upper limit of the content of the organic peroxide in the resin composition is preferably 3% by mass with respect to 100% by mass of the non-volatile content in the resin composition from the viewpoint of preventing increase in dielectric loss tangent and thermal expansion coefficient. 2 mass% is more preferable. On the other hand, the lower limit value of the content of the organic peroxide in the resin composition is 0.05 mass relative to 100 mass% of the non-volatile content in the resin composition from the viewpoint of preventing adhesion deterioration with the underlying conductor layer. % Is preferable, and 0.1% by mass is more preferable.

[(E) Metal-based curing accelerator]
The resin composition of the present invention can efficiently cure the cyanate ester resin by further containing (E) a metal curing accelerator. The type of the metal curing accelerator is not particularly limited, and examples thereof include an organometallic complex or an organometallic salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. Of these, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate, and iron (III) acetylacetonate are preferable from the viewpoints of curability and solvent solubility. Cobalt (II) acetylacetonate and zinc naphthenate are more preferable. You may use these 1 type or in combination of 2 or more types.

There is no restriction | limiting in particular in the addition amount of the metal type hardening accelerator in a resin composition. The upper limit of the addition amount of the metal-based curing accelerator in the resin composition is the acceleration of the metal-based curing with respect to 100% by mass of the non-volatile content in the resin composition from the viewpoint of preventing storage stability and deterioration of insulation. The metal content based on the agent is preferably 500 ppm, more preferably 200 ppm. On the other hand, the lower limit of the addition amount of the metal-based curing accelerator in the resin composition is preferably 25 ppm with respect to 100% by mass of the non-volatile content in the resin composition from the viewpoint of preventing the deterioration of adhesion with the underlying conductor layer. 40 ppm is more preferable.

[(F) Vinylbenzyl compound]
The dielectric composition can be improved by further containing (F) a vinylbenzyl compound in the resin composition of the present invention. The vinyl benzyl compound used in the present invention is not particularly limited, but is a compound having two or more vinyl benzyl groups in the molecule, and the indene compound is reacted with (i) vinyl benzyl halide in the presence of an alkali. (Ii) a method of reacting vinylbenzyl halide and a C2-C20 dihalomethyl compound in the presence of an alkali, or (iii) reaction of fluorene compound, vinylbenzyl halide and a C2-C20 dihalomethyl compound in the presence of an alkali. (Iv) a method of reacting a fluorene compound and vinyl benzyl halide in the presence of an alkali (WO 02/083610 pamphlet) or the like. From the viewpoint of low dielectric loss tangent, the vinylbenzyl compound preferably does not contain a hetero atom in the molecule.

  The content of the vinyl benzyl compound in the resin composition is not particularly limited. The upper limit of the content of the vinylbenzyl compound in the resin composition is preferably 50% by mass and more preferably 40% by mass with respect to 100% by mass of the non-volatile content in the resin composition from the viewpoint of preventing a decrease in adhesion. Preferably, 25 mass% is more preferable. On the other hand, the lower limit of the content of the vinylbenzyl compound in the resin composition is preferably 2% by mass, preferably 5% by mass with respect to 100% by mass of the nonvolatile content in the resin composition, from the viewpoint of preventing an increase in dielectric loss tangent. % Is more preferable, and 8% by mass is still more preferable.

式（５）中、Ｒ^３は、同一又は異なっていてもよく、水素原子、ハロゲン原子、アルキル基（好ましくは炭素数１〜５のアルキル基）、アルコキシ基（好ましくは炭素数１〜５のアルコキシ基）及びチオアルコキシ基（好ましくは炭素数１〜５のチオアルコキシ基）からなる群より選択される１つの基を示し（または２以上のＲ^３が一体となって環を形成していてもよい）、ｐは０〜４の整数を示す。環を形成する場合としては、５〜８員のシクロアルキル環、ベンゼン環等の環が縮環した構造を挙げることができる。 Examples of the indene compound include indene compounds represented by the following formula (5) .

In Formula (5), R ³ may be the same or different, and is a hydrogen atom, a halogen atom, an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), or an alkoxy group (preferably having 1 to 5 carbon atoms). One group selected from the group consisting of an alkoxy group) and a thioalkoxy group (preferably a thioalkoxy group having 1 to 5 carbon atoms) (or two or more R ³ groups together to form a ring) P) represents an integer of 0 to 4. Examples of forming a ring include a structure in which a ring such as a 5- to 8-membered cycloalkyl ring or a benzene ring is condensed.

式（６）中、Ｒ^２は、同一又は異なっていてもよく、水素原子、ハロゲン原子、アルキル基（好ましくは炭素数１〜５のアルキル基）、アルコキシ基（好ましくは炭素数１〜５のアルコキシ基）及びチオアルコキシ基（好ましくは炭素数１〜５のチオアルコキシ基）からなる群より選択される１つの基を示し（または２以上のＲ^２が一体となって環を形成していてもよい）、ｍは０〜４の整数を示す。環を形成する場合としては、５〜８員のシクロアルキル環、ベンゼン環等の環が縮環した構造を挙げることができる。 Examples of the fluorene compound include fluorene compounds represented by the following formula (6).

In formula (6), R ² may be the same or different, and is a hydrogen atom, a halogen atom, an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), or an alkoxy group (preferably having 1 to 5 carbon atoms). One group selected from the group consisting of an alkoxy group) and a thioalkoxy group (preferably a thioalkoxy group having 1 to 5 carbon atoms) (or two or more R ² groups together to form a ring) And m represents an integer of 0 to 4. Examples of forming a ring include a structure in which a ring such as a 5- to 8-membered cycloalkyl ring or a benzene ring is condensed.

  Examples of the vinyl benzyl halide include those described above. Examples of the dihalomethyl compound having 2 to 20 carbon atoms include 1,2-dichloroethane, 1,2-dibromoethane, 1,3-dichloropropane, 1,3-dibromopropane, 1,4-dichlorobutane, 1,4- Alkylene dihalides such as dibromobutane, o-xylylene dichloride, o-xylylene dibromide, m-xylylene dichloride, m-xylylene dibromide, p-xylylene dichloride, p-xylylene dibromide, 4,4'-bis (Chloromethyl) biphenyl, 4,4′-bis (chloromethyl) diphenyl ether, 4,4′-bis (chloromethyl) diphenyl sulfide, 2,6-bis (bromomethyl) naphthalene, 1,8-bis (bromomethyl) naphthalene 1,4-bis (chloromethyl) naphthalene and the like.

  Examples of the alkali include sodium methoxide, sodium ethoxide, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide and the like.

  Such a vinyl benzyl compound can be easily produced according to the description in JP-A No. 2003-277440 and WO 02/083610.

  The kind of the vinylbenzyl compound is not particularly limited, but those represented by the following formula (7) are preferable.

式（７）中、Ｒ^１は炭素数２〜２０の２価の有機基を示し、Ｒ^２は、同一又は異なっていてもよく、水素原子、ハロゲン原子、アルキル基（好ましくは炭素数１〜５のアルキル基）、アルコキシ基（好ましくは炭素数１〜５のアルコキシ基）及びチオアルコキシ基（好ましくは炭素数１〜５のチオアルコキシ基）からなる群より選択される１つの基を示し（または２以上のＲ^２が一体となって環を形成していてもよい）、ｍは０〜４の整数を示し、ｎは平均値として０〜２０の数を示す。環を形成する場合としては、５〜８員のシクロアルキル環、ベンゼン環等の環が縮環した構造を挙げることができる。

In Formula (7), R ¹ represents a divalent organic group having 2 to 20 carbon atoms, and R ² may be the same or different, and may be a hydrogen atom, a halogen atom, or an alkyl group (preferably having a carbon number of 1 to 5 group), an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms) and a thioalkoxy group (preferably a thioalkoxy group having 1 to 5 carbon atoms). Alternatively, two or more R ² may be integrated to form a ring), m represents an integer of 0 to 4, and n represents an average value of 0 to 20. Examples of forming a ring include a structure in which a ring such as a 5- to 8-membered cycloalkyl ring or a benzene ring is condensed.

（式（８）中、Ｒ^４は炭素数２〜２０の２価の有機基（好ましくはアルキル基）、ｎは平均値として０〜２０の数を示す） As the vinylbenzyl compound, those represented by the following formula (8) are more preferable.

(In the formula (8), R ⁴ is a divalent organic group (preferably an alkyl group) having 2 to 20 carbon atoms, and n is an average value of 0 to 20)

  As commercially available products, polyvinyl benzyl resin V-5000X (Tg 154 ° C. of cured product, relative dielectric constant 2.63, dielectric loss tangent 0.0016) manufactured by Showa Polymer Co., Ltd., V-6000X (of cured product) Tg 136 ° C., relative dielectric constant 2.59, dielectric loss tangent 0.0013) and the like.

  The vinyl benzyl compound in the present invention may be a vinyl benzyl ether compound. It can be obtained by reacting a compound having two or more hydroxybenzyl groups in one molecule (polyphenol compound) with vinylbenzyl halide in the presence of an alkali (JP-A-9-31006, JP-A-2001-181383). See the official gazette).

  Examples of the polyphenol compound include hydroquinone, bisphenol A, bisphenol F, bisphenol S, biphenol, phenol novolac resin, a phenol / benzaldehyde condensate, and a xylok type phenol resin. The aromatic ring of these compounds is preferably substituted with an alkyl group, halogen or the like.

  Examples of the vinyl benzyl halide include p-vinyl benzyl chloride, m-vinyl benzyl chloride, and any mixture thereof.

Although there is no restriction | limiting in particular in the kind of vinylbenzyl ether compound, The thing represented by the following formula | equation (9) can be mentioned (refer Unexamined-Japanese-Patent No. 9-31006, Unexamined-Japanese-Patent No. 2001-181383 etc.).

式（９）中、Ｒ^１はメチル基又はエチル基、Ｒ^２は水素原子又は１〜１０の炭化水素基、Ｒ^３は水素原子又はビニルベンジル基（但し、水素原子とビニルベンジル基のモル比は６０：４０〜０：１００の範囲である）、ｎは平均値として２〜４の数を表す。

In formula (9), R ¹ is a methyl group or an ethyl group, R ² is a hydrogen atom or a hydrocarbon group of 1 to 10, R ³ is a hydrogen atom or a vinylbenzyl group (provided that the molar ratio of the hydrogen atom to the vinylbenzyl group) Is a range of 60:40 to 0: 100), and n represents a number of 2 to 4 as an average value.

  These polyvinyl benzyl ether compounds can be easily produced according to the descriptions in JP-A-9-31006 and JP-A-2001-181383.

  The products available on the market are Showa Polymer Co., Ltd. V-1000X (Tg 160 ° C. of cured product, relative dielectric constant 2.7, dielectric loss tangent 0.0045), V-1100X (Tg 171 ° C. of cured product, ratio) Dielectric constant 2.56, dielectric loss tangent 0.0038) and the like.

  You may use these 1 type or in combination of 2 or more types.

[(G) polymer compound]
The resin composition of the present invention can further improve the mechanical strength of the cured product by containing (G) a polymer compound. Furthermore, the film molding ability when used in the form of an adhesive film can also be improved. Such (G) polymer compound is not particularly limited, but polyvinyl acetal resin, phenoxy resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate Examples thereof include resins, polyether ether ketone resins, and polyester resins. Of these, polyvinyl acetal resin and phenoxy resin are preferable. As the polyvinyl acetal resin, a polyvinyl butyral resin is more preferable. You may use these 1 type or in combination of 2 or more types.

  Specific examples of the polyvinyl acetal resin include those manufactured by Denki Kagaku Kogyo Co., Ltd., electrified butyral 4000-2, 5000-A, 6000-C, 6000-EP, and Sekisui Chemical Co., Ltd., ESREC BH series, BX series, and KS. Series, BL series, BM series and the like. Specific examples of the phenoxy resin include FX280 and FX293 manufactured by Toto Kasei Co., Ltd., YX8100, YX6954, YL6974, YL7482, YL7553, YL6794, YL7213, YL7290, and the like manufactured by Japan Epoxy Resins Co., Ltd. The polyvinyl acetal resin having a glass transition temperature of 80 ° C. or higher is particularly preferable. The “glass transition temperature” here is determined according to the method described in JIS K7197. When the glass transition temperature is higher than the decomposition temperature and the glass transition temperature is not actually observed, the decomposition temperature can be regarded as the glass transition temperature in the present invention. The decomposition temperature is defined as the temperature at which the mass reduction rate is 5% when measured according to the method described in JIS K 7120.

  The weight average molecular weight of the polymer compound is preferably in the range of 5,000 to 200,000. If it is smaller than this range, the effect of improving the film forming ability and mechanical strength tends to be insufficient. If it is larger than this range, the compatibility with the cyanate ester resin and the epoxy resin is lowered, and the surface of the insulating layer is roughened. Later roughness tends to increase.

  In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L is measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  The content of the polymer compound is not particularly limited. The upper limit of the content of the polymer compound in the resin composition is 20% by mass with respect to 100% by mass of the nonvolatile content in the resin composition from the viewpoint of preventing the roughness of the insulating layer surface after the roughening from increasing. Is preferable, and 15 mass% is more preferable. On the other hand, the lower limit of the content of the polymer compound in the resin composition is 1% by mass with respect to 100% by mass of the non-volatile content in the resin composition from the viewpoint of obtaining an effect of improving film molding ability and mechanical strength. Is preferable, and 2 mass% is more preferable.

[(H) inorganic filler]
The resin composition of the present invention can further reduce the thermal expansion coefficient of the insulating layer by further blending (H) an inorganic filler. The inorganic filler is not particularly limited, but silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Examples include barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica is preferable, and amorphous silica, fused silica, crystalline silica, and synthetic silica are more preferable. The shape of silica is preferably spherical. You may use these 1 type or in combination of 2 or more types.

The average particle diameter of the inorganic filler is not particularly limited. The upper limit value of the average particle size of the inorganic filler is preferably 5 μm, more preferably 1 μm, and still more preferably 0.7 μm, from the viewpoint of enabling fine wiring formation on the insulating layer. On the other hand, the lower limit of the average particle size of the inorganic filler is preferably 0.05 μm from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing when the resin composition is a resin varnish. 0.1 μm is more preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba Ltd. can be used.

  The inorganic filler is preferably one that has been surface treated with a surface treatment agent to improve its moisture resistance. As the surface treatment agent, aminosilane-based cups such as aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-2 (aminoethyl) aminopropyl trimethoxysilane, etc. Epoxy silanes such as ring agents, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane Coupling agents, mercaptosilane coupling agents such as mercatopropyltrimethoxysilane, mercatopropyltriethoxysilane, methyltrimethoxysilane, octadecyltrimethoxysilane Silane coupling agents such as lan, phenyltrimethoxysilane, methacroxypropyltrimethoxysilane, imidazolesilane, triazinesilane, hexamethyldisilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, 1,1,3,3 , 5,5-hexametacyclotrisilazane and other organosilazane compounds, butyl titanate dimer, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (Dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxy titanium monostearate, Tra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) Bis (ditridecyl) phosphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tri Dodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) Titanate, isopropyl tri (N- amidoethyl-aminoethyl) titanate coupling agents such as titanates.

  The addition amount of the inorganic filler is not particularly limited. The upper limit of the amount of the inorganic filler added is preferably 80% by mass with respect to 100% by mass of the non-volatile content in the resin composition from the viewpoint of preventing the cured product from becoming brittle and reducing the peel strength. 75 mass% is more preferable, and 70 mass% is still more preferable. On the other hand, the lower limit of the addition amount of the inorganic filler is preferably 10% by mass and 20% by mass with respect to 100% by mass of the non-volatile content in the resin composition from the viewpoint of sufficiently obtaining the effect of blending the inorganic filler. % Is more preferable, and 30% by mass is still more preferable.

[(I) Rubber particles]
The resin composition of the present invention can improve plating adhesion by further containing (I) rubber particles. The rubber particles are not particularly limited, but those that do not dissolve in the organic solvent used when preparing the varnish of the resin composition and are incompatible with the essential components cyanate ester resin and epoxy resin are used. be able to. Accordingly, the rubber particles exist in a dispersed state in the varnish of the resin composition of the present invention. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles.

  The rubber particles that can be used in the present invention are preferably core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and the like. The core-shell type rubber particle is a rubber particle having a core layer and a shell layer. The outer shell layer is made of a glassy polymer, and the inner core layer is made of a rubbery polymer. Examples include a three-layer structure in which the shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glass layer is made of a polymer of methyl methacrylate, and the rubbery polymer layer is made of a butyl acrylate polymer (butyl rubber). Two or more rubber particles may be used in combination. Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N (trade name, manufactured by Ganz Kasei Co., Ltd.), and Metabrene KW-4426 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size: 0.5 μm, manufactured by JSR Corporation). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include methabrene W300A (average particle size 0.1 μm), W450A (average particle size 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.), and the like. You may use these 1 type or in combination of 2 or more types.

  The average particle diameter of the rubber particles to be blended is preferably 0.005 to 1 μm, and more preferably 0.2 to 0.6 μm. The average particle diameter of the rubber particles used in the present invention can be measured using a dynamic light scattering method. The rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of the rubber particles is created on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.) It can be measured by setting the median diameter as the average particle diameter.

  1-10 mass% is preferable with respect to 100 mass% of non volatile matters in a resin composition, and, as for content of a rubber particle, 2-5 mass% is more preferable.

[(J) Flame retardant (excluding (meth) acrylate compounds having a phosphaphenanthrene skeleton)]
The resin composition of the present invention can further impart flame retardancy by further containing (J) a flame retardant (excluding a (meth) acrylate compound having a phosphaphenanthrene skeleton). Although it does not specifically limit as a flame retardant (except the (meth) acrylate compound which has a phosphaphenanthrene skeleton), An organic phosphorus flame retardant, an organic nitrogen containing phosphorus compound, a nitrogen compound, a silicone flame retardant, metal hydroxide Thing etc. are mentioned. Examples of organic phosphorus flame retardants include phenanthrene-type phosphorus compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd., and Ajinomoto Co., Inc. Reefos 30, 50, 65, 90, 110, Fine Techno Co., TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, PPQ, Clariant (made by Hokuko Chemical Co., Ltd.) Phosphoric acid ester compounds such as OP930 manufactured by Daihachi Chemical Co., Ltd., FX289 compounds manufactured by Tohto Kasei Co., Ltd., phosphorus-containing epoxy resins such as FX305, phosphorus such as ERF001 manufactured by Tohto Kasei Co., Ltd. And a phosphorus-containing epoxy resin such as YL7613 manufactured by Japan Epoxy Resin Co., Ltd. Examples of organic nitrogen-containing phosphorus compounds include phosphate ester compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP-series manufactured by Fushimi Seisakusho Co., Ltd. Examples thereof include phosphazene compounds. As the metal hydroxide, magnesium hydroxide such as UD65, UD650, UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308 manufactured by Sakai Kogyo Co., Ltd. Examples thereof include aluminum hydroxide such as B-303 and UFH-20. You may use these 1 type or in combination of 2 or more types.

[(K) curing accelerator (excluding metal-based curing accelerator and organic peroxide)]
The resin composition of the present invention can further improve the curing performance of the resin composition by containing (K) a curing accelerator (excluding metal-based curing accelerators and organic peroxides). Although it does not specifically limit as a hardening accelerator (a metal type hardening accelerator and an organic peroxide are remove | excluded), An imidazole type hardening accelerator, an amine type hardening accelerator, an azo type compound etc. are mentioned. You may use these 1 type or in combination of 2 or more types.

  The type of imidazole curing accelerator is not particularly limited, but 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl- 2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate 1-cyano Ethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'- Undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2, 4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl- Examples thereof include imidazole compounds such as 2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.

  The type of amine curing accelerator is not particularly limited, but trialkylamine such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, And amine compounds such as 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU).

  The type of the azo compound is not particularly limited, and examples thereof include azo compounds such as azobisisobutyronitrile and azobisdiethylvaleronitrile.

There is no restriction | limiting in particular in content of a hardening accelerator (except for a metal type hardening accelerator and an organic peroxide). The upper limit of the content of the curing accelerator (excluding metal-based curing accelerators and organic peroxides) in the resin composition is from the viewpoint of preventing increase in dielectric loss tangent and coefficient of thermal expansion. 3 mass% is preferable with respect to 100 mass% of non volatile matters, and 2 mass% is more preferable. On the other hand, the lower limit of the content of the curing accelerator (except for the metal-based curing accelerator and the organic peroxide) in the resin composition is within the resin composition from the viewpoint of preventing a decrease in adhesion with the underlying conductor layer. The non-volatile content of 100% by mass is preferably 0.05% by mass, and more preferably 0.1% by mass.

  The resin composition of this invention can use the various additives which can be mix | blended with a resin composition to such an extent that the effect of this invention is not inhibited. Specifically, organic fillers such as silicon powder, nylon powder, and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based, polymer-based antifoaming or leveling agents, imidazole-based, thiazole-based Examples thereof include adhesion imparting agents such as triazole-based and silane-based coupling agents, and colorants such as phthalocyanine / blue, phthalocyanine / green, iodin / green, disazo yellow, and carbon black.

  The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a compounding component is added with a solvent or the like as necessary and mixed using a rotary mixer or the like.

  The resin composition of the present invention can be used as a sheet-like material such as an adhesive film or a prepreg.

[Adhesive film]
The adhesive film of the present invention can be produced by methods known to those skilled in the art. A resin varnish in which a resin composition is dissolved in an organic solvent is prepared. It can be produced by forming a physical layer.

  As organic solvents, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetate esters such as carbitol acetate, carbitols such as cellosolve, butyl carbitol, Aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like can be mentioned. Two or more organic solvents may be used in combination.

  Although drying conditions are not specifically limited, 10 mass% or less is preferable and, as for content of the organic solvent to the resin composition layer after drying, 5 mass% or less is more preferable. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for 3 to 10 minutes. Can do. Those skilled in the art can appropriately set suitable drying conditions through simple experiments.

  The thickness of the resin composition layer formed in the adhesive film is preferably equal to or greater than the thickness of the conductor layer. When the thickness of the conductor layer included in the circuit board is 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm.

  Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. Various plastic films are listed. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. The support and a protective film described later may be subjected to surface treatment such as mud treatment or corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.

  Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

  A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, 1-40 micrometers is preferable and 10-30 micrometers is more preferable. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can also be stored in a roll.

[Prepreg]
The prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing base material made of fibers by a hot melt method or a solvent method, and heating and semi-curing. That is, it can be set as the prepreg which will be in the state which the resin composition of this invention impregnated the sheet-like reinforcement base material which consists of fibers. As the sheet-like reinforcing substrate made of fibers, those made of fibers commonly used as prepreg fibers such as glass cloth and aramid fibers can be used.

  In the hot melt method, the resin composition of the present invention is once coated on a coated paper having good releasability from the resin without dissolving it in an organic solvent, and then laminated on a sheet-like reinforcing substrate, or resin In this method, the prepreg is produced by directly coating a sheet-like reinforcing substrate with a die coater without dissolving it in an organic solvent. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying.

[Multilayer printed wiring board]
The resin composition of the present invention can be suitably used for forming an insulating layer in the production of a multilayer printed wiring board. The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but industrially, it is preferably used in the form of a sheet-like material such as an adhesive film or a prepreg. The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminate property of the sheet-like laminated material.

  First, an example of a method for producing a multilayer printed wiring board using the adhesive film produced as described above will be described.

  First, an adhesive film is laminated on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

In the above laminate, when the adhesive film has a protective film, after removing the protective film, the adhesive film and the circuit board are preheated as necessary, and the adhesive film is pressed and heated to the circuit board. Crimp. In the adhesive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. Lamination conditions are not particularly limited, but the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9). × 10 ⁴ N / m ² ) and laminating under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll.

  The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include Nichigo Morton's vacuum applicator, Maki Seisakusho's vacuum pressurizing laminator, Hitachi Industries' roll-type dry coater, Hitachi AIC Co., Ltd. A vacuum laminator etc. can be mentioned.

  After laminating the adhesive film on the circuit board, it is cooled to around room temperature, and when the support is peeled off, the insulating film can be formed on the circuit board by peeling and thermosetting. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, and the curing temperature is preferably 150 ° C to 220 ° C, more preferably 160 ° C to 200 ° C. The curing time is preferably 20 minutes to 180 minutes, more preferably 30 to 120 minutes.

  If the support is not peeled off after the insulating layer is formed, it is peeled off here. Next, if necessary, holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed by a known method such as drilling, laser, plasma, or a combination of these methods if necessary. Of these, drilling with a laser such as a carbon dioxide laser or a YAG laser is preferred.

  Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, the surface of the hardened insulating layer is first oxidized with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. Roughening treatment is performed with an agent to form uneven anchors. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, a subtractive method, a semi-additive method, or the like known to those skilled in the art can be used.

  Next, an example of a method for producing a multilayer printed wiring board using the prepreg produced as described above will be described.

First, one or several prepregs of the present invention are stacked on a circuit board, sandwiched by a metal plate through a release film, and press laminated under pressure and heating conditions. The pressurization / heating conditions are preferably a pressure of 5 to 40 kgf / cm ² (49 × 10 ^{4 to} 392 × 10 ⁴ N / m ² ), a temperature of 120 to 200 ° C., and a time of 20 to 100 minutes. Similarly to the adhesive film, the prepreg can be laminated on a circuit board by a vacuum laminating method and then cured by heating. Thereafter, in the same manner as described above, the surface of the cured prepreg is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.

    EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “part” means “part by mass”.

[Measurement and evaluation methods]
First, various measurement methods and evaluation methods will be described.

<Measurement of linear thermal expansion coefficient and glass transition temperature>
Adhesive films of resin composition layers in Examples and Comparative Examples were obtained using PET ("Fluorogen RL50KSE" manufactured by Mitsubishi Resin Co., Ltd.) treated with a fluororesin mold release agent (ETFE) on the support. The adhesive film was thermally cured at 190 ° C. for 90 minutes to obtain a sheet-like cured product, which was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and heat / stress produced by SII Nanotechnology.・ Thermomechanical analysis was performed by the tensile load method using a strain measuring device (EXSTAR TMA / SS6100) After mounting the test piece on the device, under the measurement conditions of 1 g load and 5 ° C./min. The average linear thermal expansion coefficient (ppm) was calculated from 25 ° C. to 150 ° C. in the second measurement, and the difference in slope of the dimensional change signal in the second measurement was calculated. To calculate the transition temperature (℃).

<Measurement of dielectric loss tangent>
Adhesive films of resin composition layers in Examples and Comparative Examples were obtained using PET ("Fluorogen RL50KSE" manufactured by Mitsubishi Resin Co., Ltd.) treated with a fluororesin mold release agent (ETFE) on the support. The adhesive film was cured by heating at 190 ° C. for 90 minutes, and the support was peeled off to obtain a sheet-like cured product, which was cut into a length of 80 mm and a width of 2 mm as an evaluation sample. The evaluation sample was measured for dielectric loss tangent at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using an HP 8362B apparatus manufactured by Agilent Technologies.

<Evaluation of flame retardancy>
A batch of 80 μm adhesive films prepared in Examples and Comparative Examples was applied to both sides of a base material from which the copper foil of a copper-clad laminate (“679-FG” manufactured by Hitachi Chemical Co., Ltd.) having a substrate thickness of 0.2 mm was removed by etching. The laminate was laminated on both sides of the laminated plate using a vacuum pressurizing laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.). Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. After peeling the PET film from the support, it was thermoset at 190 ° C. for 90 minutes to obtain a flame retardant test sample. The width was cut to 12.7 mm and the length was 127 mm, and the cut surface was polished with a polishing machine (Struers, RotoPol-22). The above five samples were made into one set, and the flame retardant test was performed according to the UL94 vertical flame retardant test. When there was no unburned sample after 10 seconds of indirect flame, it was set as x.
<Measurement of adhesion strength between CZ-treated copper foil and resin composition>
(1) Substrate treatment of laminated board Both sides of glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.3mm, Matsushita Electric Works R5715ES) on which inner layer circuits were formed The surface of the copper was roughened by being immersed in Mek Et Bond CZ8100 manufactured by Co., Ltd. (Ra value 1 μm).
(2) Lamination of adhesive film The adhesive film created in Examples and Comparative Examples was laminated on both sides of a laminate using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.). . Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.
(3) Substrate treatment of copper foil The glossy surface of 3EC-III (electrolytic copper foil, 35 μm) manufactured by Mitsui Mining Co., Ltd. is immersed in Mec Etch Bond CZ-8100 manufactured by Mec Co., Ltd., and roughened on the copper surface. (Ra value 1 μm).
(4) Lamination of copper foil and formation of insulating layer The PET film is peeled from the adhesive film laminated in (2) above, and the treated surface of the copper foil treated in (3) is set to the resin composition layer side. Under the same conditions as in 2), the copper foil was laminated on the resin composition layer formed on both surfaces of the circuit board. A sample was prepared by curing the resin composition at 190 ° C. for 90 minutes to form an insulating layer.
(5) Measurement of adhesion strength Sample 510 × 340 mm of (4) above was cut into small pieces of 150 × 30 mm. Cut the copper foil part of the small piece with a width of 10 mm and a length of 100 mm, peel off one end of the copper foil and grab it with a gripper, and use an Instron universal testing machine at room temperature, 50 mm / min. The load when peeling 35 mm in the vertical direction at a speed of was measured in accordance with JIS C6481, and was defined as the adhesion strength (kgf / cm).
(6) Measurement of adhesion strength under high temperature and high humidity The sample of (4) above is subjected to a HAST test (highly accelerated temperature and humidity Stress Test) that is allowed to stand for 100 hours at 130 ° C. in an environment of 85% RH. Carried out. Thereafter, the temperature was returned to room temperature, and the adhesion strength was measured in the same manner as in (5) above.

[Example 1]
Prepolymer of bisphenol A dicyanate (“BA230S75” manufactured by Lonza Japan Co., Ltd., 13 parts by mass of methyl ethyl ketone (hereinafter abbreviated as MEK) solution having a cyanate equivalent of about 232 and a non-volatile content of 75% by mass, a phenol novolac type polyfunctional cyanate ester resin ( After 9 parts by mass of “PT30” manufactured by Lonza Japan Co., Ltd., cyanate equivalent weight of about 124) together with 20 parts of cyclohexanone was heated and dissolved, “ESN-475V” manufactured by Tohto Kasei Co., Ltd. as a naphthol type epoxy resin (the above general formula ( 1) 15 parts by mass of a toluene solution with an epoxy equivalent of about 340 having a nonvolatile content of about 340, and 3 parts by mass of a liquid bisphenol A type epoxy resin (“jER828EL” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent of about 185) Part, biphenyl type epoxy tree (MEK solution having an epoxy equivalent of about 328 with a nonvolatile content of 75% by mass, “NC3000FH-75M” manufactured by Nippon Kayaku Co., Ltd.), phosphorus-containing epoxy resin (“FX289EK75” manufactured by Toto Kasei Co., Ltd.), epoxy equivalent of about 306 7 parts by mass of a MEK solution having a nonvolatile content of 75% by mass, phosphaphenanthrene skeleton-containing acrylate (“HFA-6007M” manufactured by Showa Polymer Co., Ltd.) 2-methoxypropanol having a nonvolatile content of 65% by mass, phosphorus content of 8.6 %) 7 parts by mass, 11 parts by mass of phenoxy resin solution (“YX-6654” manufactured by Japan Epoxy Resin Co., Ltd., a mixed solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass), dicumyl peroxide as an organic peroxide (Nippon Yushi Co., Ltd. “Park Mill D” 0.5 parts by mass, adduct of imidazole compound and epoxy resin 3 parts by mass (Japan Epoxy Resin Co., Ltd. “jERcure P200H50”, propylene glycol monomethyl ether solution having a nonvolatile content of 50% by mass), cobalt (II) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) % N, N-dimethylformamide (DMF) solution 4 parts by mass and spherical silica (“SOC2” manufactured by Admatechs Co., Ltd., surface-treated with aminosilane, average particle size 0.5 μm, 3 um upper limit cut product) 85 Mass parts were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a varnish of a thermosetting resin composition.
In the nonvolatile content of the resin composition, 26% by mass of epoxy resin, 12% by mass of cyanate ester resin, 3% by mass of acrylate containing phosphaphenanthrene skeleton, 0.3% of organic peroxide, 0.2% by mass of curing accelerator, organic The metal (cobalt) added as a metal catalyst is 48 ppm, the polymer resin is 2% by mass, and the inorganic filler is 56% by mass.
Next, such a resin composition varnish is uniformly applied on a polyethylene terephthalate film (thickness 38 μm, hereinafter abbreviated as PET film) with a die coater so that the thickness of the resin composition layer after drying is 40 μm, It dried for 6 minutes at 80-120 degreeC (average 100 degreeC) (residual solvent amount in a resin composition layer: about 1.5 mass%). Subsequently, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film on the surface of a resin composition layer. The roll-like adhesive film was slit to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 × 336 mm.

[Example 2]
Dicyclopentadiene type cyanate ester resin (Lonza Japan Co., Ltd. "DT-4000", cyanate equivalent of about 140, non-volatile content 85% by weight toluene solution) 13.8 parts by weight, bisphenol A dicyanate prepolymer (Lonza Japan ( "BA230S75" manufactured by Co., Ltd., 21 parts by mass of methyl ethyl ketone (hereinafter abbreviated as MEK) solution having a cyanate equivalent of about 232 and a non-volatile content of 75% by mass, and biphenyl type epoxy resin (epoxy equivalent 269, manufactured by Nippon Kayaku Co., Ltd. "NC3000L" ”) 15 parts together with 20 parts of cyclohexanone was heated and dissolved, and then 3 parts by weight of a naphthalene type bifunctional epoxy resin (DIC Corporation“ HP4032SS ”epoxy equivalent of about 145), a phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd.) “FX289EK75”, epoxy equivalent of about 30 21 parts by mass of a MEK solution having a nonvolatile content of 75% by mass, 7 parts by mass of a vinylbenzyl compound (“V5000X” manufactured by Showa Polymer Co., Ltd., a toluene solution having a nonvolatile content of 65% by mass), an acrylate containing a phosphaphenanthrene skeleton (Showa) 6 parts by mass of “HFA-6007M” manufactured by Polymer Co., Ltd., 2-methoxypropanol having a nonvolatile content of 65% by mass and a phosphorus content of 8.6%) was added. Thereto, 50 parts of a polyvinyl butyral resin solution (glass transition temperature 105 ° C., “KS-1” manufactured by Sekisui Chemical Co., Ltd.) is mixed with 50 parts of a solid solution of cyclohexanone and MEK having a solid content of 15%, and further organic. Dicumyl peroxide (Nippon Yushi Co., Ltd. “Park Mill D” 0.5 part by mass, adduct of imidazole compound and epoxy resin (Japan Epoxy Resin Co., Ltd. “jERcure P200H50”) 0.4 Parts by mass, 3 parts by mass of a 3% by mass cyclohexanone solution of zinc naphthenate (II) (manufactured by Tokyo Chemical Industry Co., Ltd., mineral spirit solution having a zinc content of 8%), and spherical silica ("SOC2" manufactured by Admatechs Co., Ltd.) ”Surface treated with aminosilane, average particle size 0.5 μm, 3 um upper limit cut product) A varnish of a thermosetting resin composition was prepared by uniformly dispersing with a xer.
In the nonvolatile content of the resin composition, 19% by mass of epoxy resin, 15% by mass of cyanate ester resin, 3% by mass of vinylbenzyl compound, 2% by mass of acrylate containing phosphaphenanthrene skeleton, 0.3% by mass of organic peroxide, acceleration of curing 0.1 mass% of the agent, 39 ppm of metal (zinc) added as the organometallic catalyst, 4 mass% of the polymer resin, and 57 mass% of the inorganic filler.
Next, using this resin composition varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

Example 3
Dicyclopentadiene type cyanate ester resin (Lonza Japan Co., Ltd. "DT-4000", cyanate equivalent of about 140, non-volatile content 85% by weight toluene solution) 13.8 parts by weight, bisphenol A dicyanate prepolymer (Lonza Japan ( "BA230S75" manufactured by Co., Ltd., 21 parts by mass of methyl ethyl ketone (hereinafter abbreviated as MEK) solution having a cyanate equivalent of about 232 and a non-volatile content of 75% by mass, and biphenyl type epoxy resin (epoxy equivalent 269, manufactured by Nippon Kayaku Co., Ltd. "NC3000L" ”) 15 parts together with 20 parts of cyclohexanone was heated and dissolved, and then 3 parts by weight of a naphthalene type bifunctional epoxy resin (DIC Corporation“ HP4032SS ”epoxy equivalent of about 145), a phosphorus-containing epoxy resin (manufactured by Toto Kasei Co., Ltd.) “FX289EK75”, epoxy equivalent of about 30 21 parts by mass of a MEK solution having a nonvolatile content of 75% by mass, 7 parts by mass of a vinylbenzyl compound (“V5000X” manufactured by Showa Polymer Co., Ltd., a toluene solution having a nonvolatile content of 65% by mass), an acrylate containing a phosphaphenanthrene skeleton (Showa) 12 parts by mass of “HFA-6007M” manufactured by Polymer Co., Ltd., 2-methoxypropanol having a nonvolatile content of 65% by mass and phosphorus content of 8.6%) was added. Thereto, 50 parts of a polyvinyl butyral resin solution (glass transition temperature 105 ° C., “KS-1” manufactured by Sekisui Chemical Co., Ltd.) is mixed with 50 parts of a solid solution of cyclohexanone and MEK having a solid content of 15%, and further organic. Dicumyl peroxide (Nippon Yushi Co., Ltd. “Park Mill D” 0.5 part by mass, adduct of imidazole compound and epoxy resin (Japan Epoxy Resin Co., Ltd. “jERcure P200H50”) 0.4 Parts by mass, 3 parts by mass of a 3% by mass cyclohexanone solution of zinc naphthenate (II) (manufactured by Tokyo Chemical Industry Co., Ltd., mineral spirit solution having a zinc content of 8%), and spherical silica ("SOC2" manufactured by Admatechs Co., Ltd.) ”Surface treated with aminosilane, average particle size 0.5 μm, 3 um upper limit cut product) A varnish of a thermosetting resin composition was prepared by uniformly dispersing with a xer.
In the nonvolatile content of the resin composition, 18% by mass of epoxy resin, 15% by mass of cyanate ester resin, 2% by mass of vinylbenzyl compound, 4% by mass of acrylate containing phosphaphenanthrene skeleton, 0.3% by mass of organic peroxide, acceleration of curing 0.1 mass% of the agent, 39 ppm of metal (zinc) added as the organometallic catalyst, 4 mass% of the polymer resin, and 56 mass% of the inorganic filler.
Next, using this resin composition varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

Example 4
Prepolymer of bisphenol A dicyanate (“BA230S75” manufactured by Lonza Japan Co., Ltd., 13 parts by mass of methyl ethyl ketone (hereinafter abbreviated as MEK) solution having a cyanate equivalent of about 232 and a non-volatile content of 75% by mass, a phenol novolac type polyfunctional cyanate ester resin ( After 9 parts by mass of “PT30” manufactured by Lonza Japan Co., Ltd., cyanate equivalent weight of about 124) together with 20 parts of cyclohexanone was heated and dissolved, “ESN-475V” manufactured by Tohto Kasei Co., Ltd. as a naphthol type epoxy resin (the above general formula ( 1) 15 parts by mass of a toluene solution with an epoxy equivalent of about 340 having a nonvolatile content of about 340, and 3 parts by mass of a liquid bisphenol A type epoxy resin (“jER828EL” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent of about 185) Part, biphenyl type epoxy tree (MEK solution having an epoxy equivalent of about 328 with a nonvolatile content of 75% by mass, “NC3000FH-75M” manufactured by Nippon Kayaku Co., Ltd.), phosphorus-containing epoxy resin (“FX289EK75” manufactured by Toto Kasei Co., Ltd.), epoxy equivalent of about 306 7 parts by mass of MEK solution having a nonvolatile content of 75% by mass, phosphaphenanthrene skeleton-containing methacrylate (“HFM-9B” manufactured by Showa Polymer Co., Ltd.), propylene glycol monomethyl ether solution having a nonvolatile content of 80% by mass, phosphorus content 7 0.2%) 7 parts by mass, 11 parts by mass of phenoxy resin solution (“YX-6654” manufactured by Japan Epoxy Resin Co., Ltd., a mixed solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass), dicumyl as an organic peroxide Peroxide (0.5 parts by weight of “Park Mill D” manufactured by NOF Corporation), imidazole compound and epoxy Adduct with resin ("JERcure P200H50" manufactured by Japan Epoxy Resin Co., Ltd., 0.5 parts by mass of propylene glycol monomethyl ether solution having a nonvolatile content of 50% by mass), cobalt (II) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 3 mass% N, N-dimethylformamide (DMF) solution 4 parts by mass, and spherical silica ("SOC2" manufactured by Admatechs Co., Ltd., surface-treated with aminosilane, average particle size 0.5 μm, 3 um upper limit Cut product) 85 parts by mass were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a varnish of a thermosetting resin composition.
In the nonvolatile content of the resin composition, epoxy resin 25% by mass, cyanate ester resin 12% by mass, phosphaphenanthrene skeleton-containing acrylate 4% by mass, organic peroxide 0.3% by mass, curing accelerator 0.2% by mass, The metal (cobalt) added as an organometallic catalyst is 47 ppm, the polymer resin is 2 mass%, and the inorganic filler is 56 mass%. Next, using this resin composition varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

<Comparative Example 1>
In Example 1, a curable resin composition not containing phosphaphenanthrene-containing acrylate (“HFA-6007M” manufactured by Showa Polymer Co., Ltd., 2-methoxypropanol having a nonvolatile content of 65% by mass, phosphorus content of 8.6%) An adhesive film was obtained in the same manner as in Example 1 except that the above varnish was used.

<Comparative Example 2>
In Example 2, a curable resin composition containing no phosphaphenanthrene-containing acrylate ("HFA-6007M" manufactured by Showa Polymer Co., Ltd., 2-methoxypropanol having a nonvolatile content of 65% by mass, phosphorus content of 8.6%) An adhesive film was obtained in the same manner as in Example 1 except that the above varnish was used.

<Comparative Example 3>
In Example 1, instead of 7 parts by mass of phosphaphenanthrene-containing acrylate (“HFA-6007M” manufactured by Showa Polymer Co., Ltd., 2-methoxypropanol having a nonvolatile content of 65% by mass, phosphorus content of 8.6%) An adhesive film was prepared in exactly the same manner as in Example 1 except that a varnish of a curable resin composition to which 5 parts by mass of hydroxyethyl methacrylate phosphate ester (“JPA-514” manufactured by Johoku Chemical Industry Co., Ltd.) was added was used. Obtained.

The results are shown in Table 1.

From the results of Table 1, the insulating layer formed by the adhesive films obtained in Examples 1 to 4 has improved flame retardancy and does not deteriorate the thermal expansion coefficient and dielectric loss tangent, and CZ after the HAST test. It turns out that the fall rate of adhesiveness with copper foil is suppressed.
On the other hand, Comparative Examples 1 and 2 that do not contain a (meth) acrylate compound having a phosphaphenanthrene skeleton have insufficient flame retardancy compared to Examples 1 to 4, and the CZ copper foil after the HAST test Adhesion is also greatly reduced. In Comparative Example 3 containing methacrylate phosphate, although the flame retardancy was improved, the cured film was brittle, and various physical properties (linear thermal expansion coefficient, glass transition temperature, dielectric loss tangent) could not be measured. Furthermore, the adhesion with the CZ copper foil after the HAST test was greatly reduced.

  By containing a specific acrylate compound, epoxy resin, and cyanate ester resin, the dielectric loss tangent and thermal expansion coefficient of the formed insulating layer are low, and flame retardancy is maintained while maintaining more stable adhesion between the conductor layer and the insulating resin. It is significant that an improved resin composition, and further an adhesive film, a prepreg, and a circuit board can be provided.

Claims (14)

(A) A resin composition comprising a (meth) acrylate compound having a phosphaphenanthrene skeleton, (B) an epoxy resin, and (C) a cyanate ester resin.   When the nonvolatile content of the resin composition is 100% by mass, the content of the component (A) is 1 to 20% by mass, the content of the component (B) is 5 to 60% by mass, and the content of the component (C) is 2. The resin composition according to claim 1, wherein the resin composition is 5 to 50% by mass, and the ratio of the cyanate ester group to the epoxy group is 1: 0.4 to 1: 2.   3. The resin composition according to claim 1, further comprising (D) an organic peroxide.   Furthermore, (E) metal type hardening accelerator is contained, The resin composition of any one of Claims 1-3 characterized by the above-mentioned.   (E) The metal-based curing accelerator is an organometallic complex or an organometallic salt of one or more metals selected from cobalt, copper, zinc, iron, nickel, manganese, and tin. The resin composition described in 1.   The resin composition according to any one of claims 1 to 5, further comprising (F) a vinylbenzyl compound.   Furthermore, (G) a high molecular compound is contained, The resin composition of any one of Claims 1-6 characterized by the above-mentioned.   Furthermore, (H) inorganic filler is contained, The resin composition of any one of Claims 1-7 characterized by the above-mentioned.   Furthermore, (I) rubber particles are contained, The resin composition of any one of Claims 1-8 characterized by the above-mentioned.   Furthermore, (J) a flame retardant (except the (meth) acrylate compound which has a phosphaphenanthrene skeleton) is contained, The resin composition of any one of Claims 1-9 characterized by the above-mentioned.     Furthermore, (K) hardening accelerator (a metal type hardening accelerator and an organic peroxide are excluded) is contained, The resin composition of any one of Claims 1-10 characterized by the above-mentioned. The dielectric loss tangent characteristic is 0.001 to 0.018, and the decrease rate of adhesion strength before and after the environmental test is 0.1% to 70%, according to any one of claims 1 to 11. Resin composition.   A sheet-like material comprising the resin composition according to claim 1.   A multilayer printed wiring board comprising the sheet-like material according to claim 13.