JP2010285594A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition that provides a cured product having a low dielectric dissipation factor, and is adhered extremely strongly with a conductor after being subjected to accelerated environmental testing. <P>SOLUTION: The resin composition contains (A) an epoxy resin, (B) a cyanate ester resin, (C) an active ester curing agent, and (D) a curing accelerator. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition suitable for forming an insulating layer such as a multilayer printed wiring board.

  In recent years, computers and information communication devices have become increasingly high-performance and highly functional, and in order to process a large amount of data at high speed, the signals handled tend to be high-frequency. In particular, the frequency range of radio waves used in mobile phones and satellite broadcasts is in the high frequency range of the GHz band, and in order to suppress transmission loss due to higher frequencies, as an organic insulating material used in the high frequency range, A material having a low dielectric constant and dielectric loss tangent has been desired. As a resin composition used for an insulating layer of a multilayer printed wiring board, it is known that a resin composition containing a cyanate ester resin can form an insulating layer having excellent dielectric properties. Discloses a resin composition for a multilayer printed wiring board containing a cyanate ester resin, an epoxy resin, or the like, but its low dielectric loss tangent is not necessarily sufficient.

International Publication 2003/099952 Pamphlet International Publication No. 2008/044766 Pamphlet

  The present invention is a resin composition suitable for forming an insulating layer of a multilayer printed wiring board, wherein the dielectric tangent of the insulating layer is low, and the adhesion between the conductor layer and the insulating layer is improved before and after an environmental test under high temperature and high humidity. It is an object to provide a resin composition that can be stably maintained.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing (A) an epoxy resin, (B) a cyanate ester resin, (C) an active ester curing agent, and (D) a curing accelerator. The present invention has found that the above-mentioned problems can be achieved, and has completed the present invention. That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin, (B) a cyanate ester resin, (C) an active ester curing agent and (D) a curing accelerator.
[2] The resin composition according to the above [1], wherein the (D) curing accelerator is at least one selected from a metal curing accelerator, an amine curing accelerator, and an imidazole curing accelerator.
[3] (D) A metal-based curing accelerator comprising an organometallic complex or an organometallic salt of at least one metal selected from cobalt, copper, zinc, iron, nickel, manganese, and tin The resin composition according to the above [1] or [2].
[4] When the nonvolatile content of the resin composition is 100% by mass, the content of (A) epoxy resin is 5 to 60% by mass, the content of (B) cyanate ester resin is 5 to 50% by mass, (C ) The resin composition according to any one of [1] to [3], wherein the content of the active ester curing agent is 2 to 20% by mass.
[5] (D) When the curing accelerator contains a metal curing accelerator and the nonvolatile content of the resin composition is 100% by mass, the metal content based on the metal curing accelerator is 25 to 500 ppm. The resin composition according to any one of [1] to [4] above.
[6] (D) When the curing accelerator includes an amine curing accelerator and / or an imidazole curing accelerator and the nonvolatile content of the resin composition is 100% by mass, the amine curing accelerator and / or imidazole. Resin composition in any one of said [1]-[4] whose content of a system hardening accelerator is 0.05-3 mass%.
[7] The above [1] to [6], wherein the ratio of cyanate ester group to epoxy group is 1: 0.4 to 1: 2, and the ratio of ester group to epoxy group is 1: 2 to 1:20. The resin composition in any one of.
[8] The resin composition according to any one of [1] to [7], further including (E) an inorganic filler.
[9] The resin composition according to the above [8], wherein the inorganic filler is talc and silica.
[10] When the nonvolatile content of the resin composition is 100% by mass, the total content of talc and silica is 35% by mass to 70% by mass, and the content of talc is 5% by mass to 20% by mass. The resin composition as described in [9] above.
[11] The resin composition according to any one of [1] to [10], further comprising (F) a vinylbenzyl compound.
[12] The resin composition according to [11] above, wherein the content of the (F) vinylbenzyl compound is 2 to 50% by mass when the nonvolatile content of the resin composition is 100% by mass.
[13] Further (G) polyvinyl acetal resin, phenoxy resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin The resin composition according to any one of the above [1] to [12], which contains one or more polymer compounds selected from the group consisting of:
[14] The resin composition according to [13] above, wherein the content of the polymer compound is 1 to 20% by mass when the nonvolatile content of the resin composition is 100% by mass.
[15]
The dielectric loss tangent characteristic is 0.004 to 0.009, and the decrease rate of adhesion strength before and after the environmental test is 0% to 59%. Resin composition.
[16] An adhesive film in which the resin composition according to any one of [1] to [15] is layered on a support.
[17] A prepreg in which the resin composition according to any one of [1] to [15] is impregnated in a sheet-like reinforcing base material.
[18] A multilayer printed wiring board in which an insulating layer is formed of a cured product of the resin composition according to any one of [1] to [15].

  According to the present invention, a resin composition suitable for forming an insulating layer of a multilayer printed wiring board, wherein the insulating layer formed by the resin composition has a low dielectric loss tangent, and the insulating layer and the conductor after the accelerated environment test A resin composition having excellent layer adhesion is provided.

The present invention is a resin composition comprising (A) an epoxy resin, (B) a cyanate ester resin, (C) an active ester curing agent and (D) a curing accelerator.

[(A) Epoxy resin]
The epoxy resin used in the present invention is not particularly limited. For example, 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 condensate of phenol and aromatic aldehyde having phenolic hydroxyl group, biphenyl aralkyl Type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, triglycidyl isocyanurate and the like. Epoxy resins may be used alone or in combination of two or more. 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- 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 0.1 to The range is 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.

  Examples of 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. "HP4700" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation, "ESN-475V" and "ESN-185V" (naphthol type epoxy resin) manufactured by Toto Kasei Co., Ltd., "PB" manufactured by Daicel Chemical Industries, Ltd. -3600 "(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 "YX4000" (biphenyl type) Carboxymethyl resins), Japan Epoxy Resins Co., Ltd. "YX8800" (anthracene skeleton-containing epoxy resin) and the like.

  The content of the epoxy resin in the resin composition is not particularly limited, but is preferably 5 to 60% by mass, more preferably 10% when the nonvolatile content in the resin composition is 100% by mass. -50 mass%. If the content of the epoxy resin is too small, the adhesion strength with the underlying conductor layer tends to decrease. If the content of the epoxy resin is too large, the content of the cyanate ester resin is relatively decreased. Tangency tends to increase.

[(B) Cyanate ester resin]
The cyanate ester resin used in the present invention is not particularly limited, and examples thereof include 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, bisphenol S type, etc.) cyanate ester resins and prepolymers in which these are partially triazines. These may be used alone or in combination of two or more. The weight average molecular weight of the cyanate ester resin is not particularly limited, but preferably 500 to
It is 4500, More preferably, it is 600-3000.

Specific examples of the cyanate ester resin include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5- Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, phenol Novolac and Crezo Examples thereof include polyfunctional cyanate resins derived from lenovolac, dicyclopentadiene structure-containing phenol resins, etc., prepolymers in which these cyanate resins are partially triazines, etc. Cyanate ester resins are used alone or in combination of two or more. May be.

  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.)

  The content of the cyanate ester resin in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 5 to 50% by mass, more preferably It is 7-40 mass%, More preferably, it is 10-30 mass%. When there is too little content of cyanate ester resin, it exists in the tendency for heat resistance to fall and for a dielectric loss tangent to increase. When there is too much content of cyanate ester resin, it exists in the tendency for the adhesive strength of a base conductor layer and an insulating layer to fall.

  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, more preferably 1: 0.5 to 1: 1.5, Preferably it is 1: 0.6-1: 1.1. When the equivalence ratio is less than 1: 0.4, the adhesion strength between the base conductor layer and the insulating layer tends to decrease, and when the equivalence ratio is more than 1: 2, the dielectric loss tangent tends to increase. is there.

[(C) Active ester curing agent]
The active ester curing agent used in the present invention has an ester group with high reaction activity such as a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, an esterified compound of a heterocyclic hydroxy compound, and an epoxy resin. It has the hardening effect of. In particular, a phenol ester compound composed of a compound having two or more phenolic hydroxy groups in one molecule and a carboxylic acid derivative is preferable. Such a phenol ester compound is, for example, two or more phenolic hydroxy groups in one molecule. It can be produced by a method of reacting a curing agent having an ester with an esterifying agent, a method of polycondensing a polyfunctional carboxylic acid and an aromatic polyhydroxy compound, and esterifying the carboxy group with an aromatic monohydroxy compound. . For example, an active ester curing agent described in JP-A-2004-2277460 can be used. Different types of active ester curing agents may be used alone or in combination of two or more.

  Examples of commercially available active ester curing agents include EXB 9460-65T (manufactured by DIC Corporation, active group equivalent 223), DC808 (manufactured by Japan Epoxy Resin Co., Ltd., active group equivalent 149), YLH1026 (Japan Epoxy Resin Co., Ltd.). ), Active group equivalent 200), YLH1030 (manufactured by Japan Epoxy Resin Co., Ltd., active group equivalent 201), YLH1048 (manufactured by Japan Epoxy Resin Co., Ltd., active group equivalent 245), and the like.

  The content of the active ester curing agent in the resin composition is not particularly limited, but the upper limit of the content of the active ester curing agent is that the curing is slow and the curing time is long and the mechanical properties are lowered. From the viewpoint of preventing this, when the nonvolatile content in the resin composition is 100% by mass, 20% by mass is preferable, 19% by mass is more preferable, 18% by mass is further preferable, and 17% by mass is even more preferable. 16% by mass is particularly preferable, and 15% by mass is particularly preferable. On the other hand, the lower limit of the content of the active ester curing agent is preferably 1% by mass, preferably 2% by mass, when the nonvolatile content in the resin composition is 100% by mass, from the viewpoint of preventing increase in dielectric loss tangent. % Is more preferable, and 3% by mass is still more preferable.

  The ratio of the equivalent amount of the active ester curing agent to the epoxy group of the epoxy resin is preferably 1: 2 to 1:20, more preferably 1: 3 to 1:18, still more preferably 1: 3 to 1: 1. 16. When the equivalence ratio is less than 1: 2, unreacted active ester remains and the mechanical properties tend to decrease. When the equivalence ratio is more than 1:20, the dielectric loss tangent tends to increase. .

[(D) Curing accelerator]
Examples of the curing accelerator used in the present invention include a metal curing accelerator, an imidazole curing accelerator, and an amine curing accelerator. The curing accelerator may be used alone or in combination of two or more.

  Examples of the metal curing accelerator include organometallic complexes or organometallic salts of metals 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. As metal-based curing accelerators, from the viewpoint of curability and solvent solubility, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate, iron (III) Acetylacetonate is preferable, and cobalt (II) acetylacetonate and zinc naphthenate are particularly preferable. You may use a metal type hardening accelerator 1 type or in combination of 2 or more types.

  The addition amount of the metal-based curing accelerator is a range in which the metal content based on the metal-based curing accelerator is 25 to 500 ppm, more preferably 40 to 200 ppm when the nonvolatile content in the resin composition is 100% by mass. Is preferably added. If it is less than 25 ppm, it tends to be difficult to form a conductor layer having excellent adhesion to the surface of the low-roughness insulating layer, and if it exceeds 500 ppm, the storage stability and insulation of the resin composition tend to decrease. It becomes.

  Examples of the imidazole curing accelerator include 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-cyanoethyl-2- Feni Louis imidazolium 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-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-be Examples thereof include imidazole compounds such as benzyl imidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.

  Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5 , 4, 0) -undecene (hereinafter abbreviated as DBU) and the like.

  The content of curing accelerators other than metal-based curing accelerators such as imidazole-based curing accelerators and amine-based curing accelerators is 0.05 to 3% by mass when the nonvolatile content in the resin composition is 100% by mass. It is preferable that it is the range of 0.1-2 mass%. If it is less than 0.05% by mass, the adhesion strength with the underlying conductor layer tends to decrease, and if it exceeds 3% by mass, the dielectric loss tangent of the cured product tends to increase. When using a combination of a metal-based curing accelerator and other curing accelerators (imidazole-based curing accelerator, amine-based curing accelerator, etc.), the content of the metal-based curing accelerator and other curing accelerators (imidazole) It is preferable that the system-based curing accelerator, the amine-based curing accelerator, and the like are within the above ranges.

  The resin composition of the present invention comprises (A) component, (B) component, (C) component, and (D) component, the dielectric tangent of the insulating layer is low, and the adhesion between the conductor layer and the insulating resin is more stable. Can keep.

  The dielectric loss tangent of the resin composition of the present invention can be grasped by the measurement method described in <Measurement and evaluation of dielectric loss tangent> described later.

  The upper limit of the dielectric loss tangent of the resin composition of the present invention is preferably 0.009, more preferably 0.0089, still more preferably 0.0087, still more preferably 0.0085, still more preferably 0,0083, and 0 .0081 is particularly preferred. The lower limit of the dielectric loss tangent of the resin composition of the present invention is preferably 0.0072, more preferably 0.0070, still more preferably 0.0065, still more preferably 0.006, even more preferably 0.005, and 0 .004 is particularly preferred.

  The adhesion strength before and after the environmental test of the resin composition of the present invention can be grasped by the measurement method described in <Measurement and evaluation of adhesion strength between CZ-treated copper foil and resin composition> described later.

  59% is preferable, 45% is more preferable, 36% is further more preferable, 33% is still more preferable, and 30% is still more preferable, as for the upper limit of the adhesive strength fall rate before and after the environmental test of the resin composition of this invention. 25% is particularly preferred. The lower limit value of the adhesion strength reduction rate of the resin composition of the present invention is preferably 17%, more preferably 13%, still more preferably 10%, still more preferably 5%, particularly preferably 1%, and particularly preferably 0%. preferable.

[(E) Inorganic filler]
The resin composition of the present invention may contain an inorganic filler in order to further reduce the coefficient of thermal expansion of the insulating layer obtained from the resin composition. Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Examples include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica and talc are preferable from the viewpoint of improving the adhesion between the conductor layer and the insulating layer. The inorganic filler may be used alone or in combination of two or more.
The average particle diameter of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 4 μm or less, still more preferably 2.5 μm or less, from the viewpoint of forming fine wiring on the insulating layer. 3 μm or less is even more preferable, 1 μm or less is particularly preferable, and 0.7 μm or less is particularly preferable. If the average particle size of the inorganic filler is too small, when the epoxy resin composition is used as a resin varnish, the viscosity of the varnish tends to increase and the handleability tends to decrease. The thickness is preferably 05 μm or more, more preferably 0.1 μm or more, and even more preferably 0.5 μm or more.

  From the viewpoint of preventing the cured product from becoming brittle and preventing the adhesion strength of the resin composition from decreasing, the upper limit of the amount of inorganic filler added is 100% by mass. 70 mass% is preferable, 67 mass% is more preferable, 64 mass% is still more preferable, and 61 mass% is still more preferable. On the other hand, the lower limit of the addition amount of the inorganic filler is preferably 5% by mass, preferably 10% by mass, when the nonvolatile content in the resin composition is 100% by mass from the viewpoint of reducing the thermal expansion coefficient of the insulating layer. Is more preferred, 35% by weight is still more preferred, 40% by weight is even more preferred, 42% by weight is particularly preferred, 44% by weight is particularly preferred, and 46% by weight is particularly preferred.

  In the resin composition of the present invention, it is preferable to use talc as the inorganic filler from the viewpoint of further improving the adhesion between the conductor layer comprising the copper wiring after the accelerated environmental test and the insulating layer. On the other hand, since a relatively large amount of talc is required to maintain sufficient adhesion and lower the coefficient of thermal expansion of the insulating layer, it prevents the melt viscosity of the resin composition from becoming too high to be suitable for lamination. Therefore, it is more preferable to use silica in combination. By using a combination of talc and silica, it is possible to form a good insulating layer that balances the adhesion of the conductor layer, the low coefficient of thermal expansion, and the laminating property.

  The talc used in the present invention is not particularly limited, and various talc can be used, and calcined talc may be used. The upper limit of the average particle diameter of talc is preferably 5 μm or less, more preferably 4 μm or less, still more preferably 2.5 μm or less, even more preferably 1.3 μm or less, and even more preferably 1 μm from the viewpoint of fine wiring and insulation reliability. The following is particularly preferable, and 0.7 μm or less is particularly preferable. On the other hand, the lower limit of the average particle diameter of talc is preferably 0.05 μm or more from the viewpoint of preventing the resin from becoming too high in viscosity and preventing the resin from being embedded between fine wires. It is more preferably 1 μm or more, and further preferably 0.5 μm or more.

  Commercially available talc includes D-600 (average particle size 0.6 μm), D-800 (average particle size 0.8 μm), D-1000 (average particle size 1.0 μm) manufactured by Nippon Talc Co., Ltd. SG-95S (average particle size 1.2 μm), FG-15 (average particle size 1.2 μm), SG-95 (average particle size 2.5 μm), P-8 (average particle size 3.3 μm), P- 6 (average particle size: 4.0 μm), P-4 (average particle size: 4.5 μm), P-3 (average particle size: 5.0 μm), P-2 (average particle size: 7.0 μm), L-1 ( Average particle diameter 5.0 μm), K-1 (average particle diameter 8.0 μm), LG (average particle diameter 5.0 μm) and the like.

  The silica used in the present invention is not particularly limited, and various silicas such as amorphous silica, fused silica, crystalline silica, and synthetic silica are used, and spherical fused silica is particularly preferable. Although the average particle diameter of silica is not particularly limited, the average particle diameter is preferably 5 μm or less, more preferably 4 μm or less, and further preferably 2.5 μm or less from the viewpoint of enabling formation of fine wiring and improving insulation reliability. It is preferably 1.3 μm or less, more preferably 1 μm or less. On the other hand, the lower limit of the average particle diameter of the silica is 0.05 μm or more from the viewpoint of preventing the resin from becoming too thick and difficult to be embedded between fine wirings if the average particle diameter is too small. Preferably, it is 0.1 μm or more, and more preferably 0.5 μm or more.

  When talc and silica are used in combination, the upper limit of the total blending amount of talc and silica is 100% by mass of the non-volatile content in the resin composition from the viewpoint of preventing the laminate property to the circuit board from deteriorating. In this case, 70% by mass is preferable, 68% by mass is more preferable, 66% by mass is further preferable, 64% by mass is still more preferable, 62% by mass is particularly preferable, and 61% by mass is particularly preferable. On the other hand, the lower limit of the total blending amount of talc and silica is preferably 5% by mass, preferably 10% by mass, when the nonvolatile content in the resin composition is 100% by mass from the viewpoint of lowering the thermal expansion coefficient of the insulating layer. %, More preferably 35% by weight, still more preferably 40% by weight, still more preferably 42% by weight, particularly preferably 44% by weight, and particularly preferably 46% by weight.

And when using together talc and silica, the upper limit of the amount of talc is when the non-volatile content in the resin composition is set to 100% by mass from the viewpoint of preventing the laminate property to the circuit board from deteriorating. 20% by weight, more preferably 19% by weight, still more preferably 18% by weight, still more preferably 17% by weight, still more preferably 16% by weight, and particularly preferably 15% by weight. On the other hand, the lower limit of the amount of talc is 5 when the nonvolatile content in the resin composition is 100% by mass from the viewpoint of preventing the adhesion strength between the conductor layer and the insulating layer after the environmental test from being reduced. % By weight is preferred, 6% by weight is more preferred, 7% by weight is more preferred, 8% by weight is even more preferred, 9% by weight is even more preferred, and 10% by weight is particularly preferred.

The inorganic filler in the present invention is preferably one that has been surface treated with a surface treatment agent such as an epoxy silane coupling agent, an aminosilane coupling agent, or a titanate coupling agent to improve its moisture resistance. You may use a surface treating agent 1 type or in combination of 2 or more types. 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 average particle diameter of the inorganic filler containing talc and silica can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis with 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.

[(F) Vinylbenzyl compound]
The resin composition of the present invention may contain a vinylbenzyl compound in order to further reduce the dielectric loss tangent of the insulating layer obtained from the resin composition. The curable polyvinyl benzyl compound used in the present invention is a compound having two or more vinyl benzyl groups in the molecule. For example, (i) a method of reacting a vinyl benzyl halide with an alkali in the presence of an alkali, ii) a method of reacting a vinylbenzyl halide and a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali; or (iii) a method of reacting a fluorene compound, vinylbenzyl halide and a dihalomethyl compound having 2 to 20 carbon atoms in the presence of an alkali. (Refer to Unexamined-Japanese-Patent No. 2003-277440), or (iv) It can manufacture by the method (International publication 02/083610 pamphlet) etc. which make a fluorene compound and vinylbenzyl halide react with alkali presence. The curable polyvinyl benzyl compound preferably contains no hetero atom in the molecule from the viewpoint of low dielectric loss tangent.

  The content of the curable polyvinyl benzyl compound in the resin composition is not particularly limited, but when the nonvolatile content of the resin composition is 100% by mass, it is preferably 2 to 50% by mass, and more preferably Is 5 to 25% by mass. When the content of the curable polyvinyl benzyl compound is too small, the dielectric loss tangent tends to increase. On the other hand, when there is too much content of a curable polyvinyl benzyl compound, it exists in the tendency for adhesiveness to fall.

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 indene compounds 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, Alkylene dihalides such as 4-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) ) Diphthal such as naphthalene, 1,4-bis (chloromethyl) naphthalene It can be exemplified methyl compound.

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

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

  Preferred curable polyvinyl benzyl compounds include those represented by the following formula (7).

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） Particularly preferable curable polyvinyl benzyl compounds include those represented by the following formula (8).

(In 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 curable polyvinyl benzyl compound in the present invention may be a curable polyvinyl benzyl ether compound. For example, 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-2001-2001). 181383).

  Examples of the polyphenol compound include hydroquinone, bisphenol A, bisphenol F, bisphenol S, biphenol, phenol novolak resin, a condensate of phenol and benzaldehyde, xylok type phenol resin, and the like. The aromatic ring of these compounds may be 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.

Typical polyvinyl benzyl ether compounds include those represented by the following formula (9) (see JP-A-9-31006, JP-A-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.

  These polyvinyl benzyl compounds may be used alone or in combination of two or more.

[(G) polymer compound]
The resin composition of the present invention can improve the mechanical strength of the cured product and the film molding ability when used in the form of an adhesive film by further containing a specific polymer compound (G). Examples of such a polymer compound include polyvinyl acetal resin, phenoxy resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester. Resins can be mentioned. You may use a high molecular compound 1 type or in combination of 2 or more types. As the polymer compound, polyvinyl acetal resin and phenoxy resin are particularly preferable.

  As the polyvinyl acetal resin, a polyvinyl butyral resin is particularly preferable. 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 Resin 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 5000 to 200000, more preferably in the range of 10000 to 150,000, still more preferably in the range of 15000 to 100,000, and in the range of 20000 to 80000. Is even more preferred. 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 can be 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.

  Although content of the high molecular compound in a resin composition is not specifically limited, Preferably it is 0.5-20 mass% with respect to 100 mass% of non volatile matters in a resin composition, More preferably 1 to 10% by mass. If the content of the polymer compound is too small, the effect of improving the film forming ability and the mechanical strength tends to be hardly exhibited. If the content is too large, the roughness of the surface of the insulating layer after the roughening process tends to increase.

[Rubber particles]
The resin composition of the present invention can further contain rubber particles from the viewpoint of improving plating adhesion. The rubber particles that can be used in the present invention are, for example, 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 such as cyanate ester resin and epoxy resin. is there. 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.

Preferable examples of rubber particles that can be used in the present invention include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is made of a glassy polymer and an inner core layer is made of a rubbery polymer, or Examples include a three-layer structure in which the outer 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 composed of, for example, a polymer of methyl methacrylate,
The rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). The rubber particles may be used alone or in combination of two or more. 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 Methbrene W300A (average particle size 0.1 μm) and W450A (average particle size 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).

  The average particle diameter of the rubber particles to be blended is preferably in the range of 0.005 to 1 μm, more preferably in the range of 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. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of rubber particles is created on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). And it can measure by making the median diameter into an average particle diameter.

  The content of the rubber particles is preferably 1 to 10% by mass, and more preferably 2 to 5% by mass with respect to 100% by mass of the nonvolatile content in the resin composition.

[Flame retardants]
The resin composition of the present invention can further contain a flame retardant from the viewpoint of improving flame retardancy. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. 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, Hokuko Chemical Industries (
PPQ manufactured by Clariant Co., Ltd., OP930 manufactured by Clariant Co., Ltd., phosphate ester compounds such as PX200 manufactured by Daihachi Chemical Co., Ltd., phosphorus-containing epoxy resins such as FX289 and FX305 manufactured by Toto Kasei Co., Ltd. Examples thereof include phosphorus-containing phenoxy resins such as ERF001 manufactured by Co., Ltd. and phosphorus-containing epoxy resins 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.

[Other ingredients]
In the resin composition of the present invention, other components can be blended as necessary within a range not inhibiting the effects of the present invention. Other components include, for example, organic fillers such as silicon powder, nylon powder, and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based, polymer-based antifoaming agents or leveling agents, and imidazole-based materials. Examples thereof include adhesion imparting agents such as thiazole, triazole, and silane coupling agents, and coloring agents 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 the components are mixed using a rotary mixer or the like, if necessary, by adding a solvent or the like.

  The use of the resin composition of the present invention is not particularly limited, but includes insulating resin sheets such as adhesive films and prepregs, circuit boards, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, and component embeddings. It can be used in a wide range of applications where a resin composition is required, such as a resin. Especially, it can use suitably in order to form an insulating layer in manufacture 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 in general, it is preferably used in the form of a sheet-like laminated 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.

[Adhesive film]
The adhesive film of the present invention is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a support using a die coater or the like. It can be produced by drying the organic solvent by heating or blowing hot air to form the resin composition layer.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. , Aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. You may use an organic solvent combining 1 type (s) or 2 or more types.

  The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, 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 about 3 to 10 minutes. Is done.

  The thickness of the resin composition layer formed in the adhesive film is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 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, For example, it is 1-40 micrometers. 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.

[Multilayer printed wiring board using adhesive film]
A multilayer printed wiring board can be manufactured using the adhesive film manufactured as described above. An example of the method will be described next.

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, a thermosetting polyphenylene ether substrate, and the like. 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. For example, 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). 9.9 × 10 ⁴ N / m ² ), and lamination is preferably performed 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, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

Moreover, the lamination process which heats and pressurizes under reduced pressure can also be performed using a general vacuum hot press machine. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side.

The pressing condition is that the degree of vacuum is usually 1 × 10 −2 MPa or less, preferably 1 × 10 −3 MPa or less. Although heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin. For example, the first stage press has a temperature of 70 to 150 ° C. and the pressure is in a range of 1 to 15 kgf / cm 2, and the second stage press has a temperature of 150 to 200 ° C. and a pressure of 1 to 40 kgf / cm 2 It is preferred to do so. The time for each stage is preferably 30 to 120 minutes. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

  After laminating the adhesive film on the circuit board, it is cooled to around room temperature, and then the support is peeled off, and then the resin composition is thermally cured to form an insulating layer on the circuit board. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to 200 ° C. It is selected in the range of 30 to 120 minutes at ° C.

  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, for example, by a known method such as drilling, laser, or plasma, and if necessary, by combining these methods. However, drilling with a laser such as a carbon dioxide laser or YAG laser is the most common method. is there.

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, first, the surface of the cured resin composition layer (insulating layer) is coated with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / Roughening treatment is performed with an oxidizing agent such as sulfuric acid or nitric acid to form an uneven anchor. 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, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

[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, for example, those made of fibers that are commonly used as prepreg fibers such as glass cloth and aramid fibers can be used.

  In the hot melt method, the resin 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 the resin is used in an organic solvent. This is a method for producing a prepreg by directly coating a sheet-like reinforcing substrate with a die coater without dissolving it. 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 using prepreg]
A multilayer printed wiring board can be produced using the prepreg produced as described above. An example of the method will be described next. One or several prepregs of the present invention are stacked on a circuit board, sandwiched between metal plates through a release film, and press-laminated under pressure and heating conditions. The pressurizing / heating conditions are preferably a pressure of 5 to 40 kgf / cm ² (49 × 10 ^{4 to} 392 × 10 ⁴ N / m ² ) and a temperature of 120 to 200 ° C. for 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.

<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 232 and a nonvolatile content of 75% by mass, a phenol novolac type polyfunctional cyanate ester resin (Lonza) “PT30” manufactured by Japan Co., Ltd., and 9 parts by mass of cyanate equivalent 124) were stirred and mixed together with 10 parts of MEK, and “ESN-475V” manufactured by Toto Kasei Co., Ltd. as a naphthol type epoxy resin (represented by the above general formula (1)). 40 parts by mass of a MEK solution having a nonvolatile content of 65% by mass with an epoxy equivalent of 340), 3 parts by mass of a liquid bisphenol A type epoxy resin (“JER828EL” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 185), and a phosphorus-containing epoxy resin ("FX2 made by Tohto Kasei Co., Ltd. 9EK75 ", MEK solution having an epoxy equivalent of 306 with a nonvolatile content of 75% by mass) 8 parts by mass, active ester curing agent (" EXB9460-65T "manufactured by DIC Corporation, toluene solution with an active group equivalent of 223 having a nonvolatile content of 65% by mass) 10 parts by mass, 6 parts by mass of a phenoxy resin solution (“YX-6554” manufactured by Japan Epoxy Resin Co., Ltd., a mixed solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass), an imidazole compound and an epoxy resin as a curing accelerator 3 parts of adduct (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.) 4 parts by mass of a mass% N, N-dimethylformamide (DMF) solution And 85 parts by weight of spherical silica (“SOC2” manufactured by Admatechs Co., Ltd., surface-treated with aminosilane, average particle size 0.5 μm) are mixed and dispersed uniformly with a high-speed rotary mixer to produce a thermosetting resin composition A product varnish was prepared.
In the nonvolatile content of the resin composition, epoxy resin 24% by mass, cyanate ester resin 13% by mass, active ester curing agent 4% by mass, imidazole curing accelerator 0.1% by mass, metal added as metal curing accelerator ( Cobalt) 49 ppm, polymer compound 1 mass%, inorganic filler 58 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: 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>
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 232 and a nonvolatile content of 75% by mass, a phenol novolac type polyfunctional cyanate ester resin (Lonza) “PT30” manufactured by Japan Co., Ltd., and 9 parts by mass of cyanate equivalent 124) were stirred and mixed together with 10 parts of MEK, and “ESN-475V” manufactured by Toto Kasei Co., Ltd. as a naphthol type epoxy resin (represented by the above general formula (1)). 40 parts by mass of a MEK solution having a nonvolatile content of 65% by mass with an epoxy equivalent of 340), 3 parts by mass of a liquid bisphenol A type epoxy resin (“JER828EL” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 185), and a phosphorus-containing epoxy resin ("FX2 made by Tohto Kasei Co., Ltd. 9EK75 ", MEK solution having an epoxy equivalent of 306 with a nonvolatile content of 75% by mass) 8 parts by mass, active ester curing agent (" EXB9460-65T "manufactured by DIC Corporation, toluene solution with an active group equivalent of 223 having a nonvolatile content of 65% by mass) 10 parts by mass, 6 parts by mass of a 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), a guanidine compound and an epoxy resin as a curing accelerator Adduct body (15 parts by mass of dicyandiamide (“JERcure DICY7” manufactured by Japan Epoxy Resin Co., Ltd.)) and 30 parts by mass of bisphenol A type epoxy resin (“jER 828US” manufactured by Japan Epoxy Resin Co., Ltd.) 55 masses of 1-methoxypropanol solution Nonvolatile content reacted at 100 ° C. for 2 hours in the part 45 mass% solution) 1.5 mass parts, cobalt (II) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 3 mass% N, N-dimethylformamide (DMF) solution 4 mass parts, and spherical silica (Surface treatment of “SOC2” manufactured by Admatechs Co., Ltd. with aminosilane, average particle size 0.5 μm) is mixed with 85 parts by mass and dispersed uniformly with a high-speed rotary mixer, and the varnish of the thermosetting resin composition Was made.
In the nonvolatile content of the resin composition, epoxy resin 24% by mass, cyanate ester resin 13% by mass, active ester curing agent 4% by mass, amine curing accelerator 0.1% by mass, metal derived from metal curing accelerator ( Cobalt) 49 ppm, polymer compound 1 mass%, inorganic filler 58 mass%.
Next, using this resin composition varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

<Example 3>
15 parts by mass of dicyclopentadiene type cyanate ester resin (Lonza Japan Co., Ltd. “DT-4000”, cyanate equivalent 140, toluene solution with non-volatile content of 85% by mass), phenol novolac type polyfunctional cyanate ester resin (Lonza Japan Co., Ltd.) ) "PT30", cyanate equivalent 124) together with 4.5 parts by mass and 10 parts of MEK, and mixed as a naphthol type epoxy resin "ESN-475V" (epoxy equivalent 340 non-volatile content 65 mass%) After adding 10 parts by mass of biphenyl type epoxy resin (epoxy equivalent 269, “NC3000L” manufactured by Nippon Kayaku Co., Ltd.) together with 20 parts by mass of cyclohexanone to 15 parts by mass of MEK solution, a naphthalene type bifunctional epoxy resin ( "HP4032SS" epoxy equivalent manufactured by DIC Corporation 1 5) 3 parts by mass, phosphorus-containing epoxy resin (“FX289EK75” manufactured by Tohto Kasei Co., Ltd., MEK solution having an epoxy equivalent of 306 with a nonvolatile content of 75% by mass), 10 parts by mass, biphenyl type epoxy resin (nonvolatile content with an epoxy equivalent of 328 of 75 4% by mass of MEK solution by mass%, “NC3000FH-75M” manufactured by Nippon Kayaku Co., Ltd., active ester curing agent (“EXB 9460-65T” manufactured by DIC Corporation), 65% by mass of nonvolatile content of active group equivalent 223 10 parts by mass of a toluene solution) and 10 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) were added. Thereto, 10 parts of a polyvinyl butyral resin solution (glass transition temperature 105 ° C., “KS-1” manufactured by Sekisui Chemical Co., Ltd.) is mixed with 15 parts of a solid solution of cyclohexanone and MEK having a solid content of 15%, and further cured. 0.5 parts by mass of adduct of imidazole compound and epoxy resin ("jERcure P200H50" manufactured by Japan Epoxy Resin Co., Ltd.) as a promoter, zinc naphthenate (II) (manufactured by Tokyo Chemical Industry Co., Ltd., zinc content 8% 3 parts by mass of a cyclohexanone solution of 3% by mass of mineral spirit solution) and 85 parts by mass of spherical silica (“SOC2” manufactured by Admatechs Co., Ltd., surface-treated with aminosilane, average particle size 0.5 μm). A thermosetting resin composition varnish was prepared by uniformly dispersing with a high-speed rotary mixer.
In the nonvolatile content of the resin composition, 22% by mass of epoxy resin, 11% by mass of cyanate ester resin, 4% by mass of active ester curing agent, 4% by mass of vinylbenzyl compound, 0.17% by mass of imidazole curing accelerator, metal curing The metal (zinc) derived from the accelerator is 48 ppm, the polymer compound is 1% by mass, and the inorganic filler is 57% by mass.
Next, using this resin composition varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

<Example 4>
Dicyclopentadiene-type cyanate ester resin (Lonza Japan Co., Ltd. “DT-4000”, cyanate equivalent 140, toluene solution with non-volatile content of 85% by mass) 15.3 parts by mass, bisphenol A dicyanate prepolymer (Lonza Japan Co., Ltd.) ) “BA230S75”, 12 parts by mass of methyl ethyl ketone (hereinafter abbreviated as MEK) solution having a cyanate equivalent of 232 and a non-volatile content of 75% by mass are stirred and mixed together, and liquid bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.) jER828EL ", epoxy equivalent 185) 8 parts by mass, biphenyl type epoxy resin (epoxy equivalent 269, Nippon Kayaku Co., Ltd." N
C3000L ") 15 parts by mass with 20 parts of cyclohexanone, phosphorus-containing epoxy resin (" FX289EK75 "manufactured by Tohto Kasei Co., Ltd., MEK solution having an epoxy equivalent of 306 with a nonvolatile content of 75% by mass), active ester 20 parts by mass of a curing agent (“EXB 9460-65T” manufactured by DIC Corporation, a toluene solution having an active group equivalent of 223 with a nonvolatile content of 65% by mass), a vinylbenzyl compound (“V5000X” manufactured by Showa Polymer Co., Ltd.), a nonvolatile content of 65 5 parts by mass of a toluene solution (mass%) and 6 parts by mass of a phenoxy resin solution (“YX-6554” manufactured by Japan Epoxy Resin Co., Ltd., a mixed solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass) were added. 0.5 parts by mass of an adduct of an imidazole compound and an epoxy resin (“jERcure P200H50” manufactured by Japan Epoxy Resin Co., Ltd.) as a curing accelerator, 0.1 part by mass of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) , 4.5 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.) Was subjected to surface treatment with aminosilane, an average particle diameter of 0.5 μm), 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, 21% by mass of epoxy resin, 15% by mass of cyanate ester resin, 8% by mass of active ester curing agent, 2% by mass of vinylbenzyl compound, 0.15% by mass of imidazole-based curing accelerator, metal-based curing The metal (zinc) derived from the accelerator is 44 ppm, the polymer compound is 1% by mass, and the inorganic filler is 53% by mass.
Next, using this resin composition varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

<Example 5>
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 232 and a nonvolatile content of 75% by mass, a phenol novolac type polyfunctional cyanate ester resin (Lonza) “PT30” manufactured by Japan Co., Ltd., and 9 parts by mass of cyanate equivalent 124) were stirred and mixed together with 10 parts by mass of MEK, and “ESN-475V” manufactured by Tohto Kasei Co., Ltd. as a naphthol type epoxy resin (in the general formula (1)) 40 parts by mass of MEK solution having an epoxy equivalent of 340 with a nonvolatile content of 65% by mass), 3 parts by mass of liquid bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd. “jER828EL”, epoxy equivalent 185), phosphorus-containing epoxy Resin (“F” manufactured by Toto Kasei Co., Ltd. 289EK75 ", MEK solution having an epoxy equivalent of 306 with a nonvolatile content of 75% by mass), 8 parts by mass, active ester curing agent (DIC Corporation" EXB9460-65T ", active group equivalent of 223 with a nonvolatile content of 65% by mass in toluene) 10 parts by mass, 6 parts by mass of a phenoxy resin solution (“YX-6594BH30” manufactured by Japan Epoxy Resin Co., Ltd., a mixed solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass), an imidazole compound and an epoxy resin as a curing accelerator 1 part of adduct body (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.) Mass% N, N-dimethylformamide (DMF) 4 parts by mass of liquid, spherical silica ("SOC2" manufactured by Admatechs Co., Ltd., surface-treated with aminosilane, 74 parts by mass of average particle diameter 0.5 µm) and talc ("D800" manufactured by Nippon Talc Co., Ltd.) And 11 parts by mass (average particle diameter 0.8 μm) 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, epoxy resin 24% by mass, cyanate ester resin 13% by mass, active ester curing agent 4% by mass, imidazole-based curing accelerator 0.1% by mass, metal derived from metal-based curing accelerator ( Cobalt) 49 ppm, polymer compound 1 mass%, inorganic filler 58 mass%.
Next, using this resin composition varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

<Example 6>
15 parts by mass of dicyclopentadiene type cyanate ester resin (Lonza Japan Co., Ltd. “DT-4000”, cyanate equivalent 140, toluene solution with non-volatile content of 85% by mass), phenol novolac type polyfunctional cyanate ester resin (Lonza Japan Co., Ltd.) ) "PT30", cyanate equivalent 124) together with 4.5 parts by mass and 10 parts of MEK, and mixed as a naphthol type epoxy resin "ESN-475V" (epoxy equivalent 340 non-volatile content 65 mass%) 10 parts of biphenyl type epoxy resin (epoxy equivalent 269, “NC3000L” manufactured by Nippon Kayaku Co., Ltd.) is added to 15 parts by mass of cyclohexanone 2
After heating and dissolving together with 0 parts, 3 parts by mass of a naphthalene-type bifunctional epoxy resin (DIC Corporation "HP4032SS" epoxy equivalent 145), phosphorus-containing epoxy resin (Tofu Kasei Co., Ltd. "FX289EK75", epoxy equivalent 306 10 parts by mass of MEK solution having a nonvolatile content of 75% by mass, 4 parts by mass of biphenyl type epoxy resin (MEK solution having a nonvolatile content of 75% by mass of epoxy equivalent 328, “NC3000FH-75M” manufactured by Nippon Kayaku Co., Ltd.), activity 10 parts by mass of an ester curing agent (“EXB 9460-65T” manufactured by DIC Corporation, a toluene solution having a nonvolatile content of 65% by mass with an active group equivalent of 223), a vinylbenzyl compound (“V5 manufactured by Showa Polymer Co., Ltd.)
000X ", a toluene solution having a nonvolatile content of 65% by mass) was added 10 parts by mass. Thereto, 10 parts of a polyvinyl butyral resin solution (glass transition temperature 105 ° C., “KS-1” manufactured by Sekisui Chemical Co., Ltd.) is mixed with 15 parts of a solid solution of cyclohexanone and MEK having a solid content of 15%, and further cured. 0.5 parts by mass of adduct of imidazole compound and epoxy resin ("jERcure P200H50" manufactured by Japan Epoxy Resin Co., Ltd.) as a promoter, zinc naphthenate (II) (manufactured by Tokyo Chemical Industry Co., Ltd., zinc content 8% 3 parts by mass of a cyclohexanone solution of 3% by mass of mineral spirit solution), 74 parts by mass of spherical silica (“SOC2” manufactured by Admatechs Co., Ltd., surface-treated with aminosilane, average particle size 0.5 μm), and talc ( 11 parts by mass of “D800” manufactured by Nippon Talc Co., Ltd., surface-treated with aminosilane, average particle size 0.8 μm) Uniformly dispersed in a high-speed rotary mixer to prepare a varnish of a thermosetting resin composition.
In the nonvolatile content of the resin composition, 22% by mass of epoxy resin, 11% by mass of cyanate ester resin, 4% by mass of active ester curing agent, 4% by mass of vinylbenzyl compound, 0.17% by mass of imidazole curing accelerator, metal curing The metal (zinc) derived from the accelerator is 48 ppm, the polymer compound is 1% by mass, and the inorganic filler is 57% by mass.
Next, using this resin composition varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

<Example 7>
Dicyclopentadiene-type cyanate ester resin (Lonza Japan Co., Ltd. “DT-4000”, cyanate equivalent 140, toluene solution with non-volatile content of 85% by mass) 15.3 parts by mass, bisphenol A dicyanate prepolymer (Lonza Japan Co., Ltd.) ) “BA230S75”, 12 parts by mass of cyanate equivalent 232, methyl ethyl ketone (hereinafter abbreviated as MEK) solution with a non-volatile content of 75% by mass are stirred and mixed together, and a biphenyl type epoxy resin (epoxy equivalent 269, manufactured by Nippon Kayaku Co., Ltd.) "NC3000L") 15 parts by mass with 20 parts by mass of cyclohexanone, and then 15 parts by mass of a phosphorus-containing epoxy resin ("FX289EK75" manufactured by Tohto Kasei Co., Ltd., MEK solution having a nonvolatile content of 75% by mass with an epoxy equivalent of 306) Liquid bisphenol A type epoxy resin Japan Epoxy Resin Co., Ltd. “jER828EL”, epoxy equivalent 185) 8 parts by mass, active ester curing agent (DIC Co., Ltd. “EXB 9460-65T”, active group equivalent 223 non-volatile content 65 mass% toluene solution) 20 5 parts by mass of vinyl benzyl compound (“V5000X” manufactured by Showa Polymer Co., Ltd., toluene solution having a nonvolatile content of 65% by mass), phenoxy resin solution (“YX-6554” manufactured by Japan Epoxy Resins Co., Ltd.), nonvolatile content 6 parts by mass of a mixed solution of 30% by mass of MEK and cyclohexanone) was added. 0.5 parts by mass of an adduct of an imidazole compound and an epoxy resin (“jERcure P200H50” manufactured by Japan Epoxy Resin Co., Ltd.) as a curing accelerator, 0.1 part by mass of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) , 4.5 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 diameter 0.5 μm) 74 parts by mass and talc (“ D800 ”manufactured by Nippon Talc Co., Ltd., surface-treated with aminosilane, average particle diameter 0.8 μm) 11 parts by mass And were uniformly dispersed with a high-speed rotary mixer to prepare a varnish of a thermosetting resin composition.
In the non-volatile content of the fat composition, 21% by mass of epoxy resin, 15% by mass of cyanate ester resin, 8% by mass of active ester curing agent, 2% by mass of vinylbenzyl compound, 0.15% by mass of imidazole curing accelerator, metal curing The metal (zinc) derived from the accelerator is 44 ppm, the polymer compound is 1% by mass, and the inorganic filler is 53% by mass.
Next, using this resin composition varnish, an adhesive film was obtained in exactly the same manner as in Example 1.

<Example 8>
Dicyclopentadiene-type cyanate ester resin (Lonza Japan KK "DT-4000", cyanate equivalent 140, non-volatile content 85% by weight toluene solution) 11 parts by mass, bisphenol A dicyanate prepolymer (Lonza Japan KK) 30 parts by mass of “BA230S75”, methylate ketone (hereinafter abbreviated as MEK) solution having a cyanate equivalent of 232 and a non-volatile content of 75% by mass are stirred and mixed together to produce “ESN-475V” (epoxy) as a naphthol type epoxy resin. 10 parts of a biphenyl type epoxy resin (epoxy equivalent 269, “NC3000L” manufactured by Nippon Kayaku Co., Ltd.) and 25 parts by mass of 20 parts of cyclohexanone were dissolved in 25 parts by mass of naphthalene. Type Bifunctional Epoxy Resin (DIC Corporation ) “HP4032SS” epoxy equivalent 145) 3 parts by mass, active ester curing agent (“EXB 9460-65T” manufactured by DIC Corporation, toluene solution 65% by mass of nonvolatile content of active group equivalent 223), phenoxy resin solution ( “YX-6654BH30” manufactured by Japan Epoxy Resin Co., Ltd., 6 parts by mass of a mixed solution of MEK and cyclohexanone with a nonvolatile content of 30% by mass, an adduct of an imidazole compound and an epoxy resin as a curing accelerator (Japan Epoxy Resin Co., Ltd.) ) “JERcure P200H50”, propylene glycol monomethyl ether solution with a nonvolatile content of 50% by mass) 0.5 part by mass, zinc naphthenate (II, manufactured by Tokyo Chemical Industry Co., Ltd., mineral spirit solution with a zinc content of 8%) 3 parts by weight of 3% by weight cyclohexanone solution and spherical silica 97 parts by mass of “SOC2” manufactured by Admatechs Co., Ltd., with aminosilane, average particle diameter of 0.5 μm, and talc (“D800” manufactured by Nippon Talc Co., Ltd., surface treated with aminosilane, average particles A varnish of a thermosetting resin composition was prepared by mixing 13 parts by mass (diameter 0.8 μm) and uniformly dispersing with a high-speed rotary mixer.
In the nonvolatile content of the resin composition, epoxy resin 16% by mass, cyanate ester resin 18% by mass, active ester curing agent 4% by mass, vinylbenzyl compound 0% by mass, imidazole-based curing accelerator 0.14% by mass, metal-based curing The metal (zinc) derived from the accelerator is 40 ppm, the polymer compound is 1% by mass, and the inorganic filler is 61% by 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 thermosetting resin composition and spherical silica (AD Co., Ltd.) to which an active ester curing agent (EXB 9460-65T manufactured by DIC Corporation, toluene solution with a non-volatile content of 65% by mass of active group equivalent 223) is not added. Mattex “SOC2” surface-treated with aminosilane (average particle size 0.5 μm) was mixed in 77 parts by mass, and the inorganic filler in the non-volatile content of the resin composition was the same as in Example 1 (58% by mass). It prepared so that it might become. Using this resin composition varnish, an adhesive film was obtained in the same manner as in Example 1.

<Comparative example 2>
In Example 3, a thermosetting resin composition without adding an active ester curing agent (EXB 9460-65T manufactured by DIC Corporation, a toluene solution having an active group equivalent of 223 and a nonvolatile content of 65% by mass) and spherical silica (AD Co., Ltd.) Mattex “SOC2” surface-treated with aminosilane (average particle size 0.5 μm) was mixed in 77 parts by mass, and the inorganic filler in the nonvolatile content of the resin composition was the same as in Example 3 (57% by mass). It prepared so that it might become. Using this resin composition varnish, an adhesive film was obtained in the same manner as in Example 1.

<Measurement and evaluation of adhesion strength reduction rate>
(1) Substrate treatment of laminate 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 circuit was formed The copper surface was subjected to a roughening treatment by being immersed in Mek Et Bond CZ8100 manufactured by Co., Ltd. (Ra value = 1 μm).
(2) Lamination of adhesive film The adhesive films prepared in Examples and Comparative Examples were laminated on both surfaces 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). This copper foil is called CZ copper foil.
(4) Copper foil lamination and insulation layer formation The PET film is peeled from the adhesive film laminated in (2) above, the treated surface of the CZ copper foil in (3) is on the resin composition layer side, and (2) and Under the same conditions, the copper foil was laminated on the resin composition layer formed on both surfaces of the circuit board. And the sample was produced by hardening | curing a resin composition on 190 degreeC and the hardening conditions for 90 minutes, and forming an insulating layer.
(5) Measurement of peel strength (adhesion strength) of copper foil Sample 510 × 340 mm described in the above (4) prepared using a copper foil having a 1 μm roughening treatment on the copper surface, a piece of 150 × 30 mm Disconnected. A cutter is used to cut the copper foil part of the small piece with a width of 10 mm and a length of 100 mm, and one end of the copper foil is peeled off to grasp the tool (TSE Co., Ltd., Autocom type testing machine AC- 50C-SL), and using an Instron universal testing machine, the load when peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature was measured according to JIS C6481, The adhesion strength with the CZ copper foil before the test ”.
(6) Measurement of peel strength (adhesion strength) of copper foil under high temperature and high humidity HAST test (highly) for the sample of (4) above, left at 130 ° C. in an environment of 85% RH for 100 hours accelerated temperature and humidity Stress Test). Thereafter, the temperature was returned to room temperature and measured in the same manner as in the above (5), and was set as “adhesion strength with CZ copper foil after environmental test”.
(7) Adhesion strength reduction rate calculation method and its evaluation "(Adhesion strength with CZ copper foil before environmental test-Adhesion strength with CZ copper foil after environmental test) / Adhesion strength with CZ copper foil before environmental test The value of “× 100” was calculated as the reduction rate of adhesion strength (%). When the rate of decrease in adhesion strength is 60% or more, it is “X”, when it is less than 60% and 40% or more, “△”, when it is less than 40% and 30% or more, it is “◯”, and less than 30% and 20% or more. In this case, “◎” was assigned, and in the case of less than 20%, “◎◎”.

<Measurement and evaluation of dielectric loss tangent>
In Examples and Comparative Examples, Examples 1 to 8 and Comparative Examples were the same except that PET (Mitsubishi Resin “Fluoroge RL50KSE”) treated with a fluororesin-based release agent (ETFE) was used for the support. An adhesive film having the same resin composition layer as 1 and 2 was obtained, and the obtained adhesive film was thermally cured by heating at 190 ° C. for 90 minutes, and a sheet-like cured product was obtained by peeling the support. The cured product was cut into a length of 80 mm and a width of 2 mm to give an evaluation sample, which was measured by a cavity resonance perturbation method using an HP 8362B apparatus manufactured by Agilent Technologies, and a measurement temperature of 23 ° C. The dielectric loss tangent was measured at a value of 0.0075 or less as “◎” and 0.007. And in the case of larger 0.0085 following a "○", and "△" in the case of 0.0090 following greater than 0.0085, it was evaluated if 0.0090 is larger than the "×".

<Measurement and evaluation of coefficient of thermal expansion (CTE)>
In the examples and comparative examples, adhesive films having the same resin composition layers as those of the examples and comparative examples are the same except that PET (Mitsubishi Resin Co., Ltd. "Fluorouge RL50KSE") was used as the support in the examples and comparative examples. The obtained adhesive film was heat-cured by heating at 190 ° C. for 90 minutes, and the support was peeled off to obtain a sheet-like cured product having a width of 5 mm and a length of 15 mm. A thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Co., Ltd.) After mounting the test piece on the apparatus, the load was increased to 1 g. The measurement was carried out twice continuously under the measurement conditions of a temperature rate of 5 ° C./min.The average linear thermal expansion coefficient (ppm) from 25 ° C. to 150 ° C. in the second measurement was calculated. In the case of it was evaluated as "○".

  The results are shown in Table 1.

  From the results in Table 1, the insulating layer formed by the adhesive films obtained in Examples 1, 2, 3, and 4 has a low dielectric loss tangent and suppresses a decrease in adhesion with the CZ copper foil after the environmental test. Has been. On the other hand, Comparative Examples 1 and 2 that do not contain an active ester curing agent have a higher dielectric loss tangent than those of Example 1 that contain an active ester curing agent with the same composition, and also have good adhesion to CZ copper foil after environmental testing. It has greatly decreased. Moreover, since Examples 5-8 mix | blend silica and talc as an inorganic filler in addition to use of an active ester hardening | curing agent, rather than Examples 1-4 only of silica, adhesiveness with CZ copper foil is further included. The reduction is improved, and the adhesion strength reduction rate is suppressed to a very low level.

  An insulating layer formed of the resin composition has a low dielectric loss tangent, and can provide a resin composition, an adhesive film, a prepreg, and a multilayer printed wiring board having excellent adhesion between the insulating layer and the conductor layer after the accelerated environmental test. It became so. Furthermore, electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and aircraft equipped with these can be provided.

Claims (18)

  A resin composition comprising (A) an epoxy resin, (B) a cyanate ester resin, (C) an active ester curing agent, and (D) a curing accelerator.   The resin composition according to claim 1, wherein (D) the curing accelerator is at least one selected from a metal curing accelerator, an amine curing accelerator, and an imidazole curing accelerator. (D) The curing accelerator is a metal-based curing accelerator composed of 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 according to claim 1 or 2.   When the non-volatile content in the resin composition is 100% by mass, the content of (A) epoxy resin is 5 to 60% by mass, the content of (B) cyanate ester resin is 5 to 50% by mass, and (C) activity. Content of ester hardening | curing agent is 2-20 mass%, The resin composition of any one of Claims 1-3.   (D) When the curing accelerator contains a metal-based curing accelerator and the nonvolatile content in the resin composition is 100% by mass, the metal content based on the metal-based curing accelerator is 25 to 500 ppm. The resin composition according to any one of 1 to 4. (D) When the curing accelerator includes an amine-based curing accelerator and / or an imidazole-based curing accelerator, and the nonvolatile content in the resin composition is 100% by mass, the amine-based curing accelerator and / or imidazole-based curing. The resin composition according to any one of claims 1 to 4, wherein the content of the accelerator is 0.05 to 3% by mass.   The ratio of the cyanate ester group to the epoxy group is 1: 0.4 to 1: 2, and the ratio of the ester group to the epoxy group is 1: 2 to 1:20. The resin composition as described.   Furthermore, (E) The resin composition of any one of Claims 1-7 containing an inorganic filler.   The resin composition according to claim 8, wherein the inorganic filler is talc and silica.   When the nonvolatile content in the resin composition is 100% by mass, the total content of talc and silica is 35% by mass to 70% by mass, and the content of talc is 5% by mass to 20% by mass. The resin composition according to claim 9.   The resin composition according to any one of claims 1 to 10, further comprising (F) a vinylbenzyl compound.   The resin composition according to claim 11, wherein the content of the (F) vinylbenzyl compound is 2 to 50 mass% when the nonvolatile content in the resin composition is 100 mass%.   Furthermore, (G) selected from polyvinyl acetal resin, phenoxy resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin The resin composition of any one of Claims 1-12 containing 1 or more types of high molecular compounds.   The resin composition of Claim 13 whose content of (G) polymer compound is 1-20 mass% when the non volatile matter in a resin composition is 100 mass%. The resin according to any one of claims 1 to 14, wherein the dielectric loss tangent property is 0.004 to 0.009, and the adhesion strength reduction rate before and after the environmental test is 0% to 59%. Composition.   The adhesive film by which the resin composition of any one of Claims 1-15 was layer-formed on the support body.   A prepreg in which the resin composition according to any one of claims 1 to 15 is impregnated in a sheet-like reinforcing base material.   The multilayer printed wiring board by which the insulating layer was formed with the hardened | cured material of the resin composition of any one of Claims 1-15.