TWI632189B - Resin composition - Google Patents

Abstract

When a thin layer is formed, a resin composition having a low surface roughness and a high plating peel strength and achieving a low CTE at a high temperature can be obtained.

A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) spherical ceria, and (D) glass fiber.

Description

Resin composition

The present invention relates to a resin composition. Further, the present invention relates to an adhesive film, a cured product, a multilayer printed wiring board, and a semiconductor device using the resin composition.

In recent years, with the miniaturization and high performance of semiconductor devices, in the multilayer printed wiring board, the strength is maintained and the thickness is reduced.

Various epoxy resin compositions suitable for thin layer formation are discussed. For example, Patent Document 1 describes an epoxy resin molding material characterized by containing an epoxy resin (a), a glass fiber (b) having a fiber length of 200 μm or less, and spherical cerium oxide (c) having an average particle diameter of 30 μm or less. In Patent Document 1, by using glass fibers (b) having a fiber length of 200 μm or less, the fluidity of the resin is suppressed by the glass fibers, and the mechanical strength of the molded article is improved.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-281362

However, the present inventors conducted a lot of review on the thin layer formation of the epoxy resin composition, and found that when the epoxy resin composition containing the glass fiber is thinned, the glass fiber is easily exposed from the surface of the layer, and the surface roughness becomes coarse. .

Therefore, the present invention provides the formation of an insulating layer suitable for a printed wiring board, and by using the resin composition, a printed wiring board is manufactured, and even when thinned, low surface roughness and high plating peel strength can be attained. And it is aimed at achieving a low CTE resin composition at a high temperature. Here, CTE refers to the coefficient of thermal expansion of the wire.

The present invention has been made in view of the above circumstances, and it has been found that a resin composition containing an epoxy resin, a spherical cerium oxide, or a glass fiber contains an active ester compound, so that it is difficult to obtain a glass fiber even when it is thinned. The surface of the layer is exposed to achieve a low surface roughness and a high plating peel strength, and a resin composition having a low CTE at a high temperature can be obtained, and the present invention has been completed.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) spherical cerium oxide, and (D) glass fiber.

[2] The resin composition according to [1], wherein the resin composition is When the nonvolatile content in the product is 100% by mass, the content of (C) spherical cerium oxide and (D) glass fiber is 50% by mass to 85% by mass, and (D) the content of glass fiber is 2% by mass. ~60% by mass.

[3] The resin composition according to [2], wherein the content of the (D) glass fiber is from 10% by mass to 50% by mass based on 100% by mass of the nonvolatile component in the resin composition.

[4] The resin composition according to any one of [1] to [3] wherein (C) the spherical cerium oxide has an average particle diameter of 5 μm or less.

[5] The resin composition according to any one of [1], wherein the (D) glass fiber has an average fiber diameter of 13 μm or less and an average fiber length of 100 μm or less.

[6] The resin composition according to [5], wherein (D) the glass fiber has an average fiber diameter of 6 μm or less.

[7] The resin composition according to any one of [1] to [6] wherein the average linear thermal expansion coefficient at 150 ° C to 240 ° C is 50 ppm or less.

[8] The resin composition according to any one of [1] to [7] which is used for an insulating layer of a multilayer printed wiring board.

[9] A film comprising a layer composed of the resin composition according to any one of [1] to [8], which is formed on a support.

[10] The adhesive film according to [9], wherein the layer composed of the resin composition has a thickness of 5 μm to 40 μm.

[11] A cured product of the resin composition according to any one of [1] to [8].

[12] A multilayer printed wiring board characterized by [9] or The film is produced by the following film described in [10].

[13] A semiconductor device characterized by using the multilayer printed wiring board according to [12].

The present invention can provide a resin composition which can achieve low surface roughness and high plating peel strength even when thinned, and can achieve low CTE at high temperatures.

[Best Mode for Carrying Out the Invention]

According to an embodiment of the present invention, there is provided a resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) spherical cerium oxide, and (D) glass fiber.

<(A) Epoxy Resin>

The epoxy resin used in the present invention is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and phenol novolac. Epoxy resin, tert-butyl-catechol epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, naphthyl ether epoxy resin, epoxypropyl amine epoxy resin, Cresol novolak type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic ring Epoxy resin, spiral epoxy resin, cyclohexane dimethanol epoxy resin, trimethylol epoxy resin, halogenated ring Oxygen resin, dicyclopentadiene type epoxy resin, and the like. These may be used alone or in combination of two or more.

Among these, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, and the like are improved from heat resistance, insulation reliability, and adhesion of the conductor layer. A phenyl type epoxy resin, a naphthyl ether type epoxy resin, a fluorene type epoxy resin, an epoxy resin having a butadiene structure, and a dicyclopentadiene type epoxy resin are preferred. Specifically, for example, bisphenol A type epoxy resin ("EPIKOTE 828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin ("JER806H" and "YL983U" manufactured by Mitsubishi Chemical Corporation) 1:1 mixture of bisphenol A type and bisphenol F type ("ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and naphthalene type 2-functional epoxy resin (HP4032" and "HP4032D" manufactured by DIC Corporation ""HP4032SS", "EXA4032SS"), naphthalene type 4-functional epoxy resin ("HP4700" and "HP4710" made by DIC), and naphthol type epoxy resin ("Nippon Steel & Sumitomo Chemical Co., Ltd." ESN-475V"), epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.), and epoxy resin having a biphenyl structure ("NC3000H" manufactured by Nippon Kayaku Co., Ltd." "NC3000L", "NC3100", "YX4000", "YX4000H", "YX4000HK", "YL6121"), and dihydroanthracene epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation) , a naphthyl ether type epoxy resin (EXA-7310, "EXA-7311", "EXA-7311L", "EXA7311-G3" made by DIC), and a dicyclopentadiene type epoxy resin ( DIC (shares) "HP-7200H") and so on.

Epoxy resins may be used in combination of two or more kinds. The resin composition is preferably one containing an epoxy resin having two or more epoxy groups in one molecule. The resin composition contains an aromatic epoxy resin (hereinafter referred to as "liquid epoxy resin") having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C, and one molecule The aspect of the aromatic epoxy resin (hereinafter, "solid epoxy resin") which has three or more epoxy groups and is solid at a temperature of 20 ° C is more preferable. Further, the aromatic epoxy resin according to the present invention means an epoxy resin having an aromatic ring structure in its molecule. When an epoxy resin is used together with a liquid epoxy resin and a solid epoxy resin, when the resin composition is used in the form of a film, it has a moderate flexibility point or a cured product of a resin composition having a moderate fracture. The strength point, the ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.1 to 1:5 by mass ratio, and preferably in the range of 1:0.3 to 1:4, 1: The range of 0.6~1:3 is even better.

In the case of liquid epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, and naphthalene epoxy resin are preferred, bisphenol A epoxy resin, and A naphthalene type epoxy resin is preferred. These may be used alone or in combination of two or more.

For solid epoxy resin, 4-functional naphthalene epoxy resin, cresol novolak epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, A phenyl epoxy resin or a naphthyl ether epoxy resin is preferred, a tetrafunctional naphthalene epoxy resin, a biphenyl epoxy resin, and a naphthyl ether epoxy resin are more preferred. Such can One type or two or more types are used in combination.

In the resin composition of the present invention, when the non-volatile content in the resin composition is 100% by mass, the content of the epoxy resin is 3% by mass, from the viewpoint of mechanical strength or water resistance of the cured product of the resin composition. It is preferably from -35 mass%, more preferably from 5 mass% to 30 mass%, even more preferably from 10 mass% to 20 mass%.

The epoxy equivalent of the epoxy resin is preferably from 50 to 3,000, more preferably from 80 to 2,000, still more preferably from 110 to 1,000. In the range of the epoxy equivalent, the crosslinking density of the cured product is sufficient, and an insulating layer excellent in heat resistance is obtained. Further, the epoxy equivalent can be measured in accordance with JIS K7236 and is a mass of a resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of the epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, still more preferably from 400 to 1,500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by GPC (colloidal permeation chromatography).

<(B) Active ester compound>

The active ester compound is not particularly limited, and it is generally preferred to use two or more reactive esters in one molecule of a phenol ester, a thiophenol ester, an N-hydroxylamine, or an ester of a heterocyclic hydroxy compound. Base compound. The active ester compound is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a sulfuric acid compound with a hydroxy compound and/or a thiol compound. Particularly, from the viewpoint of improvement in heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and a carboxylic acid compound and a phenol compound and/or The active ester-based curing agent obtained from the naphthol compound is preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. For phenolic compounds or naphthol compounds, such as hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, acid phenolphthalein, methylated bisphenol A, methylated bisphenol F, Bisphenol bisphenol, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, active ester compound containing naphthalene structure, A cyclopentadiene type diphenol compound (a polycyclopentadiene type diphenol compound), a phenol novolak, and the like. One or two or more kinds of the active ester compounds can be used. As the active ester compound, an active ester compound disclosed in JP-A-2004-277460, or a commercially available product can be used. In the case of a commercially available active ester compound, an active ester compound containing a dicyclopentadiene type diphenol condensation structure, an active ester compound containing a naphthalene structure, an active ester compound containing a phenolic novolac acetylate, and a phenol novolac An active ester compound or the like of benzamidine-based compound is preferred, and an active ester compound containing a dicyclopentadiene-type diphenol condensation structure is preferred. Specifically, for example, "EXB9451", "EXB9460", and "HPC8000-65T" (manufactured by DIC Co., Ltd., active base equivalent: about 223) as an active ester compound containing a dicyclopentadiene-type diphenol condensation structure, "DC808" (manufactured by Mitsubishi Chemical Corporation, active base equivalent: 149) of the active ester compound of the acetal phenol aldehyde varnish, and "YLH1026" as the active ester compound of the phenhydrazide containing phenol novolac ( Mitsubishi Chemical Corporation , YLH1030 (Mitsubishi Chemical Co., Ltd., active base equivalent: about 201), "YLH1048" (Mitsubishi Chemical Co., Ltd., active base equivalent of about 245), etc. -8000-65T" is preferable in terms of storage stability of the varnish, thermal expansion rate of the cured product, and skeleton having high hydrophobicity.

The active ester compound reacts with the free hydroxyl group of the epoxy resin to form an ester bond, and is easy to form a highly hydrophobic hardened material, thereby preventing the surface of the insulating layer from being excessively roughened during the roughening treatment. Even if glass fiber is used, the glass fiber is not from the layer. The surface is exposed to achieve low surface roughness and high plating peel strength. On the other hand, in the case where the active ester compound is not blended, the cured layer of the surface layer is easily roughened during the roughening treatment, and the glass fiber is easily exposed from the surface of the layer as compared with the case of the active ester compound, so the surface roughness becomes High, plating peel strength is easy to become low.

An active ester compound containing a dicyclopentadiene type diphenol condensation structure, more specifically, for example, a compound of the following formula.

(wherein R is independently a phenyl or naphthyl group, k is 0 or 1, and n is an average of repeating units and is 0.05 to 2.5.)

From the viewpoint of lowering the dielectric dissipation factor and improving the heat resistance, R is preferably a naphthyl group. On the other hand, k is preferably 0, and n is preferably 0.25 to 1.5.

The content of the active ester compound is 40% by mass or less when the non-volatile content in the resin composition is 100% by mass, from the viewpoint of improving the heat resistance and preventing the hydrophobicity from being too high, and obtaining a good plating peeling strength. Preferably, it is more preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less. On the other hand, when the content of the active ester compound is 100% by mass in the resin composition, the content of the active ester compound is 100% by mass in terms of the improvement of the lamination property, the suppression of the protrusion of the glass fiber, and the low surface roughness of the cured product. It is preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 1.5% by mass or more, still more preferably 2% by mass or more.

Further, when the number of epoxy groups of the epoxy resin (A) is 1, the mechanical properties of the resin composition are improved, and the number of reactive groups of the (B) active ester compound is preferably 0.2 to 2, more preferably 0.3 to 1.5, and 0.4 to 0.4. 1 is even better. Here, the "epoxy group number of the epoxy resin" means the total value of the epoxy resin in which the solid content of each epoxy resin present in the resin composition is divided by the epoxy equivalent value. Further, the "reactive group" means a functional group reactive with an epoxy group, and "the number of reactive groups of the active ester compound" means the mass of the solid content of each active ester compound present in the resin composition divided by the equivalent of the reactive group. Total value.

<(C) Spherical cerium oxide>

The spherical cerium oxide may be used singly or in combination of two or more. The spherical cerium oxide is preferably a spherical molten cerium oxide by lowering the coefficient of thermal expansion. Commercially available spherical molten cerium oxide may, for example, be "SO-C2" or "SO-C1" manufactured by Admatechs.

The spherical ceria has an average particle diameter of preferably 0.01 μm to 5 μm, more preferably 0.05 μm to 3 μm, more preferably 0.1 μm to 1 μm, and even more preferably 0.3 μm to 0.8 μm. The average particle size of spherical cerium oxide can be obtained by laser diffraction based on the Mie scattering theory. Determined by scattering method. Specifically, the particle size distribution of the spherical cerium oxide can be prepared on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter is measured as an average particle diameter. It is preferable to use a sample in which spherical cerium oxide is dispersed in water by ultrasonic waves. For the laser diffraction scattering type particle size distribution measuring apparatus, the LA-500 manufactured by the company, Horiba, Ltd., can be used.

When the content of the spherical cerium oxide is 100% by mass based on the non-volatile content in the resin composition, 20% by mass or more is preferable, and 40% by mass or more is more preferable from the viewpoint of lowering the thermal expansion coefficient of the insulating layer. 50% by mass or more, more preferably 60% by mass or more, more preferably 65% by mass or more, and even more preferably 70% by mass or more. On the other hand, when the non-volatile component in the resin composition is 100% by mass, the upper limit of the content of the spherical cerium oxide is preferably 90% by mass or less from the viewpoint of mechanical strength of the obtained insulating layer. More preferably, it is 80% by mass or less.

Spherical cerium oxide, for example, an amine decane-based coupling agent, an epoxy decane-based coupling agent, a decyl decane-based coupling agent, a decane-based coupling agent, an organic decazane compound, or a titanate for improving moisture resistance. It is preferred to treat one or more kinds of surface treatment agents such as a coupling agent. For the commercial product of the surface treatment agent, for example, "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" manufactured by Shin-Etsu Chemical Co., Ltd. Propyl trimethoxy decane), Shin-Etsu Chemicals "KBE903" (3-aminopropyltriethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "N-phenyl-3-aminopropyltrimethoxydecane", "SZ-31" (hexamethyldioxane) manufactured by Shin-Etsu Chemical Co., Ltd.

Further, after the spherical cerium oxide surface-treated with the surface treatment agent is washed with a solvent (for example, methyl ethyl ketone (MEK)), the amount of carbon per unit surface area of the spherical cerium oxide can be measured. Specifically, a sufficient amount of MEK as a solvent was added to the spherical ceria (inorganic filler) surface-treated with a surface treatment agent, and ultrasonic cleaning was performed at 25 ° C for 5 minutes. After removing the supernatant and drying the solid portion, the amount of carbon per unit surface area of the spherical cerium oxide (inorganic filler) can be measured using a carbon analyzer. For the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The amount of carbon per unit surface area of the spherical cerium oxide is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and 0.2 mg/m from the viewpoint of improving the dispersibility of the spherical cerium oxide. ² or more is better. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish or the increase in the melt viscosity of the film form, 1 mg/m ² or less is preferable, 0.8 mg/m ² or less is more preferable, and 0.5 mg/m ² or less is more preferable. .

<(D)glass fiber>

The glass fibers may be used alone or in combination of two or more. Examples of commercially available glass fibers include, for example, chopped fibers, glass fibers obtained by grinding fibers, and the like.

The average fiber diameter of glass fiber In view of the above, it is preferably 13 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, still more preferably 6 μm or less, particularly preferably 4 μm or less, and still more preferably 2 μm or less. The lower limit is not particularly limited, but may be usually 0.5 μm or more.

The average fiber length of the glass fiber is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 20 μm or more, and still more preferably 30 μm or more from the viewpoint of lowering the coefficient of thermal expansion, from the viewpoint of compatibility of the varnish. It is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and still more preferably 50 μm or less.

In one embodiment of the present invention, it is preferred that the (D) glass fiber has an average fiber diameter of 13 μm or less and an average fiber length of 100 μm or less.

The fiber diameter and the average fiber length of the glass fiber can be measured, for example, using an optical microscope or an electron microscope.

When the content of the glass fiber is 100% by mass based on the non-volatile content in the resin composition, it is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more from the viewpoint of lowering the coefficient of thermal expansion. Moreover, from the viewpoint of the compatibility of the varnish, 60% by mass or less is preferable, 50% by mass or less is more preferable, and 40% by mass or less is more preferably 30% by mass or less.

(C) When the content of the spherical cerium oxide and the (D) glass fiber is 100% by mass in terms of the non-volatile content in the resin composition, 50% by mass or more is preferable from the viewpoint of lowering the coefficient of thermal expansion, 55 More preferably, the mass% or more is more preferably 60% by mass or more, and more preferably 65% or more. Again From the viewpoint of improving the compatibility of the varnish, it is preferably 85% by mass or less, more preferably 80% by mass or less.

In one embodiment of the present invention, when the nonvolatile content in the resin composition is 100% by mass, the total content of (C) spherical cerium oxide and (D) glass fiber is 50% by mass to 85% by mass. It is preferable that the content of the (D) glass fiber is 2% by mass to 60% by mass.

In another embodiment of the present invention, when the nonvolatile content in the resin composition is 100% by mass, the total content of (C) spherical cerium oxide and (D) glass fiber is 50% by mass to 80% by mass. %, (D) The content of the glass fiber is preferably 10% by mass to 50% by mass.

In one embodiment of the present invention, the cured product of the resin composition has an average linear thermal expansion coefficient of 25 to 150 ° C, preferably 25 ppm or less, more preferably 20 ppm or less, and still more preferably 18 ppm or less. Although the lower limit is not limited, it is generally 4 ppm or more.

In one embodiment of the present invention, the average linear thermal expansion coefficient of the cured product of the resin composition at 150 ° C to 240 ° C is 50 ppm or less from the viewpoint of reducing the mismatch of the cable termination equipment of the circuit and the insulating layer when the component is mounted. Better, 40ppm or less, and 30ppm or less. Although the lower limit is not limited, it is generally 10 ppm or more.

The coefficient of thermal expansion of the wire can be measured by thermomechanical analysis by a tensile load method using a thermoelectric analysis device (Thermo Plus TMA8310) manufactured by Rigaku.

<(E) Other ingredients>

The resin composition of the present invention may contain other components under the effect of the invention.

The resin composition of the present invention may further contain one or more of the following other components, for example, a thermoplastic resin, a cyanate ester-based curing agent, a phenol-based curing agent, a naphthol-based curing agent, and a benzene. And a hardener such as an oxazine-based hardener; a hardening accelerator; a flame retardant; rubber particles; and the like.

- Thermoplastic Resin -

Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamidoximine resin, polyether oxime resin, and polyfluorene resin. One type of the thermoplastic resin may be used alone or two or more types may be used in combination.

The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a colloidal permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is Shodex K-800P/K manufactured by Showa Denko Co., Ltd., which is used as a measuring device, and LC-9A/RID-6A manufactured by Shimadzu Corporation. -804L/K-804L, chloroform or the like as a mobile phase, measured at a column temperature of 40 ° C, and can be calculated using a calibration curve of standard polystyrene.

For phenoxy resin, for example, having a bisphenol A skeleton, double Phenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, anthracene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, A phenoxy resin having one or more kinds of skeletons selected from the group consisting of a terpene skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (all of which are bisphenol A-containing phenoxy resins) and "YX8100" (including bisphenol S skeleton benzene) manufactured by Mitsubishi Chemical Corporation. "Oxygen resin" and "YX6954" (including bisphenol acetophenone skeleton phenoxy resin), and other examples include "FX280", "FX293" and "FX293L" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. "YX7553", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi Chemical Corporation.

Specific examples of the polyvinyl acetal resin include, for example, "Electrified butyral 4000-2", "Electrified butyral 5000-A", and "Electrified butyral 6000-C" manufactured by Electrochemical Industry Co., Ltd. , "Electrochemical butyral 6000-EP", S-LEC BH series, BX series, KS series, BL series, BM series, etc., manufactured by Sekisui Chemical Industry Co., Ltd.

Specific examples of the polyimide resin include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. Specific examples of the polyimine resin include a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (JP-A-2006-37083) Remember Modified polyfluorene, such as a poly(imineimine), a polyfluorene-containing polyimine (polyimine imine described in JP-A-2002-210667, JP-A-2000-319386, etc.) Imine.

Specific examples of the polyamidoximine resin include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamidoximine resin include modified polyamines such as polyoxoxane skeleton polyamine amidoxime "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd. Yttrium.

Specific examples of the polyether oxime resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the polybenzazole resin include, for example, "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

In the content of the thermoplastic resin, when the nonvolatile content in the resin composition is 100% by mass, for example, it is 0.01% by mass to 2% by mass.

- a hardener such as a cyanate ester-based curing agent, a phenolic curing agent, a naphthol-based curing agent, or a benzoxazine-based curing agent -

In the resin composition of the present invention, in addition to the active ester compound, a cyanate ester-based curing agent, a phenol-based curing agent, a naphthol-based curing agent, a benzoxazine-based curing agent, or the like may be contained in the resin composition of the present invention. Hardener.

Cyanate ester-based hardeners, such as bisphenol A dicyanate, polyphenol cyanate (for example, oligo(3-methylene-1,5-phenylene cyanide) Ester)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A Cyanate ester, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethyl Phenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl) sulfide, and bis (4- A polyfunctional cyanate resin derived from a bifunctional cyanate resin such as cyanate phenyl) ether, a phenol novolac, a cresol novolac, or the like, and a partial triazine-based prepolymerization of the cyanate resin Things and so on. Preferred examples of the cyanate ester-based curing agent include "PT30" and "PT60" (all of which are phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza Japan Co., Ltd., and "BA230". (a part or all of the bisphenol A dicyanate is triazine-formed into a prepolymer of a terpolymer) or the like.

The phenolic curing agent and the naphthol-based curing agent are preferably a phenolic curing agent having a novolak structure or a naphthol-based curing agent having a novolac structure from the viewpoint of heat resistance. Further, from the viewpoint of adhesion to the conductor layer (circuit wiring), a nitrogen-containing phenol-based curing agent is preferred, and a triazine-based phenol-based curing agent is preferred. Among them, from the viewpoint of heat resistance and adhesion to the conductor layer (peel strength; peel strength), it is preferred to use a triazine skeleton phenol novolak resin as the curing agent.

Specific examples of the phenolic curing agent and the naphthol-based curing agent are, for example, "MEH-7700", "MEH-7810", "MEH-7851", and "Nippon Chemical Co., Ltd." manufactured by Mingwa Kasei Co., Ltd. "SN170", "SN180", "SN190", "SN475", "SN485", manufactured by Nikken, "CBN", "GPH", Nippon Steel & Sumitomo Chemical Co., Ltd. "LA7052", "SN7054", "LA3018", etc., such as "SN495", "SN375", "SN395", and DIC (share).

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industries Co., Ltd.

A curing agent such as a cyanate ester-based curing agent, a phenolic curing agent, a naphthol-based curing agent, or a benzoxazine-based curing agent may be used singly or in combination of two or more kinds. The content of the curing agent may be 0.01% by mass to 3% by mass when the nonvolatile content in the resin composition is 100% by mass.

- hardening accelerator -

Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, an oxime-based curing accelerator, and a metal-based curing accelerator, and an amine-based curing accelerator and an imidazole-based curing accelerator. A metal-based hardening accelerator is preferred.

Examples of the phosphorus-based hardening accelerator, such as triphenylphosphine, bismuth borate compound, tetraphenylphosphonium tetraphenyl borate, n-butyl phosphotetraphenyl borate, tetrabutyl decanoate , (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., with triphenylphosphine, tetrabutylphosphonium Alkanoates are preferred.

Examples of the amine-based hardening accelerator include a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, and 2,4,6-gin. (Dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]-undecene, etc., with 4-dimethylaminopyridine, 1,8-diaza Ring [5.4.0]-undecene is preferred.

Examples of the imidazole-based hardening accelerator, such as 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-undecylimidin trimellitic acid, 1-cyanoethyl-2-phenylimidazolium trimellitic acid, 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-three Pyrazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocylate cyanide, 2-phenylimidazolium Polycyanate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole [1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazole An imidazole compound of ruthenium chloride, 2-methylimidazoline, 2-phenylimidazoline or the like, and an adduct of an imidazole compound and an epoxy resin, using 2-ethyl-4-methylimidazole, 1-benzyl- 2-Phenylimidazole is preferred.

Examples of lanthanide hardening accelerators, such as dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenyl fluorene, 1-(o-methylphenyl) fluorene, dimethyl Base, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0]non-5-ene, 7-methyl-1 ,5,7-triazabicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1- N-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl Bismuth, 1-(o-methylphenyl)biguanide, etc., preferably dicyandiamide or 1,5,7-triazabicyclo[4.4.0]non-5-ene.

The metal-based hardening accelerator is not particularly limited, and is, for example, an organometallic complex or an organic metal salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese or tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetamidine acetone, cobalt (III) acetamidine acetone, and organic copper complexes such as copper (II) acetamidine acetone. , an organic zinc complex such as zinc (II) acetamidine, an organic iron complex such as iron (III) acetamidine, an organic nickel complex such as nickel (II) acetamidine, or manganese (II) An organic manganese complex such as acetonitrile or the like. Examples of the organic metal salt include zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like. These may be used alone or in combination of two or more. In the case of the metal-based hardening accelerator, an organic cobalt complex is preferably used, and in particular, cobalt (III) ethyl acetonide is preferred.

The curing accelerators may be used alone or in combination of two or more. When the content of the hardening accelerator is 100% by mass in the resin composition, it is preferably used in the range of 0.01% by mass to 3% by mass.

- Flame retardant -

Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, an anthrone-based flame retardant, and a metal hydroxide. Flame retardant The agents may be used alone or in combination of two or more. The content of the flame retardant is not particularly limited, and when the nonvolatile content in the resin composition is 100% by mass, 0.5% by mass to 10% by mass is preferred, and 1% by mass to 9% by mass is more preferably 1.5% by mass to 8% by mass. The quality is better.

-Rubber particles -

The rubber particles are, for example, those which are insoluble in an organic solvent to be described later and which are not compatible with the above-mentioned epoxy resin, curing agent, thermoplastic resin or the like. Such rubber particles generally have a molecular weight of a rubber component which is too large to be insoluble in an organic solvent or a resin grade, and is prepared in a particle form.

Examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked 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. The core-shell type rubber particles, for example, the shell layer of the outer layer is composed of a glassy polymer, the core layer of the inner layer is a two-layer structure composed of a rubbery polymer, or the shell layer of the outer layer is composed of a glass polymer, and the middle layer The layer is composed of a rubbery polymer, and the core layer is a three-layer structure composed of a glassy polymer. The glassy polymer layer is composed of, for example, a methyl methacrylate polymer, and a rubbery polymer layer such as a butyl acrylate polymer (butyl rubber). The rubber particles may be used alone or in combination of two or more.

The average particle diameter of the rubber particles is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle diameter of the rubber particles can be measured using dynamic light scattering. For example, it can be due to the proper organic solvent The rubber particles are uniformly dispersed by ultrasonic waves or the like, and a particle size analyzer of a rubber particle size (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.) is used, and the particle size distribution of the rubber particles is prepared on a mass basis, and the median diameter is an average particle diameter. The measurement was carried out. The content of the rubber particles in the resin composition is preferably from 1% by mass to 10% by mass, more preferably from 2% by mass to 5% by mass.

The resin composition of the present invention may further contain other additives as necessary, and examples of the other additives include organic fillers, tackifiers, antifoaming agents, flat agents, adhesion imparting agents, and resin additives such as coloring agents.

In the resin composition of the present invention, by mixing the above components as appropriate, a mixing means such as a three-roller, a ball mill, a bead mill, a sand mixer, or the like, or a stirring means such as a high-speed mixer or a star kneading machine is necessary. A resin varnish can be produced by kneading or stirring.

The use of the resin composition of the present invention is not particularly limited, and can be used, for example, for a sheet-like laminate such as a film, a circuit board (for laminate use, multilayer printed wiring board use, etc.), solder resist, underfill, and A wide range of uses of the resin composition can be used for the die bonding material, the semiconductor sealing material, the hole-filling resin, the part embedding resin, and the like. Among them, the resin composition of the present invention is preferably used for a resin composition for an insulating layer of a multilayer printed wiring board. In particular, the resin composition of the present invention is more preferably used for a resin composition for forming a conductor layer by plating (a resin composition for an insulating layer of a multilayer printed wiring board formed by plating a conductor layer) or a multilayer printed wiring board. A resin composition for layer formation. The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer or a sheet-like laminate which is followed by a film or the like. The form of the material is used.

<Next film>

Next, the film is formed by forming a layer composed of a resin composition on a support. The adhesive film can be produced by a known method of the manufacturer. For example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and the resin varnish is applied to a support by a die coater or the like, and then heated or dried by hot air to dry the organic solvent to form a resin. It is manufactured by the layer which consists of a composition. The layer composed of the resin composition is also referred to as a resin composition layer.

As the organic solvent, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetic acid Acetate such as ester, cellosolve, carbitol such as butyl carbitol, aromatic hydrocarbon such as toluene or xylene, dimethylformamide, dimethylacetamide, N- A amide-based solvent such as methylpyrrolidone. Two or more types of organic solvents can be used in combination.

The drying condition is not particularly limited, but the content of the organic solvent in the resin composition layer is usually 10% by mass or less, and preferably 5% by mass or less. The amount of the organic solvent in the varnish varies depending on the boiling point of the organic solvent. For example, the varnish containing 30% by mass to 60% by mass of the organic solvent is dried at 50 ° C to 150 ° C for about 3 minutes to 10 minutes to form a resin. Composition layer. The resin composition layer is also referred to as a B-stage film, and is not fully cured and can be further cured.

The resin composition layer has a melt viscosity of 100 ° C, obtained from The laminate film is excellent in lamination or embedding, preferably 35,000 poise or less, more preferably 20,000 poise or less, 10,000 poise or less, 5,000 poise or less, and 3000 poise or less. Further, from the viewpoint of preventing bleeding during lamination, it is preferably 500 poise or more, more preferably 1000 poise or more. When the resin composition layer is laminated, it is usually carried out at around 100 ° C. Therefore, the laminate of the film can be evaluated by the melt viscosity value of 100 ° C.

The melt viscosity at 100 ° C of the resin composition layer of the present invention can be measured by a dynamic viscoelastic method. Specifically, dynamic viscoelasticity measurement can be performed by using a parallel resin plate having a resin content of 1 g and a parallel plate having a diameter of 18 mm, a starting temperature of 60 ° C to 200 ° C, a temperature rising rate of 5 ° C / min, a measurement temperature interval of 2.5 ° C, and a vibration of 1 Hz / deg. The melt viscosity of the resin composition layer at 100 ° C. Such a dynamic viscoelasticity measuring device, such as (unit) U. B. M type Rheosol-G3000.

The thickness of the resin composition layer formed in the film is preferably greater than or equal to the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is usually in the range of 5 μm to 70 μm, and therefore the thickness of the resin composition layer is preferably 5 μm to 40 μm. In particular, in the present invention, even when it is thinned, a low surface roughness and a high plating peel strength can be achieved, and a low CTE at a high temperature can be achieved, so that it is preferably 5 μm to 30 μm.

Examples of the support include a film of a polyolefin such as polyethylene, polypropylene, or polyvinyl chloride, polyethylene terephthalate (hereinafter also referred to as "PET"), or polyethylene naphthalate. Various plastic films such as polyester film, polycarbonate film, and polyimide film. Again, support As the body, for example, a metal foil such as a release paper, a copper foil, or an aluminum foil can be used. Among them, the general purpose is that the plastic film is preferred and the polyethylene terephthalate film is better. A surface treatment such as a matting treatment or a corona treatment may be applied to the support and the protective film described later. Further, the support film and the protective film to be described later may be subjected to a release treatment by a release agent such as an anthrone resin release agent, an alkyd resin release agent, or a fluororesin release agent.

The thickness of the support is not particularly limited, and is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 30 μm or more. Further, when the performance cost ratio is increased or the hole is formed from the support, the effective opening may be preferably 150 μm or less, more preferably 100 μm or less, and still more preferably 50 μm or less.

The protective film according to the support may be further laminated on the opposite side of the support surface of the resin composition layer. In this case, the film then includes a support, a resin composition layer formed on the support, and a protective film formed on the resin composition layer. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion or scratching of dust or the like on the surface of the resin composition layer can be prevented. The film can then be taken up in rolls to be stored.

<hardened matter>

The cured product of the present invention is obtained by thermally curing the resin composition of the present invention.

The thermosetting condition of the resin composition is not particularly limited, and for example, the conditions generally employed in forming an insulating layer of a multilayer printed wiring board can be used.

For example, the thermosetting conditions of the resin composition vary depending on the composition of the resin composition, etc., and the curing temperature is usually in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably 190 ° C to 200 ° C). The range) and the hardening time are usually in the range of 10 minutes to 180 minutes (preferably 30 minutes to 120 minutes, more preferably 90 minutes to 120 minutes).

Before the resin composition is thermally cured, the resin composition can be preheated at a temperature lower than the curing temperature. For example, before the resin composition is thermally cured, the resin composition can be usually subjected to a temperature of 50 ° C or more and less than 120 ° C (preferably 60 ° C or more and 110 ° C or less, more preferably 70 ° C or more and 100 ° C or less). More than a minute (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes) is prepared for heating.

The thickness of the cured product of the present invention varies depending on the application, but when it is used as an insulating layer of a multilayer printed wiring board, it is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and still more preferably 40 μm or less. . The lower limit of the thickness of the cured product varies depending on the application, but when it is used as an insulating layer of a multilayer printed wiring board, it is usually 10 μm or more.

<Multilayer printed wiring board using a film followed by a film>

Next, an example of a method of producing a multilayer printed wiring board using the above-described succeeding film can be described.

First, the adhesive film is laminated (stacked) on one side or both sides of the circuit board using a vacuum press machine. Examples of the substrate used for the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Again, here The circuit board refers to a conductor layer (circuit) formed by patterning on one or both sides of the above-described substrate. Further, in the multilayer printed wiring board in which the conductor layer and the insulating layer are alternately laminated, one or both of the outermost layers of the multilayer printed wiring board are patterned conductor layers (circuits), and are also included therein. Circuit board. Further, the surface of the conductor layer may be subjected to a pre-roughening treatment by blackening treatment, copper etching or the like.

When the film has a protective film, the protective film is removed, and the film and the circuit board are preheated as necessary, and the film is laminated on the circuit board while being pressed and heated. In a preferred embodiment, the adhesive film is laminated to the circuit substrate under reduced pressure by vacuum lamination. The conditions for the lamination are not particularly limited. For example, the pressing temperature (laminating temperature) is preferably 70 to 140 ° C, and the pressing pressure (laminating pressure) is preferably 1 kgf/cm ² to 11 kgf/cm ² (9.8). ×10 ⁴ N/m ² to 107.9×10 ⁴ N/m ² ), the pressing time (lamination time) is preferably from 5 seconds to 180 seconds, and the air pressure is 20 mmHg (26.7 hPa) or less under reduced pressure. Lamination is preferred. Further, the lamination method may be batch type or continuous type of rolls. Vacuum lamination can be carried out using a commercially available vacuum press. For the vacuum press machine which is commercially available, for example, a vacuum laminator manufactured by Nichigo-Morton Co., Ltd., a vacuum press laminator manufactured by Nihon Seiki Co., Ltd., and a roll dry coater manufactured by Hitachi Industries Co., Ltd. , Vacuum press machine manufactured by Hitachi AIC Inc., etc.

After the film is laminated on the circuit board and then cooled to near room temperature, when the support is peeled off, the resin composition is thermally cured to form a cured product. Thereby, an insulating layer can be formed on the circuit substrate. The conditions for thermal hardening are the same as above. After forming the insulating layer, it is not peeled before hardening When it is away from the support, it may be peeled off if necessary.

Next, the insulating layer formed on the circuit board is subjected to a hole drilling process to form a via hole and a through hole. The drilling process can be carried out, for example, by a conventional method such as a drill, a laser, a plasma, or the like, and in combination with such a method. Among them, the drilling of lasers such as carbon dioxide gas lasers and YAG lasers is the most common method. Further, the adhesive film is laminated on the circuit board, and the resin composition layer is thermally cured to form an insulating layer, and the insulating layer formed on the circuit board is formed by opening a hole from the support to form a via hole. A multilayer printed wiring board is preferred, and the support is preferably peeled off after the opening process. Thus, by performing the drilling process from the support to form the via hole, the occurrence of the contamination can be suppressed. Further, in order to reduce the thickness of the multilayer printed wiring board, the top diameter (diameter) of the via hole is preferably 15 μm to 70 μm, more preferably 20 μm to 65 μm, and still more preferably 25 μm to 60 μm.

Next, the roughening treatment of the surface of the insulating layer is performed. The dry roughening treatment may, for example, be a plasma treatment, and the wet roughening treatment may, for example, be a method of sequentially performing a swelling treatment of a swelling liquid, a roughening treatment of an oxidizing agent, and a neutralization treatment of a neutralizing liquid. Although any of the dry type and the wet type may be used for the roughening treatment, the wet type roughening treatment may preferably be performed by forming the convex and concave anchoring edges on the surface of the insulating layer to remove the dirt in the via hole. The swelling treatment of the swelling liquid is carried out by immersing the insulating layer at 50 to 80 ° C for 5 minutes to 20 minutes (preferably 55 to 70 ° C for 8 minutes to 15 minutes). The swelling solution may, for example, be an alkali solution or a surfactant solution, and is preferably an alkali solution. Examples of the alkali solution include a sodium hydroxide solution and a potassium hydroxide solution. Commercially available swelling fluids, for example "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" by Atotech Japan Co., Ltd. The roughening treatment of the oxidizing agent can be carried out by immersing the insulating layer in an oxidizing agent solution at a temperature of usually 60 ° C to 80 ° C for 10 minutes to 30 minutes (preferably 70 ° C to 80 ° C for 15 minutes to 25 minutes). Examples of the oxidizing agent include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, or the like. Further, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. The commercially available oxidizing agent may, for example, be an alkaline permanganic acid solution such as "concentrate compact CP" manufactured by Atotech Japan Co., Ltd. or "Dosing Solution Securiganth P". The neutralizing treatment of the neutralizing solution is carried out by immersing the insulating layer in a neutralization liquid at a temperature of usually 30 ° C to 50 ° C for 3 minutes to 10 minutes (preferably 35 ° C to 45 ° C for 3 minutes to 8 minutes). In the case of the neutralizing liquid, an acidic aqueous solution is preferred, and in the case of a commercial product, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd.

Ra (arithmetic mean roughness) of the surface of the insulating layer after the roughening treatment is preferably 0.2 nm or less, more preferably 150 nm or less, more preferably 120 nm or less, and even more preferably 100 nm or less. Although the lower limit is not limited, it is generally 20 nm or more. The arithmetic mean roughness (Ra value) of the surface of the insulating layer can be measured using a non-contact surface roughness meter. Specific examples of the non-contact surface roughness meter include "WYKONT 3300" manufactured by Veeco Instruments.

Next, a conductor layer is formed by dry plating or wet plating on the insulating layer. For dry plating, for example, evaporation, sputtering, or ion can be used. Conventional methods such as drape. In the case of wet plating, for example, a method of forming a conductor layer by electroless plating and electrolytic plating, a plating resist having a pattern opposite to a conductor layer, and a method of forming a conductor layer by electroless plating are used. For the method of pattern formation thereafter, for example, the conventional Subtractive method, the semi-additive method, and the like can be used. Further, by repeating the above-described one consecutive step a plurality of times, it is possible to manufacture a multilayer printed wiring board in which a plurality of layers are laminated.

The peeling strength (peeling strength) of the plated conductor layer is preferably 0.4 kgf/cm or more, more preferably 0.5 kgf/cm or more, and still more preferably 0.6 kgf/cm or more. Although the upper limit is not limited, it is generally 1.0 kgf/cm or less. The peeling strength (peeling strength) of the plated conductor layer was such that a conductor layer was formed by plating on the surface of the cured product after the roughening treatment, and the plating peel strength of the surface of the cured product and the conductor layer was measured. For the tensile testing machine, for example, "AC-50C-SL" manufactured by TSE.

<semiconductor device>

A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. At the conduction of the multilayer printed wiring board of the present invention, a semiconductor device can be manufactured by mounting a semiconductor wafer. "Conduit" means "where a signal is transmitted through a multi-layer printed wiring board", which may be a surface or embedded. Further, the semiconductor wafer is a circuit element made of a semiconductor, and is not particularly limited.

The method for mounting a semiconductor wafer in the manufacture of the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer can be effectively operated. Specific examples include wire bonding mounting methods and flip chip mounting methods. Method, mounting method without bump type (BBUL), mounting method of anisotropic conductive film (ACF), mounting method of non-conductive film (NCF), and the like.

[Examples] <Modulation of sample for peel strength and Ra value measurement> (1) Base processing of the inner layer circuit substrate

A glass cloth base material epoxy resin-clad laminate (a copper foil having a thickness of 18 μm, a substrate thickness of 0.3 mm, and a "R5715ES" manufactured by Matsushita Electric Works Co., Ltd.) was prepared as an inner layer circuit board. Both sides of the inner layer circuit board were immersed in a CZ8100 (surface treatment agent containing an organic acid) manufactured by MEC Co., Ltd., and the copper surface was roughened.

(2) followed by lamination of the film

The adhesive film produced in the examples and the comparative examples was peeled off from the adhesive film, and then a batch type vacuum pressure laminator (manufactured by a famous machine (trade name "MVLP-500") was used. Laminated on both sides of the inner circuit board. The lamination was carried out by pressurizing for 30 seconds, and the gas pressure was 13 hPa or less, followed by pressurization at 30 ° C, 100 ° C, and a pressure of 0.74 MPa.

(3) Hardening of the resin composition

The PET film was peeled off from the laminated adhesive film, and the resin composition was cured at 80 ° C, 30 minutes, followed by 180 ° C, and 30 minutes, to form an insulating layer.

(4) roughening treatment

The inner layer circuit board (laminate plate) on which the insulating layer was formed was immersed in "Swelling Dip Securiganth P" containing diethylene glycol monobutyl ether manufactured by Atotech Japan Co., Ltd. in a swelling liquid at 60 ° C for 5 minutes. Then, the inner layer circuit board was immersed in a "concentrate compact CP" (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) manufactured by Atotech Japan Co., Ltd. as a roughening solution, and immersed at 80 ° C for 20 minutes. Finally, the inner layer circuit board was immersed in "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd. as a neutralizing solution at 40 ° C for 5 minutes. (Therefore, the roughening conditions of the roughening treatment are conditions in which the inner layer circuit substrate is immersed in a swelling liquid at 60 ° C for 5 minutes, and immersed in a roughening solution at 80 ° C for 20 minutes). The inner layer circuit board (laminate) after the roughening treatment was subjected to measurement of the surface roughness by the following method.

(5) Plating with semi-additive method

In order to form a circuit on the surface of the insulating layer, the inner layer circuit substrate is immersed in a solution for electroless plating containing PdCl ₂ and then immersed in an electroless copper plating solution. After the immersed inner layer circuit substrate was heated at 150 ° C for 30 minutes and then annealed, an etching resist was formed on the obtained substrate, and an etching pattern was formed. Thereafter, copper sulfate electrolytic plating was performed on the obtained substrate to form a conductor layer with a thickness of 30 μm. Next, the obtained substrate was annealed at 180 ° C for 60 minutes. The circuit board was subjected to measurement of the peeling strength of the plated copper.

<Tapping strength (peeling strength) of the plated conductor layer>

A cut mark of a portion having a width of 10 mm and a length of 100 mm was provided on the conductor layer of the circuit board, and one end thereof was peeled off and then clamped by a jig, and the load at the time of peeling 35 mm in the vertical direction at a speed of 50 mm/min at room temperature was measured. For the tensile tester, "AC-50C-SL" manufactured by TSE was used.

<Coarse surface roughness (Ra value)>

The Ra value was determined from a value obtained by a VSI contact mode, a 50-fold lens, and a measurement range of 121 μm × 92 μm using a non-contact surface roughness meter (WYKONT 3300, manufactured by Veeco Instruments Co., Ltd.). The Ra value is an average value of 10 points randomly selected.

<Evaluation of Thermal Expansion Rate (CTE)>

The adhesive film obtained in the examples and the comparative examples was heated at 200 ° C for 90 minutes to thermally cure the resin composition layer. The cured product was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and a thermomechanical analysis was carried out by a tensile load method using a thermal mechanical analyzer (ThermoPlusTM A8310) manufactured by Rigaku. After the test piece was placed in the above apparatus, the test piece was continuously measured twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5 ° C /min. In the second measurement, the average linear thermal expansion rate at 25 ° C to 150 ° C and 150 ° C were calculated. Average linear thermal expansion rate of ~240 °C.

<100 ° C melt viscosity measurement>

The melt viscosity of the resin composition layer in the adhesive film produced in the examples and the comparative examples was measured. Use (share) U. B. The M-type Rheosol-G3000 has a resin content of 1 g, a parallel plate having a diameter of 18 mm, a starting temperature of 60 ° C to 200 ° C, a heating rate of 5 ° C / min, a measurement temperature interval of 2.5 ° C, and a vibration of 1 Hz / deg. Melt viscosity.

[Example 1]

Mixed naphthol type epoxy resin (ESN-475V manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., MEK solution of 65% by mass of non-volatile epoxy equivalent of 340) 15 parts by mass, and further liquid bisphenol A type Epoxy resin ("JER828EL" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185, weight average molecular weight: 400) 20 parts by mass, phenoxy resin solution ("XX6954BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 40000, 20 parts by mass of a mixed solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass, and 45 parts by weight of a biphenyl aralkyl type epoxy resin (epoxy equivalent 269, "Noked Chemical Co., Ltd." "NC3000L"), Active ester compound ("HP8000-65T" manufactured by DIC Co., Ltd., toluene solution having a nonvolatile content of 65% by mass of an active base equivalent of 223) 20 parts by mass of a triazine-containing cresol novolac resin (DIC) "LA3018-50P", a phenol equivalent of about 151, a non-volatile 50% by mass solution of 2-methoxypropanol) 20 parts by mass of a 10% by mass of MEK solution of 4-dimethylaminopyridine (DMAP) quality Measured, and spherical cerium oxide ("SO-C2" made by Admatechs, surface treated with amino decane, average particle size 0.5 μm) 315 parts by mass, glass fiber A (central glass fiber (manufactured)) "EFDE50" -01", an average fiber length of 50 μm, and a fiber diameter of 6 μm), 10 parts by mass, 30 parts by mass of MEK was added, and uniformly dispersed in a high-pressure disperser to prepare a resin composition varnish.

Next, the resin composition was varnished on a polyethylene terephthalate film (thickness: 38 μm, hereinafter abbreviated as PET film), and the thickness of the resin composition layer after drying was 25 μm. The coating was dried at 80 ° C to 100 ° C for 5 minutes. Next, a polypropylene film having a thickness of 15 μm was bonded to the surface of the resin composition layer, and the resin composition layer was wound into a roll shape to obtain a roll-shaped adhesive film. The roll-shaped adhesive film was cut into a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 mm × 336 mm.

[Embodiment 2]

The resin composition varnish was prepared in the same manner as in Example 1 except that the amount of the spherical cerium oxide was changed from 315 parts by mass to 275 parts by mass, and the amount of the glass fiber A was changed from 10 parts by mass to 50 parts by mass. film.

[Example 3]

In addition to changing the amount of spherical ceria from 315 parts by mass to 225 parts by mass, the amount of glass fiber A is changed from 10 parts by mass to 100 parts. In the same manner as in Example 1, a resin composition varnish was prepared in the same manner as in Example 1 to prepare a film.

[Example 4]

The resin composition varnish was prepared in the same manner as in Example 1 except that the amount of the spherical cerium oxide was changed from 315 parts by mass to 175 parts by mass, and the amount of the glass fiber A was changed from 10 parts by mass to 150 parts by mass. Then the film.

[Example 5]

A resin composition varnish was prepared in the same manner as in Example 1 except that the amount of the spherical cerium oxide was changed from 315 parts by mass to 125 parts by mass, and the amount of the glass fiber A was changed from 10 parts by mass to 200 parts by mass. Then the film.

[Embodiment 6]

A resin composition varnish was prepared in the same manner as in Example 1 except that the glass fiber A was changed to glass fiber B (manufactured by Vilene Co., Ltd., average fiber length: 77 μm, fiber diameter: 1 μm) to prepare a film.

[Comparative Example 1]

The resin composition varnish was prepared in the same manner as in Example 1 except that the amount of the spherical cerium oxide was changed from 315 parts by mass to 325 parts by mass, and the glass film A was not used.

[Comparative Example 2]

The same procedure as in Example 1 was carried out, except that the spherical cerium oxide was not added, and the glass fiber A was changed to 325 parts by mass, and the amount of MEK was changed from 30 parts by mass to 150 parts, and an attempt was made to introduce a high-pressure disperser. It has poor compatibility with the filler and cannot be dispersed.

[Comparative Example 3]

A resin composition was prepared in the same manner as in Example 3 except that 20 parts by mass of the triazine-containing cresol novolak resin ("LA3018-50P" manufactured by DIC Co., Ltd.) was changed to 40 parts by mass. Varnish, make a film.

Claims (11)

A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) spherical ceria, and (D) a glass fiber, wherein a non-volatile component in the resin composition When it is 100% by mass, the content of (C) spherical cerium oxide and (D) glass fiber is 50% by mass to 85% by mass, and the content of (D) glass fiber is 10% by mass to 50% by mass. The resin composition according to claim 1, wherein (C) the spherical cerium oxide has an average particle diameter of 5 μm or less. The resin composition according to claim 1, wherein the (D) glass fiber has an average fiber diameter of 13 μm or less and an average fiber length of 100 μm or less. The resin composition according to claim 3, wherein (D) the glass fiber has an average fiber diameter of 6 μm or less. The resin composition according to claim 1, wherein the average linear thermal expansion coefficient at 150 ° C to 240 ° C is 50 ppm or less. The resin composition according to claim 1, which is used for an insulating layer of a multilayer printed wiring board. A film which is formed by forming a layer composed of the resin composition according to any one of claims 1 to 6 on a support. The adhesive film according to claim 7, wherein the thickness of the layer composed of the resin composition is 5 μm to 40 μm. A cured product which is a cured product of the resin composition according to any one of claims 1 to 6. A multilayer printed wiring board characterized in that it is produced using the adhesive film described in claim 7. A semiconductor device characterized by using the multilayer printed wiring board described in claim 10.