JP2015067626A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of achieving low surface roughness and high plating peel strength and achieving low CTE at high temperatures, even when being formed into a thin layer.SOLUTION: A resin composition contains (A) an epoxy resin, (B) an active ester compound, (C) spherical silica, and (D) a glass fiber.

Description

  The present invention relates to a resin composition. Furthermore, this invention relates to the adhesive film, hardened | cured material, multilayer printed wiring board, and semiconductor device which used this resin composition.

In recent years, with the miniaturization and high functionality of semiconductor devices, multilayer printed wiring boards have been required to be thinned while maintaining strength.
Various epoxy resin compositions suitable for thinning have been studied. For example, in Patent Document 1, epoxy resin (a), glass fiber (b) having a fiber length of 200 μm or less, and spherical shape having an average particle size of 30 μm or less. An epoxy resin molding material characterized by containing silica (c) is described. By using glass fiber (b) having a fiber length of 200 μm or less, resin flowability is suppressed by glass fiber, and molding is performed. The mechanical strength of the product is improved.

JP 2005-281362 A

  However, the present inventors have repeatedly studied about the thinning of the epoxy resin composition, and when the epoxy resin composition containing glass fibers is thinned, the glass fibers are easily exposed from the surface of the layer, It has been found that the surface roughness becomes rough.

  Accordingly, the present invention is a resin composition suitable for forming an insulating layer of a printed wiring board, and has a low surface even when thinned by producing a printed wiring board using the resin composition. It is an object of the present invention to provide a resin composition that can achieve roughness and high plating peel strength and can achieve low CTE at high temperatures.

  The present invention has been made in view of the above, and includes an active ester compound in a resin composition containing an epoxy resin, spherical silica, and glass fiber, so that the glass fiber is also thinned. Found that a resin composition can be obtained that is difficult to be exposed from the surface of the layer, can achieve low surface roughness and high plating peel strength, and can achieve low CTE at high temperatures. It came to do.

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 silica, and (D) glass fibers.
[2] When the nonvolatile component in the resin composition is 100% by mass, the total content of (C) spherical silica and (D) glass fiber is 50 to 85% by mass, and (D) the glass fiber The resin composition according to [1], wherein the content is 2 to 60% by mass.
[3] The resin composition according to [2], wherein the content of the glass fiber (D) is 10 to 50% by mass when the nonvolatile component in the resin composition is 100% by mass.
[4] The resin composition according to any one of [1] to [3], wherein (C) the spherical silica has an average particle size of 5 μm or less.
[5] (D) The resin composition according to any one of [1] to [4], wherein the glass fiber has an average fiber diameter of 13 μm or less and an average fiber length of 100 μm or less.
[6] (D) The resin composition according to [5], wherein 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 an average linear thermal expansion coefficient from 150 ° C. to 240 ° C. is 50 ppm or less.
[8] The resin composition according to any one of [1] to [7], which is for an insulating layer of a multilayer printed wiring board.
[9] An adhesive film in which a layer composed of the resin composition according to any one of [1] to [8] 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 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 produced using the adhesive film according to [9] or [10].
[13] A semiconductor device using the multilayer printed wiring board according to [12].

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

  One embodiment of the present invention provides a resin composition containing (A) an epoxy resin, (B) an active ester compound, (C) spherical silica, and (D) glass fibers.

<(A) Epoxy resin>
The epoxy resin used in the present invention is not particularly limited, but is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol. Type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, Epoxy resin having butadiene structure, cycloaliphatic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy Shi resins, halogenated epoxy resins, dicyclopentadiene type epoxy resins. These may be used alone or in combination of two or more.

  Of these, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type from the viewpoint of improving heat resistance, insulation reliability, and adhesion to the conductor layer. Epoxy resins, anthracene type epoxy resins, epoxy resins having a butadiene structure, and dicyclopentadiene type epoxy resins are preferred. Specifically, for example, bisphenol A type epoxy resin (“Epicoat 828EL”, “YL980” manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (“jER806H”, “YL983U” manufactured by Mitsubishi Chemical Corporation), 1: 1 mixture of bisphenol A type and bisphenol F type (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D”, “HP4032SS” manufactured by DIC Corporation), “EXA4032SS”), naphthalene type tetrafunctional epoxy resin (“HP4700”, “HP4710” manufactured by DIC Corporation), naphthol type epoxy resin (“ESN-475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), epoxy having a butadiene structure Resin ("PB-3600" manufactured by Daicel Chemical Industries, Ltd.) Epoxy resins having a phenyl structure (“NC3000H”, “NC3000L”, “NC3100” manufactured by Nippon Kayaku Co., Ltd., “YX4000”, “YX4000H”, “YX4000HK”, “YL6121” manufactured by Mitsubishi Chemical Corporation), dihydro Anthracene type epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation), naphthylene ether type epoxy resin ("EXA-7310", "EXA-7311", "EXA-7311L", "EXA7311-G3" manufactured by DIC Corporation) And dicyclopentadiene type epoxy resin (“HP-7200H” manufactured by DIC Corporation).

  Two or more epoxy resins may be used in combination, but it is preferable to contain an epoxy resin having two or more epoxy groups in one molecule. Among them, an aromatic epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”) and three or more epoxy in one molecule. An embodiment containing a group and containing a solid aromatic epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. is more preferable. In addition, the aromatic epoxy resin as used in the field of this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator. When using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, when using the resin composition in the form of an adhesive film, the resin composition has an appropriate flexibility and the cured product of the resin composition has an appropriate breaking strength. From the point of having, the mixture ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 1: 5 by mass ratio, more preferably in the range of 1: 0.3 to 1: 4. A range of 1: 0.6 to 1: 3 is more preferable.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and naphthalene type epoxy resin are preferable, and bisphenol A type epoxy resin and naphthalene type epoxy resin are more preferable. You may use these 1 type or in combination of 2 or more types.

  Examples of solid epoxy resins include tetrafunctional naphthalene type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, biphenyl type epoxy resins, and naphthylene ether type epoxy resins. A tetrafunctional naphthalene type epoxy resin, a biphenyl type epoxy resin, and a naphthylene ether type epoxy resin are more preferable. You may use these 1 type or in combination of 2 or more types.

  In the resin composition of the present invention, from the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition, the content of the epoxy resin is 3 when the nonvolatile component in the resin composition is 100% by mass. It is preferable that it is -35 mass%, It is more preferable that it is 5-30 mass%, It is still more preferable that it is 10-20 mass%.

  The epoxy equivalent of the epoxy resin is preferably 50 to 3000, more preferably 80 to 2000, and still more preferably 110 to 1000. By being in this range, the cured product has a sufficient cross-linking density, resulting in an insulating layer having excellent heat resistance. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

<(B) Active ester compound>
Although there is no restriction | limiting in particular as an active ester compound, Generally 2 ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of a heterocyclic hydroxy compound, are generally contained in 1 molecule. A compound having at least one is preferably used. The active ester compound is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, and m-cresol. P-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzene Triol, active ester compound containing naphthalene structure, dicyclopentadiene type diphenol compound (polycyclopentadiene type Diphenol compound), phenol novolac and the like. The active ester compound can use 1 type (s) or 2 or more types. As an active ester compound, the active ester compound currently disclosed by Unexamined-Japanese-Patent No. 2004-277460 may be used, and a commercially available thing can also be used. Commercially available active ester compounds include active ester compounds containing a dicyclopentadiene-type diphenol condensation structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolac, and benzoylated products of phenol novolac. An active ester compound or the like is preferable, and an active ester compound containing a dicyclopentadiene type diphenol condensation structure is more preferable. Specifically, as an active ester compound containing a dicyclopentadiene-type diphenol condensation structure, EXB9451, EXB9460, HPC8000-65T (manufactured by DIC Corporation, active group equivalent of about 223), an active ester compound containing an acetylated product of phenol novolac DC808 (Mitsubishi Chemical Corporation, active group equivalent of about 149), YLH1026 (Mitsubishi Chemical Corporation, active group equivalent of about 200), YLH1030 (Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated phenol novolak ), Active group equivalent of about 201), YLH1048 (manufactured by Mitsubishi Chemical Co., Ltd., active group equivalent of about 245), and the like. Among them, HPC-8000-65T is storage stability of varnish, thermal expansion of cured product From the viewpoint that the skeleton has a high rate and high hydrophobicity.

  Since the active ester compound reacts with the free hydroxyl group of the epoxy resin to form an ester bond, it is easy to form a highly hydrophobic cured product and prevents the insulating layer surface from being too rough during the roughening treatment. Even if glass fiber is used, the glass fiber is not exposed from the surface of the layer, and low surface roughness and high plating peel strength can be realized. On the other hand, when the active ester compound is not blended, the cured product of the surface layer is easily roughened during the roughening treatment, and the glass fibers are more easily exposed from the surface of the layer than when the active ester compound is blended. Surface roughness increases and plating peel strength tends to decrease.

  More specifically, examples of the active ester compound containing a dicyclopentadiene type diphenol condensation structure include compounds represented by the following formula.

(In the formula, R is a phenyl group or a naphthyl group, k represents 0 or 1, and n is 0.05 to 2.5 on the average of repeating units.)

  From the viewpoint of reducing the dielectric loss tangent and improving the heat resistance, R is preferably a naphthyl group, while 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 component in the resin composition is 100% by mass from the viewpoint of improving heat resistance and obtaining good plating peel strength without excessively increasing hydrophobicity. Preferably, 30 mass% or less is more preferable, 20 mass% or less is still more preferable, and 15 mass% or less is still more preferable. On the other hand, from the viewpoint of improving the laminating property and suppressing the protrusion of the glass fiber to reduce the surface of the cured product, the content of the active ester compound is 0 when the nonvolatile component in the resin composition is 100% by mass. 0.5 mass% or more is preferable, 1 mass% or more is more preferable, 1.5 mass% or more is still more preferable, and 2 mass% or more is still more preferable.

  In addition, when the number of epoxy groups of (A) the epoxy resin is 1, the number of reactive groups of the (B) active ester compound is preferably 0.2 to 2 in terms of improving the mechanical properties of the resin composition. 3-1.5 are more preferable and 0.4-1 are still more preferable. Here, “the number of epoxy groups of the epoxy resin” is a value obtained by totaling the values obtained by dividing the solid mass of each epoxy resin present in the resin composition by the epoxy equivalent for all epoxy resins. The “reactive group” means a functional group capable of reacting with an epoxy group, and the “reactive group number of the active ester compound” means the solid content mass of the active ester compound present in the resin composition. This is the total value of all values divided by equivalents.

<(C) Spherical silica>
Spherical silica may be used alone or in combination of two or more. Spherical silica is preferably spherical fused silica from the viewpoint of reducing the thermal expansion coefficient. Examples of commercially available spherical fused silica include “SO-C2” and “SO-C1” manufactured by Admatechs.

  The average particle diameter of the spherical silica is preferably in the range of 0.01 μm to 5 μm, more preferably in the range of 0.05 μm to 3 μm, still more preferably in the range of 0.1 μm to 1 μm, and even more preferably in the range of 0.3 μm to 0.8 μm. preferable. The average particle diameter of the spherical silica can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of spherical silica is prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring device, and the median diameter can be measured as an average particle size. As the measurement sample, spherical silica dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. can be used.

  The content of the spherical silica is preferably 20% by mass or more, more preferably 40% by mass or more from the viewpoint of reducing the thermal expansion coefficient of the obtained insulating layer when the nonvolatile component in the resin composition is 100% by mass. 50 mass% or more is still more preferable, 60 mass% or more, 65 mass% or more, 70 mass% or more is still more preferable. On the other hand, the upper limit of the content of the spherical silica is preferably 90% by mass or less, more preferably 80% by mass, from the viewpoint of the mechanical strength of the obtained insulating layer when the nonvolatile component in the resin composition is 100% by mass. % Or less.

  Spherical silica is one or more of aminosilane coupling agent, epoxysilane coupling agent, mercaptosilane coupling agent, silane coupling agent, organosilazane compound, titanate coupling agent and the like for improving moisture resistance. It is preferable that the surface treatment agent is used. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (Hexamethyldisilazane) manufactured by Co., Ltd.

  Further, the spherical silica surface-treated with the surface treatment agent can be measured for the amount of carbon per unit surface area of the spherical silica after washing with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

Carbon content per unit surface area of the spherical silica, from the viewpoint of improving the dispersibility of the spherical silica is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} or more Further preferred. On the other hand, 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 from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the film form. preferable.

<(D) Glass fiber>
A glass fiber may be used individually by 1 type, and may use 2 or more types together. Examples of commercially available glass fibers include chopped strands and milled fiber glass fibers.

  The average fiber diameter of the glass fiber is preferably 13 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, still more preferably 6 μm or less, particularly preferably 4 μm or less, and more particularly from the viewpoint of suppressing the surface roughness. Preferably it is 2 micrometers or less. Although a minimum is not specifically limited, Usually, it can be 0.5 micrometer or more.

  The average fiber length of the glass fiber is preferably 5 μm or more, more preferably 10 μm or more, even 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 improving the thickness, it is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and even more preferably 50 μm or less.

  In one Embodiment of this invention, it is preferable that the average fiber diameter of (D) glass fiber is 13 micrometers or less, and an average fiber length is 100 micrometers or less.

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

  The content of the glass fiber is preferably 2% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass from the viewpoint of lowering the thermal expansion coefficient when the nonvolatile component in the resin composition is 100% by mass. The above is more preferable. Moreover, from a viewpoint of improving the compatibility of a varnish, 60 mass% or less is preferable, 50 mass% or less is more preferable, 40 mass% or less is still more preferable, 30 mass% or less is especially preferable.

  The total content of (C) spherical silica and (D) glass fiber is preferably 50% by mass or more from the viewpoint of lowering the coefficient of thermal expansion when the nonvolatile component in the resin composition is 100% by mass. 55 mass% or more is more preferable, 60 mass% or more is still more preferable, and 65% or more is especially preferable. Moreover, from a viewpoint of improving the compatibility of a varnish, 85 mass% or less is preferable and 80 mass% or less is more preferable.

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

  In another embodiment of the present invention, when the nonvolatile component in the resin composition is 100% by mass, the total content of (C) spherical silica and (D) glass fiber is 50 to 80% by mass. (D) It is preferable that content of glass fiber is 10-50 mass%.

  In one embodiment of the present invention, the average linear thermal expansion coefficient from 25 ° C. to 150 ° C. of the cured product of the resin composition is preferably 25 ppm or less, preferably 20 ppm or less, and 18 ppm or less. Further preferred. Although there is no restriction | limiting in a lower limit, generally it will be 4 ppm or more.

  In one embodiment of the present invention, the average linear thermal expansion coefficient from 150 ° C. to 240 ° C. of the cured resin composition is 50 ppm or less from the viewpoint of reducing CTE mismatch between the circuit and the insulating layer at the time of component mounting. It is preferably 40 ppm or less, more preferably 30 ppm or less. Although there is no restriction | limiting in a lower limit, generally it will be 10 ppm or more.

  The linear thermal expansion coefficient can be measured by performing thermomechanical analysis by a tensile load method using a thermomechanical analyzer manufactured by Rigaku Corporation (Thermo Plus TMA8310).

<(E) Other ingredients>
The resin composition of the present invention may contain other components as long as the effects of the present invention can be achieved.

  The resin composition of the present invention includes the following other components such as a thermoplastic resin; a curing agent such as a cyanate ester curing agent, a phenol curing agent, a naphthol curing agent, and a benzoxazine curing agent; a curing accelerator. One or more additives such as flame retardant, rubber particles, and the like may be further included as necessary.

-Thermoplastic resin-
Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, and polysulfone resin. A thermoplastic resin may be used individually by 1 type, or may use 2 or more types together.

  The weight average molecular weight in terms of polystyrene 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 still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-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.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, or may use 2 or more types together. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280”, “FX293” and “FX293L” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YX7553”, “YL6794” manufactured by Mitsubishi Chemical Co., Ltd., "YL7213", "YL7290", "YL7482", etc. are mentioned.

  Specific examples of the polyvinyl acetal resin include electric butyral 4000-2, 5000-A, 6000-C, and 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., and ESREC BH series and BX series manufactured by Sekisui Chemical Co. KS series, BL series, BM series, etc. are mentioned.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  As content of a thermoplastic resin, when the non-volatile component in a resin composition is 100 mass%, 0.01-2 mass% is mentioned, for example.

-Curing agents such as cyanate ester curing agents, phenolic curing agents, naphthol curing agents, benzoxazine curing agents-
In the resin composition of the present invention, as long as the effects of the present invention are exhibited, in addition to the active ester compound, a curing agent such as a cyanate ester curing agent, a phenol curing agent, a naphthol curing agent, or a benzoxazine curing agent is included. May be.

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylene bis (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, and bis (4-cyanatephenyl) ether; Phenol novolac and Polyfunctional cyanate resin derived from resol novolac, these cyanate resins and partially triazine of prepolymer. Preferable specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolac polyfunctional cyanate ester resins) and “BA230” (part of bisphenol A dicyanate or And a prepolymer which is all triazine-modified into a trimer).

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance. Moreover, from a viewpoint of adhesiveness with a conductor layer (circuit wiring), a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable. Especially, it is preferable to use a triazine skeleton containing phenol novolak resin as a hardening | curing agent from a viewpoint of heat resistance and adhesiveness (peeling strength) with a conductor layer.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN375”, “SN395” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ”,“ LA7052 ”,“ LA7054 ”,“ LA3018 ”manufactured by DIC Corporation, and the like.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Curing agents such as a cyanate ester curing agent, a phenol curing agent, a naphthol curing agent, and a benzoxazine curing agent may be used alone or in combination of two or more. Content of the said hardening | curing agent can be 0.01-3 mass%, when the non-volatile component in a resin composition is 100 mass%.

-Curing accelerator-
Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. A hardening accelerator and a metal type hardening accelerator are preferable.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

  Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8 -Diazabicyclo [5.4.0] -undecene and the like can be mentioned, and 4-dimethylaminopyridine and 1,8-diazabicyclo [5.4.0] -undecene are preferable.

  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 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-me Examples thereof include imidazole compounds such as ru-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2. -Phenylimidazole is preferred.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  Although it does not specifically limit as a metal type hardening accelerator, For example, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned. 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. These may be used alone or in combination of two or more. As the metal-based curing accelerator, an organic cobalt complex is preferably used, and in particular, cobalt (III) acetylacetonate is preferably used.

  A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type. As for content of a hardening accelerator, when the non-volatile component in a resin composition is 100 mass%, it is preferable to use in 0.01 mass%-3 mass%.

-Flame retardant-
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. A flame retardant may be used individually by 1 type, or may use 2 or more types together. The content of the flame retardant is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, 0.5% by mass to 10% by mass is preferable, and 1% by mass to 9% by mass is more preferable. 1.5 mass% to 8 mass% is more preferable.

-Rubber particles-
As the rubber particles, for example, those that do not dissolve in an organic solvent described later and are incompatible with the above-described epoxy resin, curing agent, thermoplastic resin, and the like are used. 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.

  Examples of the rubber particles 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 glassy polymer layer is made of, for example, methyl methacrylate polymer, and the rubbery polymer layer is made of, for example, butyl acrylate polymer (butyl rubber). A rubber particle may be used individually by 1 type and may be used in combination of 2 or more type.

  The average particle size 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 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 in the resin composition is preferably 1% by mass to 10% by mass, and more preferably 2% by mass to 5% by mass.

  The resin composition of the present invention may further contain other additives as necessary. Examples of such other additives include organic fillers, thickeners, antifoaming agents, leveling agents, and adhesion. Examples thereof include resin additives such as a property-imparting agent and a colorant.

  The resin composition of the present invention is appropriately mixed with the above components and, if necessary, kneaded or stirred by a kneading means such as a triple roll, ball mill, bead mill or sand mill, or a stirring means such as a super mixer or a planetary mixer. By doing so, it can be produced as a resin varnish.

  The use of the resin composition of the present invention is not particularly limited, but a sheet-like laminated material such as an adhesive film, a circuit board (for laminated board use, multilayer printed wiring board use, etc.), solder resist, underfill material, die bonding material, It can be used in a wide range of applications where a resin composition is required, such as a semiconductor sealing material, hole filling resin, and component filling resin. Among them, the resin composition of the present invention can be suitably used as a resin composition for an insulating layer of a multilayer printed wiring board, and is a resin composition for forming a conductor layer by plating (a conductor layer is formed by plating). The resin composition for an insulating layer of a multilayer printed wiring board) or a resin composition for forming a buildup layer of a multilayer printed wiring board can be used more suitably. The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, or can be used in the form of a sheet-like laminated material such as an adhesive film.

<Adhesive film>
The adhesive film is formed by forming a layer composed of a resin composition on a support. The adhesive film is a method known to those skilled in the art, for example, 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, further heating, Or it can manufacture by drying the organic solvent by hot air spraying etc. and forming the layer comprised from a resin composition. The layer comprised from a resin composition is also called a 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. And aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Two or more organic solvents may be used in combination.

  The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is 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. can do. This resin composition layer is sometimes referred to as a B-stage film, and is not completely cured, so that the curing can further proceed.

  The melt viscosity at 100 ° C. of the resin composition layer is preferably 35000 poise or less, more preferably 20000 poise or less, and more preferably 10,000 poise or less from the viewpoint of obtaining an adhesive film with good laminating properties and embedding properties. Is more preferably 5000 poise or less, and even more preferably 3000 poise or less. In addition, from the viewpoint of preventing bleeding during lamination, 500 poise or more is preferable, and 1000 poise or more is more preferable. Since laminating the resin composition layer is usually performed at around 100 ° C., the laminating property of the adhesive film can be evaluated by the melt viscosity value at 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, a parallel plate having a resin amount of 1 g and a diameter of 18 mm is used, and the measurement conditions are a start temperature of 60 ° C. to 200 ° C., a temperature increase rate of 5 ° C./min, a measurement temperature interval of 2.5 ° C., and vibration of 1 Hz / deg. By measuring the dynamic viscoelasticity at, the melt viscosity at 100 ° C. of the resin composition layer can be measured. Examples of such a dynamic viscoelasticity measuring apparatus include model Rhesol-G3000 manufactured by UBM Co., Ltd.

  The thickness of the resin composition layer formed in the adhesive film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is more preferably 5 to 40 μm. In particular, in the present invention, even when 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.

  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. Among these, from the viewpoint of versatility, a plastic film is preferable, and a polyethylene terephthalate film is more preferable. 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.

  The thickness of the support is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more in terms of improved handling properties. Further, from the viewpoint of improving cost performance and enabling efficient drilling when drilling from the support, it is preferably 150 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less.

  A protective film according to the support can be further laminated on the surface of the resin composition layer opposite to the surface to which the support is in close contact. In this case, the adhesive film includes a support, a resin composition layer formed on the support, and a protective film formed on the resin composition layer. 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.

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

  The thermosetting conditions for the resin composition are not particularly limited, and for example, the conditions normally employed when forming the insulating layer of the multilayer printed wiring board may be used.

  For example, the thermosetting conditions of the resin composition vary depending on the composition of the resin composition and the like, but the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably in the range of 190 ° C to 200 ° C. C.) and the curing time can be 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 may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition, the resin composition is kept at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower) for 5 minutes. Preheating may be performed as described above (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  The thickness of the cured product of the present invention varies depending on the application, but when 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 even more preferably 40 μm. It is as follows. Although the minimum of the thickness of hardened | cured material changes with uses, when using as an insulating layer of a multilayer printed wiring board, it is 10 micrometers or more normally.

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

  First, the adhesive film is laminated (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.

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 laminated to the circuit board while being pressurized and heated. In one preferred embodiment, the adhesive film is laminated to the circuit board under reduced pressure by a vacuum laminating method. 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 (laminating pressure) is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), the pressure bonding time (laminating time) is preferably 5 to 180 seconds, and the 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 Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

  After laminating the adhesive film on the circuit board, the substrate is cooled to around room temperature and then peeled off when the support is peeled off, and the resin composition is thermally cured to form a cured product. Thereby, an insulating layer can be formed on the circuit board. The conditions for thermosetting are as described above. After the insulating layer is formed, if the support is not peeled before curing, it can be peeled off here if necessary.

  Next, a hole is formed in the insulating layer formed on the circuit board to form a via hole and a through hole. The drilling can be performed by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. Of these, drilling with a laser such as a carbon dioxide laser or a YAG laser is the most common method. Also, by laminating an adhesive film on a circuit board, thermosetting the resin composition layer to form an insulating layer, and forming a via hole by drilling the insulating layer formed on the circuit board from above the support. It is preferable to produce a multilayer printed wiring board, and it is preferable to peel the support after drilling. Thus, by forming a via hole by drilling from the support, it is possible to suppress the occurrence of smear. Further, in order to cope with the thinning of the multilayer printed wiring board, the top diameter (diameter) of the via hole is preferably 15 to 70 μm, more preferably 20 to 65 μm, and still more preferably 25 to 60 μm.

  Next, the surface of the insulating layer is roughened. Examples of the dry roughening treatment include plasma treatment, and examples of the wet roughening treatment include a method in which a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution are performed in this order. Either dry or wet roughening treatment may be adopted, but wet roughening treatment can remove smear in the via hole while forming uneven anchors on the insulating layer surface. preferable. The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes (preferably at 55 to 70 ° C. for 8 to 15 minutes). Examples of the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include sodium hydroxide solution and potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securigant P (Swelling Dip Securiganth P), Swelling Dip Securigant SBU (Swelling Dip Securiganth SBU) manufactured by Atotech Japan Co., Ltd. be able to. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C. for 10 to 30 minutes (preferably at 70 to 80 ° C. for 15 to 25 minutes). Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as concentrate compact CP and dosing solution securigant P manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is performed by immersing the insulating layer in the neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably at 35 to 45 ° C. for 3 to 8 minutes). The neutralizing solution is preferably an acidic aqueous solution, and a commercially available product is Reduction Solution Securigant P manufactured by Atotech Japan Co., Ltd.

  The Ra (arithmetic mean roughness) of the surface of the insulating layer after the roughening treatment is preferably 200 nm or less, more preferably 150 nm or less, and 120 nm or less from the viewpoint of enabling fine wiring formation. Is still more preferable, and it is especially preferable that it is 100 nm or less. The lower limit is not limited, but is generally 20 nm or more. The arithmetic average roughness (Ra value) of the insulating layer surface can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Becoins Instruments is cited.

  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. Examples of wet plating include a method in which a conductive layer is formed by combining electroless plating and electrolytic plating, a method in which a plating resist having a pattern opposite to that of the conductive layer is formed, and a conductive layer is formed only by electroless plating. It is done. 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. And the multilayer printed wiring board which laminated | stacked the buildup layer in multiple stages can be manufactured by repeating the above-mentioned series of processes several times.

  The peel strength of the plated conductor layer is preferably 0.4 kgf / cm or more, more preferably 0.5 kgf / cm or more, and even more preferably 0.6 kgf / cm or more. Although there is no restriction | limiting in an upper limit, Generally it will be 1.0 kgf / cm or less. As for the peel strength of the plated conductor layer, a conductor layer is formed on the cured product surface after the roughening treatment by plating, and the plating peel strength between the cured product surface and the conductor layer is measured. Examples of the tensile tester include “AC-50C-SL” manufactured by TSE Corporation.

<Semiconductor device>
A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion of the multilayer printed wiring board of the present invention. The “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

<Preparation of peel strength and Ra value measurement sample>
(1) Underlayer treatment of inner layer circuit board Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works R5715ES) on which an inner layer circuit is formed The copper surface was roughened by dipping in CZ8100 (a surface treatment agent containing an organic acid) manufactured by MEC Co., Ltd.

(2) Lamination of Adhesive Film The adhesive films produced in the examples and comparative examples were laminated on both sides of the inner circuit board 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) Curing of resin composition The PET film was peeled off from the laminated adhesive film, and the resin composition was cured under curing conditions of 80 ° C, 30 minutes, then 180 ° C, 30 minutes to form an insulating layer. .

(4) Roughening treatment The laminate is immersed in a swelling liquid, a swelling ring dip securigant P containing diethylene glycol monobutyl ether manufactured by Atotech Japan Co., Ltd., and then used as a roughening liquid. ) Manufactured by Concentrate Compact CP (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution), and finally at 40 ° C. as a neutralizing solution, reduced solution securigant P manufactured by Atotech Japan Co., Ltd. (Roughening conditions: the laminate was immersed in the swelling liquid at 60 ° C. for 5 minutes and immersed in the roughening liquid at 80 ° C. for 20 minutes). About the laminated board after this roughening process, the surface roughness was measured with the following method.

(5) Plating by semi-additive method In order to form a circuit on the surface of the insulating layer, the inner layer circuit board was immersed in an electroless plating solution containing PdCl ₂ and then immersed in an electroless copper plating solution. After the immersion, the inner layer circuit board was heated at 150 ° C. for 30 minutes for annealing treatment, and then an etching resist was formed on the obtained substrate to form a pattern by etching. 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 peel strength of the plated copper was measured for this circuit board.

<Stripping strength of peeled conductor layer (peel strength)>
When a notch with a width of 10 mm and a length of 100 mm is cut into the conductor layer of the circuit board, this one end is peeled off and gripped with a gripper, and 35 mm is peeled off vertically at a speed of 50 mm / min at room temperature The load of was measured. As a tensile tester, “AC-50C-SL” manufactured by TSE Co., Ltd. was used.

<Surface roughness after roughening (Ra value)>
Using a non-contact type surface roughness meter (BYCO Instruments WYKO NT3300), the Ra value was obtained from the numerical value obtained by measuring the measurement range to 121 μm × 92 μm with a VSI contact mode and a 50 × lens. For the Ra value, an average value of 10 points randomly selected was obtained.

<Evaluation of linear thermal expansion coefficient (CTE)>
The adhesive films obtained in Examples and Comparative Examples were 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 thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer manufactured by Rigaku Corporation (Thermo Plus TMA8310). After mounting the test piece on the apparatus, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. In the second measurement, an average linear thermal expansion coefficient from 25 ° C. to 150 ° C. and an average linear thermal expansion coefficient from 150 ° C. to 240 ° C. were calculated.

<Measurement of melt viscosity at 100 ° C.>
The melt viscosity of the resin composition layer in the adhesive films prepared in Examples and Comparative Examples was measured. Using UBM Model Rheosol-G3000, using a parallel plate with a resin amount of 1 g and a diameter of 18 mm, starting temperature from 60 ° C. to 200 ° C., heating rate of 5 ° C./min, measurement The melt viscosity was measured under the measurement conditions of a temperature interval of 2.5 ° C. and a vibration of 1 Hz / deg.

[Example 1]
15 parts by mass of naphthol type epoxy resin (“ESN-475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., MEK solution having a nonvolatile content of 65% by mass with an epoxy equivalent of about 340), and liquid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation) 20 parts by mass of “jER828EL”, epoxy equivalent of about 185), 20 parts by mass of a phenoxy resin solution (“YX6954BH30” manufactured by Mitsubishi Chemical Co., Ltd., weight average molecular weight 40000, non-volatile content of 30% by mass of MEK and cyclohexanone) 45 parts of biphenyl aralkyl type epoxy resin (epoxy equivalent 269, “NC3000L” manufactured by Nippon Kayaku Co., Ltd.), active ester compound (“HP8000-65T” manufactured by DIC Corporation), non-volatile content 65% by mass of active group equivalent about 223 Toluene solution) 20 parts by mass, triazine-containing cresol novolak 20 parts by mass of fat (“LA3018-50P” manufactured by DIC Corporation, phenol equivalent of about 151, 2-methoxypropanol solution having a nonvolatile content of 50% by mass), 10% by mass of MEK solution of 10% by mass of 4-dimethylaminopyridine (DMAP) 3 Parts by weight, and spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., surface-treated with aminosilane, average particle size 0.5 µm), 315 parts by weight, glass fiber A ("EFDE50" manufactured by Central Glass Fiber Co., Ltd.) -01 ", average fiber length 50 μm, fiber diameter 6 μm) After mixing 10 parts by mass, MEK 30 parts by mass was added and uniformly dispersed with a high-pressure disperser to prepare a resin composition varnish.
Next, such a resin composition varnish is uniformly coated 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 25 μm. And dried at 80 to 100 ° C. for 5 minutes. Subsequently, the resin composition layer was wound up in a roll shape while a 15 μm-thick polypropylene film was bonded to the surface of the resin composition layer to obtain a roll-shaped adhesive film. 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]
Resin composition varnish in the same manner as in Example 1, except that the amount of spherical silica was changed from 315 parts by weight to 275 parts by weight and the amount of glass fiber A was changed from 10 parts by weight to 50 parts by weight. To prepare an adhesive film.

[Example 3]
Resin composition varnish in the same manner as in Example 1, except that the amount of spherical silica was changed from 315 parts by weight to 225 parts by weight and the amount of glass fiber A was changed from 10 parts by weight to 100 parts by weight. To prepare an adhesive film.

[Example 4]
Resin composition varnish in the same manner as in Example 1 except that the amount of spherical silica was changed from 315 parts by weight to 175 parts by weight and the amount of glass fiber A was changed from 10 parts by weight to 150 parts by weight. To prepare an adhesive film.

[Example 5]
Resin composition varnish in the same manner as in Example 1 except that the amount of spherical silica was changed from 315 parts by weight to 125 parts by weight and the amount of glass fiber A was changed from 10 parts by weight to 200 parts by weight. To prepare an adhesive film.

[Example 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 Japan Vilene Co., Ltd., average fiber length 77 μm, fiber diameter 1 μm). Produced.

[Comparative Example 1]
The resin composition varnish was prepared in the same manner as in Example 1 except that the amount of the spherical silica was changed from 315 parts by mass to 325 parts by mass and the glass fiber A was not added, and an adhesive film was produced. .

[Comparative Example 2]
Although the spherical silica was not blended, 10 parts by weight of the glass fiber A was changed to 325 parts by weight, and except that 150 parts of MEK was added, the same blending as in Example 1 was attempted, and an attempt was made to put into a high-pressure disperser. Dispersion was impossible due to poor compatibility between the resin and the filler.

[Comparative Example 3]
Resin composition in the same manner as in Example 3 except that no active ester compound was blended and 20 parts by mass of triazine-containing cresol novolac resin (“LA3018-50P” manufactured by DIC Corporation) was changed to 40 parts by mass. A varnish was prepared to produce an adhesive film.

Claims (13)

  A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) spherical silica, and (D) glass fibers.   When the nonvolatile component in the resin composition is 100% by mass, the total content of (C) spherical silica and (D) glass fiber is 50 to 85% by mass, and (D) the content of glass fiber is The resin composition of Claim 1 which is 2-60 mass%.   The resin composition of Claim 2 whose content of (D) glass fiber is 10-50 mass% when the non-volatile component in a resin composition is 100 mass%.   (C) The resin composition of any one of Claims 1-3 whose average particle diameter of spherical silica is 5 micrometers or less.   (D) The resin composition of any one of Claims 1-4 whose average fiber diameter of glass fiber is 13 micrometers or less, and whose average fiber length is 100 micrometers or less.   (D) The resin composition of Claim 5 whose average fiber diameter of glass fiber is 6 micrometers or less.   The resin composition according to any one of claims 1 to 6, wherein an average linear thermal expansion coefficient from 150 ° C to 240 ° C is 50 ppm or less.   The resin composition according to any one of claims 1 to 7, which is used for an insulating layer of a multilayer printed wiring board.   The adhesive film by which the layer comprised from the resin composition of any one of Claims 1-8 is formed on a support body.   The adhesive film of Claim 9 whose thickness of the layer comprised from a resin composition is 5-40 micrometers.   Hardened | cured material of the resin composition of any one of Claims 1-8.   The multilayer printed wiring board manufactured using the adhesive film of Claim 9 or 10.   13. A semiconductor device using the multilayer printed wiring board according to claim 12.