JP2020136542A - Manufacturing method of print circuit board - Google Patents

Abstract

To provide a manufacturing method of a print circuit board, capable of suppressing the generation of cracking along a pattern in an inner-layer substrate.SOLUTION: A manufacturing method of a print circuit board comprises: (A) a step of forming an insulation layer in which a resin component layer of a lamination body, having an inner layer substrate and the resin component layer including a resin component so as to be jointed to the inner layer substrate is thermally hardened at 130°C or more and 220°C or less, and which contains a hardening material of the resin component; (C) a step in which the insulation layer is anneal-treated under 60°C or more and 150°C or less; and (D) a step of performing a desmear process of the insulation layer with an oxidant solution in this order. In the manufacturing method of the print circuit board, a water absorption of the hardening material of the resin component is 0.6% or less.SELECTED DRAWING: None

Description

The present invention relates to a method for manufacturing a printed wiring board.

As a manufacturing technique for a multilayer printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked on an inner layer substrate is known. The insulating layer is generally formed by curing the resin composition.

For example, Patent Document 1 discloses that a resin composition containing a cyanate ester resin, a specific epoxy resin, and an active ester curing agent is used to form an insulating layer in a printed wiring board. It is described that both low roughness and high peel strength of the conductor layer formed by plating are achieved, and a low thermal expansion rate is achieved.

Japanese Unexamined Patent Publication No. 2011-144361

In recent years, due to the needs for miniaturization of electronic devices and electronic components, there is a demand for thinner and larger substrates. Therefore, the thickness can be reduced by reducing the amount of the resin composition forming the insulating layer.

However, when the amount of the resin composition forming the insulating layer is small, cracks along the shape of the lower layer copper such as wiring and pads in the inner layer substrate, that is, cracks along the pattern of the inner layer substrate occur after the roughening step. I have come to understand.

An object of the present invention is to provide a method for manufacturing a printed wiring board capable of suppressing the occurrence of cracks along a pattern of an inner layer substrate.

The present inventors considered the cause of cracking along the pattern of the substrate after the roughening step as follows. In the pattern of the inner layer substrate, stress concentration is generally likely to occur on the insulating layer in the portion on the convex portion such as the wiring and the pad. However, since the insulating layer on the convex portion is locally thinned, the durability of the insulating layer against stress is reduced when the ratio of the resin composition to the entire substrate is reduced even though the stress is increased. The sex has become low. Therefore, it was considered that the insulating layer could not withstand the stress and cracks would occur. As a result of studies by the present inventors based on this, by heating under certain conditions and setting the water absorption rate of the cured product of the resin composition to a predetermined value or less, cracks occur along the pattern of the inner layer substrate. We have found that it is possible to suppress the above, and have completed the present invention.

That is, the present invention includes the following contents.
[1] (A) The resin composition layer of the laminate including the inner layer substrate and the resin composition layer containing the resin composition bonded on the inner layer substrate is thermoset at 130 ° C. or higher and 220 ° C. or lower. A step of forming an insulating layer containing a cured product of a resin composition,
A method for manufacturing a printed wiring board, which includes (C) a step of annealing the insulating layer at 60 ° C. or higher and 150 ° C. or lower, and (D) a step of desmearing the insulating layer with an oxidizing agent solution in this order.
A method for manufacturing a printed wiring board, wherein the cured product of the resin composition has a water absorption rate of 0.6% or less.
[2] Step (A) is
(A-1) A step of preparing a resin sheet containing a support and a resin composition layer containing the resin composition provided on the support.
(A-2) A step of laminating resin sheets so that the resin composition layer is bonded to the inner layer substrate to obtain a laminate, and (A-3) thermosetting the resin composition layer at 130 ° C. or higher and 220 ° C. or lower. The method for producing a printed wiring board according to [1], which comprises a step of forming an insulating layer containing a cured product of the resin composition.
[3] (A) After the process (C) Before the process
(B) The method for manufacturing a printed wiring board according to [1] or [2], which comprises a step of cooling the insulating layer to room temperature.
[4] The production of the printed wiring board according to any one of [1] to [3], wherein the step (C) is carried out by immersing the insulating layer in a liquid heated to a temperature of 60 ° C. or higher and 150 ° C. or lower. Method.
[5] The method for manufacturing a printed wiring board according to [4], wherein the pH of the liquid is 6 or more and 14 or less.
[6] The method for manufacturing a printed wiring board according to [5], wherein the pH of the liquid is 6.5 or more and 7.5 or less.
[7] The method for manufacturing a printed wiring board according to any one of [4] to [6], wherein the liquid is water.
[8] The method for producing a printed wiring board according to any one of [1] to [7], wherein the resin composition contains an active ester-based curing agent.
[9] The method for producing a printed wiring board according to any one of [1] to [8], wherein the resin composition contains an inorganic filler.
[10] The method for producing a printed wiring board according to [9], wherein the content of the inorganic filler is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.

According to the present invention, it is possible to provide a method for manufacturing a printed wiring board capable of suppressing the occurrence of cracks along the pattern of the inner layer substrate.

Before explaining in detail the method for manufacturing a printed wiring board of the present invention, a resin sheet that can be used in the method for manufacturing a printed wiring board of the present invention will be described.

[Resin sheet]
The resin sheet includes a support and a resin composition layer provided on the support. Hereinafter, the resin composition layer and the support of the resin sheet will be described.

(Resin composition layer)
As the resin composition used for the resin composition layer, a resin composition having a water absorption rate of 0.6% or less of the cured product cured under the conditions described in the step (A) can be used. By forming the insulating layer using a resin composition having a water absorption rate of 0.6% or less, it is possible to suppress the occurrence of cracks along the pattern of the inner layer substrate.

The water absorption rate of the cured product of the resin composition is 0.6% or less, preferably 0.55% or less, more preferably 0.5% or less, preferably 0.1% or more, and more preferably. It is 0.15% or more, more preferably 0.2% or more. The water absorption rate can be measured by the method described in Examples described later.

In order to reduce the water absorption rate of the cured product of the resin composition to 0.6% or less, for example, a method of incorporating an active ester-based curing agent in the resin composition, a method of incorporating an inorganic filler in the resin composition, and the like can be mentioned. Be done. Further, as the resin composition, a curable resin used when forming an insulating layer of a printed wiring board can be used. Therefore, in one embodiment, the resin composition comprises (A) an active ester-based curing agent, (B) a thermosetting resin, and (C) an inorganic filler. The resin composition may further contain (D) a thermoplastic resin, (E) a curing accelerator, and (F) other additives, if necessary. Hereinafter, each component contained in the resin composition will be described in detail.

-(A) Active ester-based curing agent-
In one embodiment, the resin composition may contain an active ester-based curing agent as the component (A). When an active ester-based curing agent (A) is used, the water absorption rate of the cured product can usually be lowered. Further, since the bond between the component (A) and the thermosetting resin described later is strong, the mechanical strength of the cured product can be improved. The component (A) may be used alone or in combination of two or more.

(A) As the active ester-based curing agent, generally, 2 ester groups having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are contained in one molecule. Compounds having more than one are preferably used. The active ester-based curing agent 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-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. 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. 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, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Specifically, a dicyclopentadiene-type active ester-based curing agent, an active ester-based curing agent containing a naphthalene structure, an active ester-based curing agent containing an acetylated product of phenol novolac, and an active ester-based curing agent containing a benzoyl compound of phenol novolac. Of these, an active ester-based curing agent containing a naphthalene structure and a dicyclopentadiene-type active ester-based curing agent are more preferable, and a dicyclopentadiene-type active ester-based curing agent is further preferable. As the dicyclopentadiene type active ester type curing agent, an active ester type curing agent containing a dicyclopentadiene type diphenol structure is preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

(A) Commercially available products of the active ester-based curing agent include "EXB9451" (manufactured by DIC, active ester group equivalent 223) and "EXB9460" (DIC) as active ester-based curing agents containing a dicyclopentadiene-type diphenol structure. "EXB9460S" (manufactured by DIC, active ester group equivalent 223), "HPC-8000-65T" (manufactured by DIC, active ester group equivalent 223), "HPC-8000H-65TM" (DIC, active ester group equivalent 224), "HPC8000L-65TM" (DIC, active ester group equivalent 220), "EXB-8100L-65T" (DIC) as an active ester-based curing agent containing a naphthalene structure. , "EXB8150-60T" (manufactured by DIC, active ester group equivalent 226), "EXB9416-70BK" (manufactured by DIC, active ester group equivalent 274), "PC1300-02" (air) -Water Co., Ltd., active ester group equivalent 200), phosphorus-containing active ester-based curing agent "EXB9401" (DIC Co., Ltd., active ester group equivalent 307), phenol novolac acetylated active ester-based curing agent "DC808" (Made by Mitsubishi Chemical Co., Ltd., active ester group equivalent 149), "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" as an active ester-based curing agent which is a benzoyl compound of phenol novolac (Manufactured by Mitsubishi Chemical Co., Ltd.) and the like.

The active ester group equivalent of the active ester-based curing agent (A) is preferably 50 g / eq. From the viewpoint of obtaining a cured product having a low water absorption rate. ~ 500 g / eq. , More preferably 50 g / eq. ~ 400 g / eq. , More preferably 100 g / eq. ~ 300 g / eq. Is. The active ester group equivalent is the mass of the active ester-based curing agent containing 1 equivalent of the active ester group.

The content of the active ester-based curing agent is preferably 1% by mass or more, more preferably 3 when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining a cured product having a low water absorption rate. It is by mass% or more, more preferably 5% by mass or more, 10% by mass or more, and 15% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 28% by mass or less, and further preferably 25% by mass or less. In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

-(B) Thermosetting resin-
In one embodiment, the resin composition contains (B) a thermosetting resin as a component (B). As the thermosetting resin, a thermosetting resin that can be used as an insulating member such as an insulating layer can be used. Examples of such thermosetting resins include epoxy resins, phenolic resins, naphthol resins, benzoxazine resins, cyanate ester resins, carbodiimide resins, amine resins, acid anhydride resins and the like. .. However, those corresponding to the component (A) are excluded from the component (B). Hereinafter, phenolic resins, naphthol resins, benzoxazine resins, cyanate ester resins, carbodiimide resins, amine resins, and acid anhydride resins may be collectively referred to as "curing agents". The thermosetting resin preferably contains an epoxy resin. As the component (B), one type may be used alone, or two or more types may be used in combination.

Examples of the epoxy resin as the component (B) include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and dicyclopentadiene type epoxy resin. Trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester Type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy Examples thereof include resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the component (B). From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferable with respect to 100% by mass of the non-volatile component of the epoxy resin as the component (B). Is 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

The epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter sometimes referred to as "liquid epoxy resin") or a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as "solid epoxy resin"). ). The resin composition may contain only the liquid epoxy resin as the component (B), may contain only the solid epoxy resin, or may contain a combination of the liquid epoxy resin and the solid epoxy resin. Good. As the component (B), a liquid epoxy resin and a solid epoxy can be obtained from the viewpoint of obtaining sufficient flexibility when used in the form of a resin sheet and improving the breaking strength of the cured product of the resin composition layer. It is preferable to use it in combination with a resin.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Examples of the solid epoxy resin include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, A bixilenol type epoxy resin is more preferable.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP-7200", "HP-7200HH", "HP" -7200H "(dicyclopentadiene type epoxy resin);" EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(made by DIC) Naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayakusha; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayakusha; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nittetsu Chemical & Materials Co., Ltd .; "ESN485" manufactured by Nittetsu Chemical & Materials Co., Ltd. (Naftor novolac type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX8800" (anthracene type epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd .; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. "YL7800" (fluorene type epoxy resin); "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. .. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. An alicyclic epoxy resin having an alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828EL", "825", and "Epicoat" manufactured by Mitsubishi Chemical Co., Ltd. 828EL (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "jER152" (phenol novolac type epoxy resin); Mitsubishi Chemical's "630", "630LSD" (glycidylamine type epoxy resin); "ZX1059" manufactured by Nittetsu Chemical & Materials Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); manufactured by Nagase ChemteX. "EX-721" (glycidyl ester type epoxy resin); "Selokiside 2021P" manufactured by Daicel Co., Ltd. (alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel Co., Ltd. (epoxy resin having a butadiene structure) Examples thereof include "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nittetsu Chemical & Materials Co., Ltd. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (B), their quantity ratio (liquid epoxy resin: solid epoxy resin) is preferably 10: 1 to 1:20 in terms of mass ratio. It is more preferably 5: 1 to 1:15, and particularly preferably 1: 1 to 1:10. When the amount ratio of the liquid epoxy resin to the solid epoxy resin is within such a range, the desired effect of the present invention can be remarkably obtained.

The epoxy equivalent of the epoxy resin as the component (B) is preferably 50 g / eq to 5000 g / eq, more preferably 50 g / eq to 3000 g / eq, still more preferably 80 g / eq to 2000 g / eq, and even more preferably 110 g. / Eq to 1000 g / eq. Within this range, the crosslink density of the cured product of the resin composition becomes sufficient, and an insulating layer having a small surface roughness can be provided. Epoxy equivalent is the mass of a resin containing 1 equivalent of an epoxy group. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin as the component (B) is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500, from the viewpoint of significantly obtaining the desired effect of the present invention. is there.
The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of the epoxy resin as the component (B) is preferably 1% by mass when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. As mentioned above, it is more preferably 3% by mass or more, still more preferably 5% by mass or more. The upper limit of the content of the epoxy resin is preferably 35% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

As the phenolic resin and the naphthol resin, those having a novolak structure are preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based resin is more preferable.

Specific examples of the phenolic resin and the naphthol resin include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. , "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel Chemical & Materials Co., Ltd. , "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc. manufactured by DIC Corporation.

Specific examples of the benzoxazine-based resin include "JBZ-OD100" (benzoxazine ring equivalent 218), "JBZ-OP100D" (benzoxazine ring equivalent 218), and "ODA-BOZ" (benzoxazine ring) manufactured by JFE Chemical Co., Ltd. Equivalent 218); "Pd" (benzoxazine ring equivalent 217), "FA" (benzoxazine ring equivalent 217) manufactured by Shikoku Kasei Kogyo Co., Ltd .; "HFB2006M" (benzoxazine ring equivalent) manufactured by Showa Polymer Co., Ltd. 432) and the like.

Examples of the cyanate ester-based resin include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4'. -Etilidendiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) ) Bifunctional cyanate resins such as methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; phenol Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak; prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester resin include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Ronza Japan. Examples thereof include "BA230S75" (a prepolymer in which part or all of bisphenol A disyanate is triazined to form a trimer).

Specific examples of the carbodiimide-based resin include carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216, V-05 (carbodiimide group equivalent: 262), V-07 (carbodiimide group equivalent: 200)) manufactured by Nisshinbo Chemical Co., Ltd. V-09 (carbodiimide group equivalent: 200); Stavaxol® P (carbodiimide group equivalent: 302) manufactured by Rheinchemy.

Examples of the amine-based resin include resins having one or more amino groups in one molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Of these, aromatic amines are preferable from the viewpoint of achieving the desired effects of the present invention. The amine-based resin is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'. -Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4'-Diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane Diamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3- Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, Examples thereof include bis (4- (3-aminophenoxy) phenyl) sulfone. Commercially available products may be used as the amine resin, for example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", "Kayahard AB", "Kayahard" manufactured by Nippon Kayaku Corporation. Examples include "AS" and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

Examples of the acid anhydride-based resin include resins having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and methylnadic hydride anhydride. Trialkyltetrahydrophthalic anhydride, succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimerit anhydride Acid, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenyl Sulphontetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1, Examples thereof include 3-dione, ethylene glycol bis (anhydrotrimeritate), and polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized.

When the component (B) contains an epoxy resin and a curing agent, the amount ratio of the epoxy resin to all the curing agents is [total number of epoxy groups in the epoxy resin]: [total number of reactive groups in the curing agent]. The ratio is preferably in the range of 1: 0.01 to 1: 5, more preferably 1: 0.5 to 1: 3, and even more preferably 1: 1 to 1: 2. Here, the "number of epoxy groups in the epoxy resin" is a total value obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. The "number of active groups of the curing agent" is a total value obtained by dividing the mass of the non-volatile component of the curing agent present in the resin composition by the active group equivalent. By setting the amount ratio of the epoxy resin and the curing agent within such a range, the effect of the present invention can be remarkably obtained.

The content of the curing agent as the component (B) is preferably 3% by mass or more, more preferably 5% by mass, based on 100% by mass of the non-volatile component in the resin composition from the viewpoint of remarkably obtaining the effect of the present invention. % Or more, more preferably 10% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less.

-(C) Inorganic filler-
In one embodiment, the resin composition contains (C) an inorganic filler as a component (C). By containing the (C) inorganic filler, a cured product having a low water absorption rate can be obtained.

(C) An inorganic compound is used as the material of the inorganic filler. Examples of materials for inorganic fillers include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconate titanate , Barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconate titanate, zirconate tungsten phosphate and the like. Of these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. (E) The inorganic filler may be used alone or in combination of two or more.

(C) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Co., Ltd .; "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Materials Co., Ltd .; "Admatex Co., Ltd." "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama; "SC2500SQ" manufactured by Admatex , "SO-C4", "SO-C2", "SO-C1"; and the like.

The average particle size of the inorganic filler (C) is preferably 0.01 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, and 1 μm or less.

(C) The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, the wavelengths of the light sources used were blue and red, and the volume-based particle size distribution of (C) the inorganic filler was measured by the flow cell method. The average particle size can be calculated as the median diameter from the diameter distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by HORIBA, Ltd.

The specific surface area of the inorganic filler (C) is preferably 1 m ² / g or more, more preferably 2 m ² / g or more, and particularly preferably 3 m ² / g or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. is there. The upper limit is not particularly limited, but is preferably 60 m ² / g or less, 50 m ² / g or less, or 40 m ² / g or less. The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. ..

The inorganic filler (C) is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilazane compounds, and titanates. Coupling agents and the like can be mentioned. In addition, one type of surface treatment agent may be used alone, or two or more types may be used in any combination.

Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-" manufactured by Shin-Etsu Chemical Co., Ltd. 7103 ”(3,3,3-trifluoropropyltrimethoxysilane) and the like.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of a surface treatment agent, and 0.2 parts by mass to 3 parts by mass is surface-treated. It is preferable that the surface is treated with 0.3 parts by mass to 2 parts by mass.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet 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 further preferable. preferable.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed 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 a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon 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. or the like can be used.

The content of the inorganic filler (C) is preferably 50% by mass or more, more preferably 55, when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining a cured product having a low water absorption rate. It is mass% or more, more preferably 60% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.

-(D) Thermoplastic resin-
In one embodiment, the resin composition may contain (D) a thermoplastic resin as the component (D). (D) By containing the thermoplastic resin, the stress of the cured product can be relaxed.

Examples of the thermoplastic resin include phenoxy resin, polycarbonate resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, and polyether. Examples thereof include ether ketone resin and polyester resin. Among them, at least one selected from a polyimide resin, a polycarbonate resin and a phenoxy resin is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. Further, the (D) thermoplastic resin may be used alone by one type, or may be used in combination of two or more types.

As the polyimide resin, a resin having an imide structure can be used. Examples of such a resin include a linear polyimide (polyimide described in JP-A-2006-37083) obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, and a polysiloxane skeleton. Examples thereof include modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).

A commercially available product can be used as the polyimide resin. Examples of commercially available products include "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd.

As the polycarbonate resin, a resin having a carbonate structure can be used. Examples of such a resin include a hydroxy group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxy group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an isocyanate group-containing carbonate resin, and a urethane group-containing carbonate resin.

A commercially available product can be used as the carbonate resin. Commercially available products include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090" and "C" manufactured by Kuraray. -3090 ”(polycarbonate diol) and the like.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpen Examples thereof include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical Co., Ltd. (both are bisphenol A skeleton-containing phenoxy resins); "YX8100" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol S skeleton-containing phenoxy resin); "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Nittetsu Chemical &Materials; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd. , "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7553BH30", "YL7482"; and the like.

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include Eslek BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

Specific examples of the polyamide-imide resin include "Vilomax HR11NN" and "Vilomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Co., Ltd.

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

Specific examples of the polyphenylene ether resin include oligophenylene ether / styrene resin “OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Company, Ltd.

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

The weight average molecular weight (Mw) of the (D) thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, and particularly preferably 20,000 or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.

The content of the thermoplastic resin (D) is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of remarkably obtaining the desired effect of the present invention. Is 0.3% by mass or more, more preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less.

-(E) Hardening accelerator-
In one embodiment, the resin composition may contain (E) a curing accelerator as the component (E). By containing the (E) curing accelerator, the thermosetting of the resin composition can be promoted.

Examples of the (E) curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable. The curing accelerator (E) may be used alone or in combination of two or more.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, and the like. 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 trimerite, 1-cyanoethyl- 2-Phenylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadesylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biganide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include 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, zinc stearate and the like.

The content of the curing accelerator (E) is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of remarkably obtaining the desired effect of the present invention. Is 0.03% by mass or more, more preferably 0.05% by mass or more, preferably 0.3% by mass or less, more preferably 0.2% by mass or less, still more preferably 0.1% by mass or less. ..

<(F) Other additives>
In addition to the above-mentioned components, the resin composition may further contain other additives as arbitrary components. Examples of such additives include flame retardants; organic fillers; resin additives such as thickeners, antifoaming agents, leveling agents, and adhesion-imparting agents; These additives may be used alone or in combination of two or more.

The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, still more preferably 40 μm or less, 30 μm or less, or 25 μm or less from the viewpoint of thinning the printed wiring board. .. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 5 μm or more, 10 μm or more, or the like.

(Support)
Examples of the support used for the resin sheet include a film made of a plastic material, a metal foil, and a paper pattern, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) Etc., polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethylmethacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), polyethersulfide (PES), polyether. Examples thereof include ketones and polyimides. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The surface of the support to be joined to the resin composition layer may be matted, corona-treated, or antistatic-treated.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples thereof include "AL-5" and "AL-7", "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Corporation, and "Unipee" manufactured by Unitika.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

[Manufacturing method of printed wiring board]
The method for manufacturing a printed wiring board of the present invention
(A) The resin composition layer of the laminate including the inner layer substrate and the resin composition layer containing the resin composition bonded on the inner layer substrate is thermoset at 130 ° C. or higher and 220 ° C. or lower to heat-cure the resin composition. The process of forming an insulating layer containing the cured product of
The steps of (C) annealing the insulating layer at 60 ° C. or higher and 150 ° C. or lower, and (D) desmearing the insulating layer with an oxidizing agent solution are included in this order, and the water absorption rate of the cured product of the resin composition is high. It is 0.6% or less.

As described above, the present inventors have found a problem that cracks such as cracks are likely to occur after the desmear treatment (roughening treatment) along the pattern shape of the inner layer substrate. On the other hand, by using a resin composition in which the water absorption rate of the cured product of the resin composition is 0.6% or less, the desmear treatment, particularly the swelling of the insulating layer due to the oxidizing agent solution can be suppressed, so that the insulation during desmearing can be suppressed. The mechanical strength of the layer can be maintained high. Further, by performing a step of thermosetting to form an insulating layer and then annealing, the stress in the insulating layer generated by the thermosetting of the resin composition is relaxed. Then, cracking can be suppressed by these actions.

Further, the method for manufacturing a printed wiring board of the present invention may include, if necessary, a step of cooling the insulating layer to room temperature after the step (A) and before the step (C).

Hereinafter, each step in the method for manufacturing a printed wiring board of the present invention will be described.

<(A) step>
In this step (A), the resin composition layer of the laminate including the inner layer substrate and the resin composition layer containing the resin composition bonded on the inner layer substrate is thermoset at 130 ° C. or higher and 220 ° C. or lower. , Form an insulating layer containing a cured product of the resin composition.

The step (A) preferably includes the following steps (A-1) to (A-3) in this order.
(A-1) A step of preparing a resin sheet containing a support and a resin composition layer containing the resin composition provided on the support.
(A-2) A step of laminating resin sheets so that the resin composition layer is bonded to the inner layer substrate to obtain a laminate, and (A-3) Thermosetting the resin composition layer at 130 ° C. or higher and 220 ° C. or lower. To form an insulating layer containing a cured product of the resin composition.

In the step (A-1), a resin sheet containing a support and a resin composition layer formed of the resin composition provided on the support is prepared. The support and the resin composition are as described in the above [resin sheet].

For the resin sheet, for example, a resin varnish in which the resin composition is dissolved in an organic solvent is prepared, the resin varnish is applied onto the support using a coating device such as a die coater, and the resin composition layer is further dried. Can be produced by forming.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like. Examples thereof include carbitols, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A material layer can be formed.

In the resin sheet, a protective film similar to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches. The resin sheet can be rolled up and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

In the step (A-2), the resin sheets are laminated so that the resin composition layer is bonded to the inner layer substrate to obtain a laminated body.

The inner layer substrate is a member that serves as a substrate for a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Further, the substrate may have a conductor layer on one side or both sides thereof, and the conductor layer may be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board". Further, an intermediate product in which an insulating layer and / or a conductor layer should be formed when the printed wiring board is manufactured is also included in the "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

A resin sheet is laminated on the inner layer substrate so that the resin composition layer is bonded to the inner layer substrate to obtain a laminated body. In one embodiment, the inner layer substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressing the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable to press the heat-bonded member not directly on the resin sheet but through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The inner layer substrate and the resin sheet may be laminated by a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.

After laminating, the laminated resin sheet may be smoothed by pressing the heat-bonded member from the support side under normal pressure (under atmospheric pressure), for example. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

In the step (A-3), the resin composition layer is thermally cured at 130 ° C. or higher and 220 ° C. or lower to form an insulating layer containing the cured product of the resin composition.

The thermosetting conditions of the resin composition layer differ depending on the type of the resin composition and the like, but the curing temperature is 130 ° C. or higher, preferably 150 ° C., and more preferably 170 ° C. The upper limit is 220 ° C. or lower, preferably 210 ° C., more preferably 200 ° C.

The curing time is preferably 5 minutes or longer, more preferably 10 minutes or longer, still more preferably 15 minutes or longer, preferably 120 minutes or shorter, more preferably 100 minutes or shorter, still more preferably 90 minutes or shorter.

Before the resin composition layer is thermoset, the resin composition layer may be preheated at a temperature lower than the curing temperature. The preheating temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, preferably less than 120 ° C., more preferably 110 ° C. or lower, still more preferably 100 ° C. or lower. The preheating time is preferably 5 minutes or longer, more preferably 10 minutes or longer, further preferably 15 minutes or longer, preferably 150 minutes or shorter, more preferably 130 minutes or shorter, still more preferably 120 minutes or shorter. is there.

The thickness of the insulating layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, still more preferably 50 μm or less or 40 μm or less, from the viewpoint of reducing the thickness of the printed wiring board. The lower limit of the thickness of the insulating layer is not particularly limited, but may be usually 1 μm or more, 5 μm or more, 10 μm or more, or the like.

<(B) process>
In one embodiment, the method for manufacturing a printed wiring board of the present invention may include (B) a step of cooling the insulating layer to room temperature. The step (B) is preferably performed between the steps (A) and (C). By performing the step (B), it is possible to prevent the stress generated by the thermosetting of the resin composition from becoming excessive. Therefore, the residual stress in the insulating layer can be further suppressed in the step (C), and the occurrence of cracks along the pattern of the inner layer substrate can be effectively suppressed. Here, room temperature usually represents 10 to 30 ° C, preferably 25 ° C.

The method of cooling is not particularly limited, and the insulating layer may be allowed to cool, or the insulating layer may be forcibly cooled. When the insulating layer is forcibly cooled, it may be cooled by various known methods, for example, a method of leaving the insulating layer to cool, a method of blowing cold air on the insulating layer, or pushing the insulating layer onto a cooled roll. There is a method of hitting.

<Step (C)>
In the step (C), the insulating layer is annealed at 60 ° C. or higher and 150 ° C. or lower. By performing the annealing treatment at a temperature lower than the thermosetting temperature in the step (A), the stress depending on the pattern shape of the inner layer substrate can be relaxed, and as a result, the pattern of the inner layer substrate generated after the step (D) It is possible to suppress the occurrence of cracks along the line.

The temperature of the annealing treatment is 60 ° C. or higher, preferably 65 ° C. or higher, and more preferably 70 ° C. or higher, from the viewpoint of suppressing the occurrence of cracks along the pattern of the inner layer substrate. The upper limit is 150 ° C. or lower, preferably 140 ° C. or lower, more preferably 130 ° C. or lower, and 100 ° C. or lower.

The annealing treatment preferably maintains a temperature of 60 ° C. or higher and 150 ° C. or lower for a predetermined time from the viewpoint of suppressing the occurrence of cracks along the pattern of the inner layer substrate. The holding time is preferably 1 minute or more, more preferably 3 minutes or more, further preferably 10 minutes or more, preferably 90 minutes or less, more preferably 60 minutes or less, still more preferably 40 minutes or less.

The annealing treatment may be performed by heating the insulating layer in the atmosphere, or may be performed by immersing the insulating layer in a liquid. From the viewpoint of further relaxing the stress in the insulating layer, it is preferable to immerse the insulating layer in the liquid. When the boiling point of the liquid is 150 ° C. or lower, the boiling point of the liquid can be the upper limit temperature of the annealing treatment.

As the liquid, a liquid having a boiling point of 60 ° C. or higher can be used. Examples of such a liquid include water; a swelling liquid such as a sodium hydroxide solution and a potassium hydroxide solution, and among them, water and a swelling liquid are preferable from the viewpoint of further relaxing the stress in the insulating layer. More preferably, it is water. A commercially available product can be used as the swelling liquid. Examples of commercially available products include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan.

The pH of the liquid is preferably 6 or more, more preferably 6.5 or more, still more preferably 7 or more, and preferably 14 or less, from the viewpoint of more effectively relaxing the stress depending on the pattern shape of the inner layer substrate. More preferably, it is 13.5 or less, 12 or less, 12.5 or less, 11 or less, 10 or less, 8 or less, 7.5 or less, and the pH is particularly preferably 7.

The annealing treatment may be performed only once or twice. In one embodiment, the annealing treatment is performed by performing the first annealing treatment at 60 ° C. or higher and 150 ° C. or lower, and then immersing the insulating layer in a swelling liquid heated to a temperature of 60 ° C. or higher and 150 ° C. or lower. Annealing process. A preferred embodiment is swelling that is further heated to a temperature of 60 ° C. or higher and 150 ° C. or lower after performing the first annealing treatment in which the insulating layer is immersed in water heated to a temperature of 60 ° C. or higher and 150 ° C. or lower. A second annealing treatment is performed in which the insulating layer is immersed in the liquid. By performing the annealing treatment twice, the surface of the insulating layer can be effectively desmeared in the step (D).

When manufacturing the printed wiring board, a step of drilling a hole in the insulating layer between the step (C) and the step (D) may be further carried out. The step of drilling holes in the insulating layer may be carried out according to various methods known to those skilled in the art used in the manufacture of printed wiring boards. When the annealing treatment in the step (C) is performed twice, the step of drilling holes in the insulating layer may be performed between the first annealing treatment and the second annealing treatment.

Via holes and through holes can be formed in the insulating layer by the step of drilling holes in the insulating layer. The step of drilling can be carried out using, for example, a drill, a laser (carbon dioxide laser, YAG laser, etc.), plasma, or the like.

<Step (D)>
In the step (D), the insulating layer is desmeared with an oxidizing agent solution, that is, the surface of the insulating layer is desmeared. The procedure and conditions for the desmear treatment are not particularly limited, and known procedures and conditions usually used for forming the insulating layer of the printed wiring board can be adopted.

As the oxidant solution, an oxidant solution used in a normal desmear treatment can be used. Examples of such an oxidizing agent solution include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidant concentration of the oxidant solution is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, preferably 20% by mass or less, and more preferably 15% by mass. Hereinafter, it is more preferably 10% by mass or less.

A commercially available product may be used as the oxidizing agent solution. Examples of commercially available oxidant solutions include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.

The oxidizing agent solution is preferably heated from the viewpoint of efficiently performing desmear treatment. The heating temperature of the oxidant solution is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, further preferably 70 ° C. or higher, preferably 90 ° C. or lower, more preferably 85 ° C. or lower, still more preferably 80 ° C. or lower. Is.

The time for immersing the insulating layer in the oxidizing agent solution is preferably 5 minutes, more preferably 10 minutes, still more preferably 15 minutes, preferably 40 minutes, more preferably 30 minutes, still more preferably 25 minutes. Is.

In the step (D), after the insulating layer is desmeared with the oxidizing agent solution, the neutralizing treatment may be performed with a neutralizing solution from the viewpoint of removing the residue of the salt of the oxidizing agent and the like.

As the neutralizing solution, it is preferable to use an acidic aqueous solution. A commercially available neutralizing solution may be used, and examples of the commercially available neutralizing solution include "Reduction Solution Security P" manufactured by Atotech Japan.

The neutralization treatment can be performed by immersing the surface of the insulating layer that has been desmeared in the step (D) in a heated neutralizing solution.

The heating temperature of the neutralizing solution is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, further preferably 30 ° C. or higher, and preferably 80 ° C. from the viewpoint of removing the residue of the salt of the oxidizing agent. Below, it is more preferably 75 ° C. or lower, still more preferably 70 ° C. or lower.

The immersion time is preferably 1 minute or longer, more preferably 3 minutes or longer, still more preferably 5 minutes or longer, preferably 30 minutes or shorter, more preferably 30 minutes or longer, from the viewpoint of removing the residue of the salt of the oxidizing agent. It is 25 minutes or less, more preferably 20 minutes or less.

When manufacturing a printed wiring board, a step (E) of forming a conductor layer on the surface of the insulating layer may be further carried out after the step (D).

The conductor material used for the conductor layer in the step (E) is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). A layer formed from a nickel alloy and a copper / titanium alloy) can be mentioned. Among them, from the viewpoint of ease of forming a conductor layer, cost, ease of pattern processing, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, Copper-nickel alloys, copper-titanium alloy alloy layers are preferred, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layers, or nickel-chromium alloy alloy layers are more preferred, copper. The single metal layer of is more preferable.

The conductor layer may have a single layer structure, a single metal layer made of different types of metals or alloys, or a multi-layer structure in which two or more alloy layers are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer is generally 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the desired printed wiring board design.

In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern, and the semi-additive can be manufactured from the viewpoint of ease of manufacture. It is preferably formed by the method. Hereinafter, an example of forming the conductor layer by the semi-additive method will be shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

The support is provided between steps (A-2) and (A-3) and steps, between steps (A-3) and (B), and between steps (B) and (C). Alternatively, it may be removed after the step (C). Further, after the completion of each step, a washing treatment may be performed as needed.

The printed wiring board obtained by the manufacturing method of the present invention has an excellent effect of being able to suppress the occurrence of cracks along the pattern of the inner layer substrate. Therefore, an insulating layer capable of suppressing the occurrence of cracks along the pattern of the inner layer substrate is provided. For example, among the surface of the insulating layer after the desmear treatment of the printed wiring board manufactured by the method for manufacturing the printed wiring board of the present invention, it is confirmed whether or not the surface is cracked along the shape of the L / S pattern of the inner layer substrate. However, the ratio of no cracks is calculated as the yield. The yield is preferably 40% or more, more preferably 60% or more, further preferably 80% or more, preferably 100% or less, more preferably 95% or less, still more preferably 90% or less. The details of the crack evaluation can be measured according to the method described in Examples described later.

[Semiconductor device]
Using the printed wiring board obtained by the manufacturing method of the present invention, a semiconductor device including such a printed wiring board can be manufactured.

Examples of semiconductor devices include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

A semiconductor device can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conduction point" is a "place for transmitting an electric signal in the printed wiring board", and the place may be a surface or an embedded place. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting the semiconductor chip in 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 thereof 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). Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to these examples. In the following, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Preparation Example 1: Preparation of Resin Sheet A>
10 parts of bisphenol A type epoxy resin (Mitsubishi Chemical "828US", epoxy equivalent about 180 g / eq.), 10 parts of biphenyl type epoxy resin (Mitsubishi Chemical "YX4000H", epoxy equivalent about 190 g / eq.), Naphthol type epoxy resin (“ESN475V” manufactured by Nittetsu Chemical & Materials Co., Ltd., epoxy equivalent 332 g / eq.), 5 parts, active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Co., Ltd., active group equivalent of about 223 g / eq.) 50 parts of a toluene solution having a solid content of 65% by mass, a phenolic curing agent having a triazine skeleton and a novolak structure (“LA-3018-50P” manufactured by DIC, active group equivalent of about 151, solid content of 50% 2- 15 parts of methoxypropanol solution, 5 parts of phenoxy resin (Mitsubishi Chemical Corporation "YL7553BH30", 1: 1 solution of MEK with a solid content of 30% by mass and cyclohexanone), 4-dimethylaminopyridine (MEK solution with a solid content of 5% by mass) ) 3 parts, MEK 30 parts, and 120 parts of spherical silica (average particle size 0.5 μm, Admatex “SO-C2”) surface-treated with an amine-based epoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Corporation). Was uniformly dispersed using a mixer to obtain a resin varnish.

The prepared resin varnish was uniformly applied on a PET film (Lintec's "AL5", thickness 38 μm) with a die coater so that the thickness after drying was 25 μm, and the temperature was 80 to 120 ° C. (average 100). The resin sheet A was obtained by drying at (° C.) for 5 minutes.

<Preparation Examples 2-7: Preparation of Resin Sheets B to G>
Resin varnishes and resin sheets B to G were obtained by uniformly dispersing using a mixer in the same manner as in Preparation Example 1 except that each component was blended in the blending ratio shown in the table below.

<Measurement of water absorption rate>
The resin composition layer of the resin sheet was heat-cured using a hot air circulation furnace under the conditions of thermosetting at 190 ° C. for 90 minutes. After thermosetting, the PET film was peeled off to obtain a cured product for evaluation.

The cured product for evaluation was cut into 40 mm square test pieces, and the test pieces were dried at 130 ° C. for 30 minutes and then weighed (the weighed mass is defined as A (g)). The test piece was immersed in boiled ion-exchanged water for 1 hour. Then, the test piece was immersed in ion-exchanged water at room temperature (25 ° C.) for 1 minute, and the test piece was weighed by wiping off water droplets on the surface of the test piece with a clean wiper (manufactured by Kuraray Laflex Co., Ltd.). B (g)). The water absorption rates of the five test pieces were calculated from the following formulas, and the average values are shown in the table below.
Water absorption rate (%) = ((BA) / A) x 100

The abbreviations in the table below are as follows.
HPC8000-65T: Active ester-based curing agent ("HPC-8000-65T" manufactured by DIC, active group equivalent of about 223 g / eq., Toluene solution having a solid content of 65% by mass)
SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.5 μm, “SO-C2” manufactured by Admatex)
828US: Bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 180 g / eq.)
YX4000H: Biphenyl type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 190 g / eq.)
ESN475V: Naftor type epoxy resin (manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 332 g / eq.)
SN485-60M: Naftol-based hardener (“SN-485” manufactured by Nippon Steel Chemical & Materials Co., Ltd., MEK solution with active group equivalent of about 215 g / eq., Solid content 60%)
SN395-60M: Naftol-based hardener (“SN395” manufactured by Nippon Steel Chemical & Materials Co., Ltd., hydroxyl group equivalent 107 g / eq., MEK solution with 60% solid content)
LA-3018-50P: Phenolic curing agent having a triazine skeleton and a novolak structure ("LA-3018-50P" manufactured by DIC, active group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%)
V-03: Carbodiimide-based curing agent (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent of about 216 g / eq., Toluene solution having a non-volatile content of 50% by mass)
LA-7054: Triazine-containing phenol novolac resin (MEK solution "LA-7054 manufactured by DIC, hydroxyl group equivalent 125 g / eq., Nitrogen content about 12% by weight, solid content 60% by weight)"
YL7553BH30: Phenoxy resin (manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass)
DMAP-5M: 4-dimethylaminopyridine, MEK solution with a solid content of 5% by mass MEK: Methyl ethyl ketone

[Example 1]
<Lamination of resin sheet>
A resin sheet A prepared in advance was prepared. Inner layer substrate having circuit conductors (copper) formed on both sides with a wiring pattern of L / S = 8 μm / 8 μm (“MCL-E700G” manufactured by Hitachi Kasei Co., Ltd., conductor layer thickness 35 μm, total thickness 0.4 mm, A resin sheet was laminated on both sides of the residual copper ratio (40%) so that the resin composition layer was in contact with the inner layer substrate. For such a laminate, a vacuum pressurizing laminator MVLP-500 manufactured by Meiki Co., Ltd. was used, and after vacuum suction at a temperature of 120 ° C. for 30 seconds, the temperature was 120 ° C. and the pressure was 7.0 kg / cm ² from the PET film. , Laminated by pressing through heat resistant rubber for 30 seconds. Next, the press was performed under atmospheric pressure using a SUS end plate for 60 seconds under the conditions of a temperature of 120 ° C. and a pressure of 5.5 kg / cm ² .

<Thermosetting of the resin composition layer>
The PET film was peeled off from the laminated resin sheet, and the resin composition layer of the resin sheet was thermoset to form an insulating layer using a hot air circulation furnace under thermosetting conditions of 170 ° C. for 30 minutes. Next, the substrate on which the insulating layer was formed was left to cool to room temperature (25 ° C.).

<Annealing treatment of resin composition layer>
The substrate on which the insulating layer was formed was heated at 80 ° C. for 30 minutes in an atmospheric environment using a hot air circulation path. Then, the PET film on the surface of the insulating layer was peeled off, and the swelling liquid was immersed in Swelling Dip Security P (pH 11) manufactured by Atotech Japan Co., Ltd. at 60 ° C. for 10 minutes.

<Desmia processing>
As an oxidizing agent, it was immersed in Concentrate Compact CP manufactured by Atotech Japan at 80 ° C. for 20 minutes. Finally, as a neutralizing solution, it was immersed in Reduction Solusin Securigant P manufactured by Atotech Japan Co., Ltd. at 40 ° C. for 5 minutes. Then it was dried at 80 ° C. for 30 minutes.

[Example 2]
In Example 1, the temperature of the annealing treatment in the air environment was changed from 80 ° C. to 130 ° C. Except for the above items, the same procedure as in Example 1 was performed.

[Example 3]
In Example 1, the annealing treatment was performed as follows. Except for the above items, the same procedure as in Example 1 was performed.

<Annealing treatment of the resin composition layer in Example 3>
The substrate on which the insulating layer was formed was immersed in a water bath (pH 7) at 60 ° C. and heated for 30 minutes. Then, the PET film on the surface of the insulating layer was peeled off, and the swelling liquid was immersed in Swelling Dip Security P (Swelling Dip Security P) manufactured by Atotech Japan Co., Ltd. at 60 ° C. for 10 minutes.

[Example 4]
In Example 3, the temperature of the water bath was changed from 60 ° C to 80 ° C. Except for the above items, the same procedure as in Example 3 was performed.

[Example 5]
In Example 3, the resin sheet A was changed to the resin sheet B. Except for the above items, the same procedure as in Example 3 was performed.

[Example 6]
In Example 3, the resin sheet A was changed to the resin sheet C. Except for the above items, the same procedure as in Example 3 was performed.

[Example 7]
In Example 3, the resin sheet A was changed to the resin sheet D. Except for the above items, the same procedure as in Example 3 was performed.

[Example 8]
In Example 1, the annealing treatment was performed as follows. Except for the above items, the same procedure as in Example 1 was performed.

<Annealing treatment of the resin composition layer in Example 8>
The PET film on the surface of the insulating layer was peeled off and immersed in a swelling liquid, Swelling Dip Security P (Swelling Dip Security P) manufactured by Atotech Japan, at 60 ° C. for 10 minutes.

[Comparative Example 1]
In Example 1, no annealing treatment (that is, heating in the air and immersion in a swollen liquid) was performed. Except for the above items, the same procedure as in Example 1 was performed.

[Comparative Example 2]
In Example 1, the heating temperature in the air environment was changed from 80 ° C. to 40 ° C., and the immersion temperature in the swelling liquid was changed from 60 ° C. to 40 ° C. Except for the above items, the same procedure as in Example 1 was performed.

[Comparative Example 3]
In Example 3, the temperature of the water bath was changed from 60 ° C. to 40 ° C., and the immersion temperature in the swelling liquid was changed from 60 ° C. to 40 ° C. Except for the above items, the same procedure as in Example 3 was performed.

[Comparative Example 4]
In Example 1, the resin sheet A was changed to the resin sheet E, and further annealing treatment (that is, heating in the air and immersion in the swelling liquid) was not performed. Except for the above items, the same procedure as in Example 1 was performed.

[Comparative Example 5]
In Example 3, the resin sheet A was changed to the resin sheet E, the temperature of the water bath was changed from 60 ° C. to 40 ° C., and the immersion temperature in the swelling liquid was changed from 60 ° C. to 40 ° C. Except for the above items, the same procedure as in Example 3 was performed.

[Comparative Example 6]
In Example 3, the resin sheet A was changed to the resin sheet F, and the temperature of the water bath was further changed from 60 ° C. to 70 ° C. Except for the above items, the same procedure as in Example 3 was performed.

[Comparative Example 7]
In Example 3, the resin sheet A was changed to the resin sheet G, and the temperature of the water bath was further changed from 60 ° C. to 40 ° C. Except for the above items, the same procedure as in Example 3 was performed.

<Evaluation method for cracks>
Of the surface of the insulating layer after the desmear treatment, the L / S pattern of the inner layer substrate was observed. It was confirmed whether or not cracks were generated on the surface along the pattern shape of the 100 inner layer substrates, and the ratio on the pattern without cracks was counted. This ratio was calculated as "yield". In addition, the calculated yield was scored according to the following criteria.
1 point: 0% or more and less than 20% 2 points: 20% or more and less than 40% 3 points: 40% or more and less than 60% 4 points: 60% or more and less than 80% 5 points: 80% or more In addition, 3 points or more are "○" , And 2 points or less were evaluated as "x".

Claims (10)

(A) The resin composition layer of the laminate including the inner layer substrate and the resin composition layer containing the resin composition bonded on the inner layer substrate is thermoset at 130 ° C. or higher and 220 ° C. or lower to heat-cure the resin composition. The process of forming an insulating layer containing the cured product of
A method for manufacturing a printed wiring board, which includes (C) a step of annealing the insulating layer at 60 ° C. or higher and 150 ° C. or lower, and (D) a step of desmearing the insulating layer with an oxidizing agent solution in this order.
A method for manufacturing a printed wiring board, wherein the cured product of the resin composition has a water absorption rate of 0.6% or less. (A) The process is
(A-1) A step of preparing a resin sheet containing a support and a resin composition layer containing the resin composition provided on the support.
(A-2) A step of laminating resin sheets so that the resin composition layer is bonded to the inner layer substrate to obtain a laminate, and (A-3) Thermosetting the resin composition layer at 130 ° C. or higher and 220 ° C. or lower. The method for manufacturing a printed wiring board according to claim 1, further comprising a step of forming an insulating layer containing a cured product of the resin composition. (A) After the process (C) Before the process
(B) The method for manufacturing a printed wiring board according to claim 1 or 2, which comprises a step of cooling the insulating layer to room temperature. The method for manufacturing a printed wiring board according to any one of claims 1 to 3, wherein the step (C) is carried out by immersing the insulating layer in a liquid heated to a temperature of 60 ° C. or higher and 150 ° C. or lower. The method for manufacturing a printed wiring board according to claim 4, wherein the pH of the liquid is 6 or more and 14 or less. The method for manufacturing a printed wiring board according to claim 5, wherein the pH of the liquid is 6.5 or more and 7.5 or less. The method for manufacturing a printed wiring board according to any one of claims 4 to 6, wherein the liquid is water. The method for producing a printed wiring board according to any one of claims 1 to 7, wherein the resin composition contains an active ester-based curing agent. The method for producing a printed wiring board according to any one of claims 1 to 8, wherein the resin composition contains an inorganic filler. The method for manufacturing a printed wiring board according to claim 9, wherein the content of the inorganic filler is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.