JP2019209523A - Resin sheet with support medium - Google Patents

Abstract

To provide a resin sheet with a support medium excellent in flexibility, and capable of acquiring a cured object in which a holoing phenomenon is suppressed.SOLUTION: There is provided a resin sheet with a support medium comprising: a support medium; and a resin sheet layer provided on the support medium. The resin sheet layer comprises: a first resin composition layer formed of a first resin composition; a second resin composition layer formed of a second resin composition whose composition is different from that of the first resin composition, in the order from the support medium side. The first and second resin compositions comprise independently respectively, an epoxy resin, a curative, and an inorganic filler, in which, an elastic modulus at 23°C of first and second cured object layers and t1/t2 when thickness of the first resin composition layer is t1, thickness of the second resin composition layer is t2, are in a prescribed range.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin sheet with a support. Furthermore, it is related with the hardened | cured material of the resin sheet layer of the said resin sheet with a support body.

  In recent years, the demand for small, high-performance electronic devices such as smartphones and tablet devices has increased, and with this, semiconductor package insulating materials (insulating layers) used in these small electronic devices are required to have higher functionality. It has been. Such an insulating layer is known to be formed by curing a resin composition (see, for example, Patent Document 1).

JP 2017-008312 A

  In recent years, electronic devices have been made lighter, thinner, and smaller. Accordingly, since a flexible wiring board that can be folded and stored in an electronic device is required, insulation having excellent flexibility is required. In order to obtain an insulating layer with excellent flexibility, it is conceivable to use a low elastic material, but as a result of investigation by the present inventors, when a low elastic modulus material is applied to the insulating layer, a haloing phenomenon occurs after the formation of the via hole. Has been found to occur. Here, the haloing phenomenon means that peeling occurs between the insulating layer and the inner layer substrate around the via hole. Such a haloing phenomenon usually occurs when the resin around the via hole deteriorates and the deteriorated portion is eroded during the roughening treatment. The deteriorated portion is usually observed as a discolored portion.

  An object of the present invention is to provide a resin sheet with a support capable of obtaining a cured product that is excellent in flexibility and can suppress a haloing phenomenon; and a cured product of a resin sheet layer of the resin sheet with the support.

As a result of intensive studies to solve the above problems, the present inventor has a resin sheet layer of a resin sheet with a support having a first resin composition layer and a second resin composition layer having different elastic moduli. The inventors have found that the above problems can be solved, and have completed the present invention.
That is, the present invention includes the following contents.

[1] A resin sheet with a support comprising a support and a resin sheet layer provided on the support,
The resin sheet layer includes a first resin composition layer formed from the first resin composition and a second resin composition formed from a second resin composition having a composition different from that of the first resin composition. Having a physical layer in this order from the support side,
The first resin composition and the second resin composition each independently contain a thermosetting resin and an inorganic filler,
The elastic modulus at 23 ° C. of the first cured product layer obtained by thermosetting the first resin composition layer at 180 ° C. for 90 minutes is 0.001 GPa or more and 0.1 GPa or less,
The elastic modulus at 23 ° C. of the second cured product layer obtained by thermosetting the second resin composition layer at 180 ° C. for 90 minutes is 3 GPa or more and 10 GPa or less,
Resin with support, wherein t1 / t2 is 1 or more and 10 or less, where t1 (μm) is the thickness of the first resin composition layer and t2 (μm) is the thickness of the second resin composition layer Sheet.
[2] The resin sheet with a support according to [1], wherein a cured product obtained by thermosetting the resin sheet layer at 180 ° C. for 90 minutes has an elastic modulus at 23 ° C. of 0.01 GPa to 4 GPa.
[3] The resin sheet with a support according to [1] or [2], wherein the cured product obtained by thermosetting the resin sheet layer at 180 ° C. for 90 minutes has an elongation at 23 ° C. of 10% or more and 50% or less.
[4] The resin sheet with a support according to any one of [1] to [3], wherein the first resin composition contains an elastomer.
[5] The resin sheet with a support according to any one of [1] to [4], wherein the elongation of the first cured product layer is 40% or more.
[6] When the content (mass%) of the inorganic filler in the first resin composition is B1, and the content (mass%) of the inorganic filler in the second resin composition is B2, B2 The resin sheet with a support according to any one of [1] to [5], wherein / B1 is 0.1 or more and 10 or less.
[7] A first cured product layer formed of a cured product of the first resin composition and a second resin having a composition different from that of the first resin composition formed on the first cured product layer A second cured product layer formed from a cured product of the resin composition of
The first resin composition and the second resin composition each independently contain an epoxy resin, a curing agent and an inorganic filler,
The elastic modulus at 23 ° C. of the first cured product layer is 0.001 GPa or more and 0.1 GPa or less,
The elastic modulus at 23 ° C. of the second cured product layer is 3 GPa or more and 10 GPa or less,
Hardened | cured material whose t3 / t4 is 5-10, when the thickness of a 1st hardened | cured material layer is set to t3 (micrometer) and the thickness of a 2nd hardened | cured material layer is set to t4 (micrometer).

  ADVANTAGE OF THE INVENTION According to this invention, the cured | curing material of the resin sheet layer of the resin sheet with a support which can obtain the hardened | cured material which is excellent in a softness | flexibility and can suppress a halo phenomenon can be provided.

FIG. 1 is a cross-sectional view schematically showing a resin sheet with a support according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically illustrating an insulating layer obtained by curing a resin sheet layer of a resin sheet with a support according to an embodiment of the present invention, together with an inner layer substrate. FIG. 3 is a plan view schematically showing the surface of the insulating layer obtained by curing the resin sheet layer of the resin sheet with a support according to one embodiment of the present invention, on the side opposite to the conductor layer. FIG. 4 is a cross-sectional view schematically showing an insulating layer after the roughening treatment, obtained by curing a resin sheet layer of a resin sheet with a support according to an embodiment of the present invention, together with an inner layer substrate.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and exemplifications, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof.

  Before describing the resin sheet with a support of the present invention in detail, in the resin sheet with a support of the present invention, the first resin composition layer and the second resin composition layer included in the resin sheet layer are formed. The 1st resin composition and 2nd resin composition which are used in the case are demonstrated.

  Here, the first and second resin compositions may be collectively referred to as “resin composition”, and the first and second resin composition layers may be collectively referred to as “resin composition layer”.

<First resin composition>
The first resin composition forming the first resin composition layer contains (A) a thermosetting resin and (B) an inorganic filler. The first resin composition further contains (C) an elastomer, (D) a flame retardant, (E) a curing accelerator, (F) a thermoplastic resin, and (G) other additives as necessary. May be. Hereinafter, each component contained in the first resin composition will be described in detail.

-(A) Thermosetting resin-
The first resin composition contains (A) a thermosetting resin as the component (A). As the thermosetting resin, a thermosetting resin capable of using the first cured product layer, which is a cured product of the first resin composition, as an insulating member such as an insulating layer can be used. Examples of such thermosetting resins include epoxy resins, phenol resins, naphthol resins, benzoxazine resins, active ester resins, cyanate ester resins, carbodiimide resins, amine resins, and acid anhydride resins. Examples thereof include resins. (A) A component may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. Hereinafter, the phenol resin, naphthol resin, benzoxazine resin, active ester resin, cyanate ester resin, carbodiimide resin, amine resin, and acid anhydride resin may be collectively referred to as “curing agent”. The first resin composition preferably contains an epoxy resin as the component (A).

  Examples of the epoxy resin as the component (A) include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, Trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak 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 butadiene structure, alicyclic Poxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. . An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  It is preferable that a 1st resin composition contains the epoxy resin which has a 2 or more epoxy group in 1 molecule as (A) component. From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 100% by mass of the nonvolatile component of the epoxy resin as the component (A). 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 an epoxy resin that is liquid at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) and an epoxy resin that is a solid at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). ) The first resin composition may contain only the liquid epoxy resin as the component (A), or may contain only the solid epoxy resin, and contains a combination of the liquid epoxy resin and the solid epoxy resin. You may go out. From the viewpoint of obtaining sufficient flexibility when used in the form of a resin sheet with a support as the component (A) or improving the breaking strength of the cured product of the resin composition layer, the solid epoxy resin It is preferable to use only.

  The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule.

  Solid epoxy resins include bixylenol 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, 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, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, Bixylenol 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; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC; “HP-7200HH”, “HP-7200H”, “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” (manufactured by DIC) Naphthylene ether type epoxy resin) “EPPN-502H” (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Resin); “NC7000L” (naphthol novolak type epoxy resin) manufactured by Nippon Kayaku; “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin) manufactured by Nippon Kayaku; Nippon Steel & Sumitomo Metal “ESN475V” (naphthol type epoxy resin) manufactured by Kagaku Co .; “ESN485” (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; “YX4000H”, “YX4000”, “YL6121” (biphenyl type) manufactured by Mitsubishi Chemical Corporation Epoxy resin); “YX4000HK” (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical; “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical; “PG-100” and “CG-” manufactured by Osaka Gas Chemical "500"; "YL" manufactured by Mitsubishi Chemical Corporation "760" (bisphenol AF type epoxy resin); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S manufactured by Mitsubishi Chemical Corporation" (Tetraphenylethane type epoxy resin) and the like. These may be used alone or in combination of two or more.

  The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexane dimethanol 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”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC; “828US”, “jER828EL”, “825”, “Epicoat” manufactured by Mitsubishi Chemical Corporation. 828EL "(bisphenol A type epoxy resin);" jER807 "and" 1750 "(bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical;" jER152 "(phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical; "630", "630LSD" (glycidylamine type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX" manufactured by Nagase ChemteX Corporation -721 "(glycidyl Steal type epoxy resin); “Celoxide 2021P” manufactured by Daicel Corporation (an alicyclic epoxy resin having an ester skeleton); “PB-3600” manufactured by Daicel Corporation (an epoxy resin having a butadiene structure); manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. “ZX1658”, “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) and the like. These may be used alone or in combination of two or more.

  When the liquid epoxy resin and the solid epoxy resin are used in combination as the component (A), their quantitative ratio (liquid epoxy resin: solid epoxy resin) is a mass ratio, preferably 1: 1 to 1:20. More preferably, it is 1: 1.5-1: 15, Most preferably, it is 1: 2-1: 10. When the quantity ratio between the liquid epoxy resin and 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 (A) 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. By becoming this range, the crosslinked density of the hardened | cured material of a 1st resin composition layer becomes enough, and can provide an insulating layer with small surface roughness. Epoxy equivalent is the mass of resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

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

  The content of the epoxy resin as the component (A) is preferably from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability when the nonvolatile component in the first resin composition is 100% by mass. 1 mass% or more, More preferably, it is 3 mass% or more, More preferably, it is 5 mass% or more. The upper limit of the content of the epoxy resin is preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention. In addition, in this invention, content of each component in a resin composition is a value when the non-volatile component in a 1st or 2nd resin composition is 100 mass% unless there is separate description.

  As the active ester resin, a resin having one or more active ester groups in one molecule can be used. Among them, the active ester resin has two or more ester groups having high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Resins are preferred. The active ester resin 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 resin obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester resin 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, 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, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Preferable specific examples of the active ester resin include an active ester resin containing a dicyclopentadiene type diphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of phenol novolac, and a benzoyl of phenol novolac. An active ester resin containing a chemical compound is exemplified. Among these, an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadiene type diphenol structure are more preferable. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  Examples of commercially available active ester resins include “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC-8000H-” as active ester resins containing a dicyclopentadiene type diphenol structure. 65TM ”,“ EXB-8000L-65TM ”(manufactured by DIC);“ EXB9416-70BK ”,“ EXB-8150-65T ”(manufactured by DIC) as an active ester resin containing a naphthalene structure; an acetylated product of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester resin containing; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester resin containing a benzoylated phenol novolac; an active ester resin as an acetylated phenol novolac “DC808” (manufactured by Mitsubishi Chemical Corporation); “YLH1026” (manufactured by Mitsubishi Chemical Corporation), “YLH1030” (manufactured by Mitsubishi Chemical Corporation), “YLH1048” (manufactured by Mitsubishi Chemical Corporation) as active ester resins that are benzoylated phenol novolac );

  As the phenol resin and 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 naphtholic resin include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., “NHN”, “CBN” manufactured by Nippon Kayaku Co., Ltd. ”,“ GPH ”,“ SN170 ”,“ SN180 ”,“ SN190 ”,“ SN475 ”,“ SN485 ”,“ SN495 ”,“ SN-495V ”,“ SN375 ”,“ SN395 ”, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., DIC “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500” and the like manufactured by the company may be mentioned.

  Specific examples of the benzoxazine-based resin include “JBZ-OD100” (benzoxazine ring equivalent 218), “JBZ-OP100D” (benzoxazine ring equivalent 218), “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 resin include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4 ′. -Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) ) Bifunctional cyanate resins such as methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; phenol Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac; prepolymer these cyanate resin is partially triazine of; and the like. Specific examples of the cyanate ester resin include “PT30” and “PT60” (phenol novolac polyfunctional cyanate ester resin), “ULL-950S” (polyfunctional cyanate ester resin), “BA230” manufactured by Lonza Japan, “BA230S75” (a prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified into a trimer) and the like.

  Specific examples of the carbodiimide 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); Stabaxol (registered trademark) P (carbodiimide group equivalent: 302) manufactured by Rhein Chemie.

  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 preferred 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, and more preferably a primary amine. Specific examples of the amine curing agent 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, bis (4- (3-aminophenoxy) phenyl) sulfone, and the like. Commercially available amine resins may be used. For example, “KAYABOND C-200S”, “KAYABOND C-100”, “Kayahard A-A”, “Kayahard A-B”, “Kayahard” manufactured by Nippon Kayaku Co., Ltd. AS ”,“ Epicure W ”manufactured by Mitsubishi Chemical Corporation, and the like.

  Examples of the acid anhydride resin include a resin having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride , Trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl Sulfonetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexa Dro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione, ethylene glycol bis (anhydrotrimellitate), styrene and maleic acid And polymer type acid anhydrides such as styrene / maleic acid resin copolymerized.

  (A) When an epoxy resin and a hardening | curing agent are contained as a component, the quantity ratio of an epoxy resin and all the hardening | curing agents is [total number of epoxy groups of an epoxy resin]: [total number of reactive groups of a hardening | 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 still more preferably 1: 1 to 1: 2. Here, the “number of epoxy groups of the epoxy resin” is a value obtained by adding up all values obtained by dividing the mass of the nonvolatile component of the epoxy resin present in the first resin composition by the epoxy equivalent. The “number of active groups of the curing agent” is a value obtained by adding up all values obtained by dividing the mass of the non-volatile component of the curing agent present in the first resin composition by the active group equivalent. By setting the quantitative ratio of the epoxy resin and the curing agent within such a range, a first cured product layer having excellent flexibility can be obtained.

  The content of the curing agent as the component (A) is preferably 5% by mass with respect to 100% by mass of the nonvolatile component in the first resin composition, from the viewpoint of obtaining a first cured product layer having excellent flexibility. Above, more preferably 8% by mass or more, further preferably 10% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.

-(B) Inorganic filler-
The first resin composition contains an inorganic filler as the component (B). (B) By including an inorganic filler in the resin composition, the elastic modulus of the first cured product layer can be adjusted.

  (B) An inorganic compound is used as the material of the inorganic filler. Examples of inorganic filler materials 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, zirconium oxide , Barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as silica, spherical silica is preferable. (B) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

  (B) Examples of commercially available inorganic fillers include “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials; “YC100C”, “YA050C”, and “YA050C-MJE” manufactured by Admatechs. "YA010C"; Denka's "UFP-30"; Tokuyama's "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N"; Admatechs' "SC2500SQ" “SO-C4”, “SO-C2”, “SO-C1”; and the like.

  (B) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. Preferably it is 5 micrometers or less, More preferably, it is 2 micrometers or less, More preferably, it is 1 micrometer or less.

  (B) The average particle diameter 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 particle size distribution measuring device and setting 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 are weighed in a vial and can be dispersed by ultrasonic for 10 minutes. Particles obtained by measuring the volume-based particle size distribution of the inorganic filler (B) using a flow cell method, using a laser diffraction particle size distribution measuring device as the measurement sample, using blue and red as the light source wavelength. The average particle diameter is calculated as the median diameter from the diameter distribution. Examples of the laser diffraction particle size distribution measuring apparatus include “LA-960” manufactured by Horiba, Ltd.

(B) The specific surface area of the inorganic filler 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. Although there is no special restriction | limiting in an upper limit, Preferably it is 60 m < ² > / g or less, 50 m < ² > / g or less, or 40 m < ² > / g or less. The specific surface area can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method. .

  (B) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanates. A coupling agent etc. are mentioned. Moreover, a surface treating agent may be used individually by 1 type, and may be used combining two or more types arbitrarily.

  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., Shin-Etsu. “KBE903” (3-aminopropyltriethoxysilane) manufactured by Chemical Industry 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 to 5 parts by mass of a surface treatment agent, and surface-treated with 0.2 to 3 parts by mass. It is preferable that the surface treatment is performed with 0.3 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, 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 preferable from the viewpoint of suppressing the melt viscosity of the resin varnish and the increase in melt viscosity in the resin sheet layer. Further preferred.

  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 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.

  (B) The content of the inorganic filler is preferably 10% by mass or more when the nonvolatile component in the first resin composition is 100% by mass from the viewpoint of obtaining the first cured product layer having a low elastic modulus. More preferably, it is 15 mass% or more, More preferably, it is 20 mass% or more, Preferably it is 40 mass% or less, More preferably, it is 35 mass% or less, More preferably, it is 30 mass% or less.

-(C) Elastomer-
The first resin composition may further contain (C) an elastomer as an optional component.

  Component (C) is one kind selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. It is preferable to have the above structure, and a resin having one or more structures selected from a polybutadiene structure, a poly (meth) acrylate structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, or a polycarbonate structure It is more preferable that the resin is one having at least one structure selected from a polybutadiene structure and a polyalkyleneoxy structure. Usually, when the first resin composition contains an elastomer having the above structure, the insulating layer has low elasticity, and a cured product having excellent MIT folding resistance can be obtained. “(Meth) acrylate” is a term including methacrylate and acrylate, and combinations thereof. These structures may be contained in the main chain or in the side chain.

  The component (C) preferably has a high molecular weight in order to reduce warpage when the resin composition is cured. The number average molecular weight (Mn) is preferably 1,000 or more, more preferably 1500 or more, and further preferably 3000 or more and 5000 or more. The upper limit is preferably 1,000,000 or less, more preferably 900,000 or less. The number average molecular weight (Mn) is a polystyrene equivalent number average molecular weight measured using GPC (gel permeation chromatography).

  Component (C) is a functional group capable of reacting with the epoxy resin as component (A) from the viewpoint of increasing the peel strength by reacting with the epoxy resin as component (A) to cure the first resin composition. It is preferable to have. In addition, as a functional group which can react with the epoxy resin as (A) component, the functional group which appears by heating shall also be included.

  In a preferred embodiment, the functional group capable of reacting with the epoxy resin as the component (A) is selected from the group consisting of a hydroxy group, a carboxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. One or more functional groups selected. Among these, the functional group is preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, or a urethane group, more preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, or an epoxy group. A functional hydroxyl group is particularly preferred. However, when an epoxy group is included as a functional group, the number average molecular weight (Mn) is preferably 5,000 or more.

  A preferred embodiment of the component (C) is a resin containing a polybutadiene structure, and the polybutadiene structure may be contained in the main chain or in the side chain. Note that part or all of the polybutadiene structure may be hydrogenated. A resin containing a polybutadiene structure is referred to as a polybutadiene resin.

  Specific examples of the polybutadiene resin include “Ricon 130MA8”, “Ricon 130MA13”, “Ricon 130MA20”, “Ricon 131MA5”, “Ricon 131MA10”, “Ricon 131MA17”, “Ricon 131MA20”, “Ricon” manufactured by Clay Valley. 184MA6 "(acid anhydride group-containing polybutadiene)," GQ-1000 "(hydroxyl group, carboxyl group-introduced polybutadiene) manufactured by Nippon Soda Co., Ltd.," G-1000 "," G-2000 "," G-3000 "(both ends) Hydroxyl group polybutadiene), “GI-1000”, “GI-2000”, “GI-3000” (hydroxylated hydrogenated polybutadiene at both ends), “FCA-061L” (hydrogenated polybutadiene skeleton epoxy manufactured by Nagase ChemteX) Resin) and the like. As one embodiment, linear polyimide (polyimide described in JP 2006-37083 A and WO 2008/153208 A) using a hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride as a raw material can be used. . The content of the butadiene structure in the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. Details of the polyimide resin can be referred to the descriptions in JP-A-2006-37083 and International Publication No. 2008/153208, the contents of which are incorporated herein.

A preferred embodiment of the component (C) is a resin containing a poly (meth) acrylate structure. A resin containing a poly (meth) acrylate structure is referred to as a poly (meth) acrylic resin.
Examples of the poly (meth) acrylic resin include Teissan resin manufactured by Nagase ChemteX Corporation, “ME-2000”, “W-116.3”, “W-197C”, “KG-25” manufactured by Negami Kogyo Co., Ltd., “ KG-3000 "and the like.

A preferred embodiment of the component (C) is a resin containing a polycarbonate structure. A resin containing a polycarbonate structure is called a polycarbonate resin.
Examples of the polycarbonate resin include "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray. It is done. A linear polyimide made from hydroxyl group-terminated polycarbonate, diisocyanate compound and tetrabasic acid anhydride can also be used. The content of the carbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. Details of the polyimide resin can be referred to the description of International Publication No. 2016/129541, the contents of which are incorporated herein.

  Another specific example of the component (C) is a resin containing a siloxane structure. A resin containing a siloxane structure is called a siloxane resin. As the siloxane resin, for example, “SMP-2006”, “SMP-2003PGMEA”, “SMP-5005PGMEA” manufactured by Shin-Etsu Silicone Co., Ltd., linear polyimide made from amine group-terminated polysiloxane and tetrabasic acid anhydride (International JP 2010/053185, JP 2002-12667 A and JP 2000-319386 A).

  Another specific example of the component (C) is a resin containing an alkylene structure or an alkyleneoxy structure. A resin containing an alkylene structure is called an alkylene resin, and a resin containing an alkyleneoxy structure is called an alkyleneoxy resin. The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and further preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. Specific examples of the alkylene resin and alkyleneoxy resin include “PTXG-1000” and “PTXG-1800” manufactured by Asahi Kasei Fibers.

  Another specific example of the component (C) is a resin containing an isoprene structure. A resin containing an isoprene structure is called an isoprene resin. Specific examples of the isoprene resin include “KL-610” and “KL613” manufactured by Kuraray Co., Ltd.

  Another specific example of the component (C) is a resin containing an isobutylene structure. A resin containing an isobutylene structure is called an isobutylene resin. Specific examples of the isobutylene resin include “SIBSTAR-073T” (styrene-isobutylene-styrene triblock copolymer) and “SIBSTAR-042D” (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

  (C) From the viewpoint of obtaining a first cured product layer having excellent flexibility, the content of the elastomer is preferably 10% by mass or more when the nonvolatile component in the first resin composition is 100% by mass. Preferably it is 20 mass% or more, More preferably, it is 30 mass% or more. An upper limit becomes like this. Preferably it is 50 mass% or less, More preferably, it is 45 mass% or less, More preferably, it is 40 mass% or less.

-(D) Flame retardant-
The first resin composition may further contain (D) a flame retardant as an optional component. Examples of the flame retardant (E) include phosphazene compounds, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides, and the like, and phosphazene compounds are preferable. (D) A flame retardant may be used individually by 1 type, or may use 2 or more types together.

  The phosphazene compound is a cyclic compound having nitrogen and phosphorus as constituent elements, and the phosphazene compound is reacted with the epoxy resin as the component (A) to cure the first resin composition and increase the peel strength. A phosphazene compound having a phenolic hydroxyl group is preferred. Specific examples of the phosphazene compound include, for example, “SPH-100”, “SPS-100”, “SPB-100”, “SPE-100” manufactured by Otsuka Chemical Co., Ltd., “FP-100” manufactured by Fushimi Pharmaceutical Co., Ltd. "FP-110", "FP-300", "FP-400", etc. are mentioned.

  Commercially available products may be used as the flame retardant other than the phosphazene compound, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd. and “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. As the flame retardant, those which are difficult to hydrolyze are preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

  (D) The content of the flame retardant is preferably 0.1% by mass or more when the nonvolatile component in the first resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. More preferably, it is 0.2 mass% or more, More preferably, it is 0.3 mass% or more. An upper limit becomes like this. Preferably it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.

-(E) Curing accelerator-
The first resin composition may further contain (E) a curing accelerator as an optional component.

  Examples of the 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 these, a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

  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 amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. (5,4,0) -undecene and the like are 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-methyl Examples include imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2- Phenylimidazole is preferred.

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  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.

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper 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.

  (E) The content of the curing accelerator is preferably 0.01% by mass or more when the nonvolatile component in the first resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. More preferably, it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more, Preferably it is 3 mass% or less, More preferably, it is 1 mass% or less, More preferably, it is 0.5 mass% or less.

<(F) Thermoplastic resin>
The first resin composition may further contain (F) a thermoplastic resin as an optional component.

  Examples of the thermoplastic resin as the component (F) include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, and polyether. Examples include ether ketone resins and polyester resins. Among these, a phenoxy resin is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention and a viewpoint of obtaining an insulating layer having a small surface roughness and particularly excellent adhesion to the conductor layer. Moreover, a thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more types.

  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 a phenoxy resin having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

  Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resins) manufactured by Mitsubishi Chemical; “YX8100” (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical; “YX6954” (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel &Chemicals; “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical; “YL7500BH30”, “YX6954BH30”, “YX7553”, “YX7553BH30” manufactured by Mitsubishi Chemical “YL7769BH30”, “YL6794”, “YL7213”, “YL7290”, “YL7482”;

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include SLECK 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 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 polyamide-imide resin include modified polyamide-imides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical.

  Specific examples of the polyethersulfone 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.

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

  (F) The weight average molecular weight (Mw) of the 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.

  (F) The content of the thermoplastic resin is preferably 0.01% by mass or more when the nonvolatile component in the first resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. More preferably, it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more, Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less.

-(G) Other additives-
The resin composition may further contain other additives as optional components in addition to the components described above. Examples of such additives include organic fillers; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; thickeners; antifoaming agents; leveling agents; adhesion promoters; These resin additives are mentioned. These additives may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

<Second resin composition>
The second resin composition forming the second resin composition layer is different in composition from the first resin composition. The second resin composition contains a thermosetting resin and an inorganic filler independently of the first resin composition. The second resin composition may further contain a flame retardant, a curing accelerator, a thermoplastic resin, and other additives as necessary.

  The thermosetting resin, inorganic filler, flame retardant, curing accelerator, thermoplastic resin, and other additives contained in the second resin composition are described in the <First resin composition> column. (A) Thermosetting resin, (B) Inorganic filler, (D) Flame retardant, (E) Curing accelerator, (F) Thermoplastic resin, (G) The same thing as another additive is mentioned. . However, the components (A) to (B) and (D) to (G) contained in the second resin composition may be the same as or different from those contained in the first resin composition.

  The second resin composition preferably contains an epoxy resin and a curing agent as the component (A) from the viewpoint of obtaining the desired effect of the present invention. The curing agent as the component (A) is preferably at least one selected from the group consisting of an active ester resin, a phenol resin, and a naphthol resin.

  The content of the epoxy resin as the component (A) in the second resin composition is such that the nonvolatile component in the second resin composition is 100 from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. In the case of mass%, it is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. The upper limit of the content of the epoxy resin is preferably 50% by mass or less, more preferably 45% by mass or less, and particularly preferably 40% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

  The content of the curing agent as the component (A) in the second resin composition is preferably 5 when the nonvolatile component in the second resin composition is 100% by mass from the viewpoint of suppressing the haloing phenomenon. It is at least mass%, more preferably at least 8 mass%, further preferably at least 10 mass%, preferably at most 30 mass%, more preferably at most 25 mass%, still more preferably at most 20 mass%.

  The amount ratio of the epoxy resin and the curing agent in the second resin composition is a ratio of [(A) the total number of epoxy groups of the epoxy resin]: [(B) the total number of reactive groups of the curing agent]. The range of 1: 0.01 to 1: 5 is preferred, 1: 0.5 to 1: 3 is more preferred, and 1: 1 to 1: 2 is even more preferred.

  The content of the inorganic filler (B) in the second resin composition is preferably 30% by mass when the nonvolatile component in the second resin composition is 100% by mass from the viewpoint of suppressing the haloing phenomenon. More preferably, it is 32 mass% or more, More preferably, it is 33 mass% or more, Preferably it is 70 mass% or less, More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less.

  When the content (mass%) of the inorganic filler in the first resin composition is B1, and the content (mass%) of the inorganic filler in the second resin composition is B2, B2 / B1 is , Preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1 or more. The upper limit is preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less and 2 or less. By setting B2 / B1 within such a range, a cured product having excellent MIT folding resistance and capable of suppressing the halo phenomenon can be obtained.

  The content of the flame retardant (D) in the second resin composition is preferably when the nonvolatile component in the second resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. Is 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more. An upper limit becomes like this. Preferably it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.

  From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the (E) curing accelerator in the second resin composition, when the nonvolatile component in the second resin composition is 100% by mass, Preferably it is 0.01 mass% or more, More preferably, it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more, Preferably it is 3 mass% or less, More preferably, it is 1 mass% or less, More preferably, it is 0 .5% by mass or less.

  From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the thermoplastic resin (F) in the second resin composition is, when the nonvolatile component in the second resin composition is 100% by mass, Preferably it is 0.01 mass% or more, More preferably, it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more, Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 1 It is below mass%.

[Resin sheet with support]
The resin sheet with a support according to the present invention is a resin sheet with a support including a support and a resin sheet layer provided on the support, and the resin sheet layer is formed of the first resin composition. The first resin composition layer and the second resin composition layer formed of the second resin composition having a composition different from that of the first resin composition in this order from the support side, The first resin composition and the second resin composition each independently contained an epoxy resin, a curing agent, and an inorganic filler, and the first resin composition layer was thermally cured at 180 ° C. for 90 minutes. The elastic modulus at 23 ° C. of the first cured product layer is 0.001 GPa or more and 0.1 GPa or less, and the second cured product layer obtained by thermosetting the second resin composition layer at 180 ° C. for 90 minutes is 23 ° C. The first resin has an elastic modulus of 3 GPa or more and 10 GPa or less The thickness of the formed product layer is t1 ([mu] m), if the thickness of the second resin composition layer was t2 (μm), t1 / t2 is 1 or more and 10 or less. By using such a resin sheet with a support, it is possible to obtain the desired effect of the present invention that a cured product having excellent flexibility and excellent suppression of the haloing phenomenon can be obtained.

  In FIG. 1, the schematic sectional drawing of an example of the resin sheet with a support body of this invention is shown. The resin sheet 1 with a support of the present invention includes a support 3 and a resin sheet layer 2. The resin sheet layer 2 includes a first resin composition layer 10 and a second resin composition layer 20 in this order from the support 3 side. The resin sheet layer 2 may include an additional layer between the first resin composition layer 10 and the second resin composition layer 20, but the first resin composition layer and the second resin It is preferable to include only the composition layer.

  When forming an insulating layer on a conductor layer, it laminates | stacks so that the resin sheet layer of a resin sheet with a support body may join with a conductor layer normally on a conductor layer, and it is carried out by carrying out thermosetting after that. In order to obtain an insulating layer with excellent flexibility, a method of lowering the elastic modulus of the cured product of the resin sheet layer can be considered, but a cured product with a low elastic modulus tends to deteriorate the resin around the via hole after forming the via hole, A haloing phenomenon is likely to occur. In contrast, the resin sheet layer in the resin sheet with a support of the present invention has first and second resin composition layers in order from the support side, and the second resin composition layer is cured. The elastic modulus of the second cured product layer is higher than that of the first cured product layer obtained by curing the first resin composition layer. For this reason, when forming an insulating layer on a conductor layer, since a 2nd hardened | cured material layer will join with the said conductor layer, a haloing phenomenon can be suppressed. Furthermore, since most of the cured product layer is formed of the first cured product layer having a low elastic modulus, the flexibility of the entire cured product layer can be increased. Therefore, both suppression of the haloing phenomenon and improvement in flexibility can be achieved.

<Resin sheet layer>
The resin sheet layer includes a first resin composition layer formed from the first resin composition and a second resin composition formed from a second resin composition having a composition different from that of the first resin composition. And a physical layer in this order from the support side. The first and second resin compositions are as described in the <First resin composition> column and the <Second resin composition> column.

  From the viewpoint of obtaining a cured product layer excellent in flexibility, the thickness (t1 (μm)) of the first resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and further preferably 35 μm or less. The lower limit is preferably 0.05 μm or more, more preferably 0.1 μm or more, and further preferably 1 μm or more.

  The thickness (t2 (μm)) of the second resin composition layer is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less from the viewpoint of obtaining a cured product layer that suppresses the haloing phenomenon. is there. The lower limit is preferably 0.05 μm or more, more preferably 0.1 μm or more, and further preferably 1 μm or more.

  t1 / t2 is 1 or more, preferably 1.5 or more, and more preferably 2 or more, from the viewpoint of obtaining a cured product layer that is excellent in flexibility and suppresses the haloing phenomenon. The upper limit is 10 or less, preferably 8 or less, more preferably 5 or less.

  The thickness (t1 + t2) of the resin sheet layer is preferably 80 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less from the viewpoint of obtaining a cured product layer that is excellent in flexibility and suppresses the haloing phenomenon. The lower limit is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 2 μm or more.

  The elastic modulus at 23 ° C. of the first cured product layer obtained by thermally curing the first resin composition layer at 180 ° C. for 90 minutes is 0.001 GPa or more from the viewpoint of obtaining a cured product having excellent flexibility. , Preferably 0.01 GPa or more, more preferably 0.05 GPa or more. The upper limit is 0.1 GPa or less, preferably 0.09 GPa or less, more preferably 0.08 GPa or less. This elastic modulus can be adjusted by the composition of the first resin composition, and can be adjusted, for example, by (C) the type and amount of elastomer and (B) the amount of inorganic filler. The elasticity modulus of a 1st hardened | cured material layer can be measured according to the method as described in the Example mentioned later.

  The elastic modulus at 23 ° C. of the second cured product layer obtained by thermosetting the second resin composition layer at 180 ° C. for 90 minutes is 3 GPa or more from the viewpoint of obtaining a cured product that suppresses the haloing phenomenon. , Preferably 3.5 GPa or more, more preferably 4 GPa or more. The upper limit is 10 GPa or less, preferably 8 GPa or less, more preferably 6 GPa or less. This elastic modulus can be adjusted by the composition of the second resin composition, for example, by adjusting the amount of (B) inorganic filler. The elasticity modulus of a 2nd hardened | cured material layer can be measured according to the method as described in the Example mentioned later.

  The elastic modulus at 23 ° C. of the cured product layer obtained by thermosetting the resin sheet layer at 180 ° C. for 90 minutes is preferably 0.01 GPa or more from the viewpoint of obtaining a cured product having excellent flexibility and suppressing the haloing phenomenon. More preferably, it is 0.1 GPa or more, and further preferably 0.5 GPa or more and 1 GPa or more. The upper limit is preferably 4 GPa or less, more preferably 3.8 GPa or less, and even more preferably 3.5 GPa or less. This elastic modulus can be adjusted by the thicknesses of the first cured product layer and the second cured product layer. The elastic modulus of the cured product layer can be measured according to the method described in Examples described later.

  The elongation at 23 ° C. of the first cured product layer obtained by thermosetting the first resin composition layer at 180 ° C. for 90 minutes is preferably 40% or more from the viewpoint of obtaining a cured product having excellent flexibility. Preferably they are 45% or more, More preferably, they are 50% or more, 55% or more. The upper limit is preferably 90% or less, more preferably 80% or less, and still more preferably 70% or less. This elongation can be adjusted by the composition of the first resin composition, and can be adjusted by, for example, the type and amount of (C) elastomer and the amount of (B) inorganic filler. The elongation of the first cured product layer can be measured according to the method described in Examples described later.

  The elongation at 23 ° C. of the second cured product layer obtained by thermally curing the second resin composition layer at 180 ° C. for 90 minutes is preferably 20% or less from the viewpoint of obtaining a cured product that suppresses the haloing phenomenon. More preferably, it is 15% or less, and further preferably 10% or less. The lower limit is preferably 1% or more, more preferably 2% or more, and further preferably 3% or more. This elongation can be adjusted by the composition of the second resin composition, for example, by adjusting the amount of (B) inorganic filler. The elongation of the second cured product layer can be measured according to the method described in Examples described later.

  The elongation at 23 ° C. of the cured product layer obtained by thermally curing the resin sheet layer at 180 ° C. for 90 minutes is preferably 10% or more from the viewpoint of obtaining a cured product having excellent flexibility and suppressing the haloing phenomenon. Preferably it is 15% or more, More preferably, it is 20% or more. The upper limit is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less. This elongation can be adjusted by the thicknesses of the first cured product layer and the second cured product layer. The elongation of the cured product layer can be measured according to the method described in Examples described later.

<Support>
Examples of the support include a film made of a plastic material, a metal foil, and a release paper, 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, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, 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.). It may be used.

  The support may be subjected to mat treatment, corona treatment, and antistatic treatment on the surface to be bonded to the resin sheet layer.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin sheet layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1”, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. AL-5 ”,“ AL-7 ”,“ Lumirror T60 ”manufactured by Toray Industries, Inc.,“ Purex ”manufactured by Teijin Limited,“ Unipeel ”manufactured by Unitika Ltd., and the like.

  Although it does not specifically limit as thickness of a support body, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  The resin sheet with a support may further include a protective film on the surface of the resin sheet layer that is not joined to the support. The protective film contributes to the prevention of adhesion and scratches of dust on the surface of the resin sheet layer. As the material of the protective film, the same material as described in the <Support> column may be used. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. The resin sheet with a support can be used by peeling off the protective film when producing a printed wiring board or the like. The thickness of the protective film is preferably thinner than the thickness of the support.

<Method for producing resin sheet with support>
As a preferred embodiment of the method for producing a resin sheet with a support, the first resin sheet provided with the first resin composition layer on the first support, and the second support Using the second resin sheet provided with the second resin composition layer, the second resin composition layer is laminated so that the second resin composition layer is bonded to the first resin composition layer to form a resin sheet with a support. Is the method. In this method, the first support becomes the support of the resin sheet with the support.

  The first and second resin sheets are prepared by, for example, preparing resin varnishes in which the first and second resin compositions are dissolved in an organic solvent, and using the resin coat varnish for each of the first and second resin varnishes. It can be manufactured by coating on a support and further drying to form the first or second resin composition layer.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol, etc. Carbitols of the above; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The resin varnish may be dried by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the first and second resin composition layers is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the first is obtained by drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. And the 2nd resin composition layer can be formed.

  As another embodiment, after applying the first resin composition to the support and drying the coating film to form the first resin composition layer, the second resin composition layer is formed on the first resin composition layer. You may manufacture a resin sheet with a support body by the method of apply | coating a resin composition, drying a coating film, and providing a 2nd resin composition layer.

  In this method, the first resin composition layer is prepared by preparing a resin varnish in which the first resin composition is dissolved in the organic solvent described above, and applying the resin varnish on a support using a die coater or the like. It can be produced by drying the resin varnish. The second resin composition layer is prepared by preparing a resin varnish in which the second resin composition is dissolved in the organic solvent described above, and the resin varnish is formed on the first resin composition layer using a die coater or the like. It can produce by apply | coating to and drying a resin varnish. The resin varnish can be dried by the same method as described above.

  Moreover, you may form the resin sheet with a support body by the tandem coating method which coats two types of resin varnish sequentially on one coating line other than an above-described manufacturing method.

  The resin sheet with a support can be stored in a roll shape. When the resin sheet with a support has a protective film, it can be used by peeling off the protective film.

<Characteristics of resin sheet with support>
By curing the resin sheet layer of the resin sheet with a support of the present invention, an insulating layer formed of a cured product of the resin sheet layer can be obtained. When a via hole is formed in this insulating layer and a roughening process is performed, the haloing phenomenon can be suppressed. Hereinafter, these effects will be described with reference to the drawings.

  FIG. 2 is a cross-sectional view schematically showing the insulating layer 100 together with the inner layer substrate 200 obtained by curing the resin sheet layer of the resin sheet with a support according to one embodiment of the present invention. FIG. 2 shows a cross section of the insulating layer 100 taken along a plane passing through the center 120C of the bottom 120 of the via hole 110 and parallel to the thickness direction of the insulating layer 100.

  As shown in FIG. 2, the insulating layer 100 is a layer obtained by curing a resin sheet layer formed on the inner layer substrate 200 including the conductor layer 210, and is a second resin in order from the conductor layer 210 side. A second cured product layer 20 ′ obtained by thermally curing the composition layer 20 and a first cured product layer 10 ′ obtained by thermally curing the first resin composition layer 10 are provided. A via hole 110 is formed in the insulating layer 100. The via hole 110 is generally formed in a forward tapered shape having a larger diameter as it is closer to the surface 100U of the insulating layer 100 on the side opposite to the conductor layer 210 and smaller as it is closer to the conductor layer 210. It is formed in a columnar shape having a constant diameter in the thickness direction of 100. The via hole 110 is usually formed by irradiating the surface 100U of the insulating layer 100 opposite to the conductor layer 210 with laser light to remove a part of the insulating layer 100.

  The bottom of the via hole 110 on the conductor layer 210 side is appropriately referred to as a “via bottom” and denoted by reference numeral 120. The diameter of the via bottom 120 is referred to as a bottom diameter Lb. An opening formed on the opposite side of the via hole 110 from the conductor layer 210 is appropriately referred to as a “via top” and is denoted by reference numeral 130. The diameter of the via top 130 is referred to as a top diameter Lt. Normally, the via bottom 120 and the via top 130 are formed in a circular shape when viewed in the thickness direction of the insulating layer 100, but may be elliptical. When the planar shapes of the via bottom 120 and the via top 130 are elliptical, the bottom diameter Lb and the top diameter Lt respectively represent the major axis of the elliptical shape.

  At this time, the shape of the via hole 110 is better as the taper ratio Lb / Lt obtained by dividing the bottom diameter Lb by the top diameter Lt is closer to 100%. If the insulating layer is formed using the resin sheet with a support according to the present invention, the shape of the normal via hole 110 can be easily controlled, so that the via hole 110 having a taper ratio Lb / Lt close to 100% is realized. be able to.

  The taper ratio Lb / Lt of the via hole 110 can be calculated from the bottom diameter Lb and the top diameter Lt of the via hole 110. Further, the bottom diameter Lb and the top diameter Lt of the via hole 110 have a cross section through the insulating layer 100 parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the via bottom 120 using FIB (focused ion beam). After cutting out, the cross section can be measured by observing it with an electron microscope.

  FIG. 3 shows the surface of the insulating layer 100 obtained by curing the resin sheet layer of the resin sheet with a support according to one embodiment of the present invention, on the side opposite to the conductor layer 210 (not shown in FIG. 3). It is a top view which shows 100U typically.

  As shown in FIG. 3, when the insulating layer 100 in which the via hole 110 is formed is seen, the insulating layer 100 is formed around the via hole 110 from the edge 180 of the via top 130 to the edge 190 on the outer peripheral side of the discoloration portion 140. A discolored portion 140 that has been discolored may be observed. The discolored portion 140 can be formed by resin degradation when the via hole 110 is formed, and is usually formed continuously from the via hole 110. In many cases, the discoloration portion 140 is a whitened portion.

FIG. 4 is a cross-sectional view schematically showing the insulating layer 100 after the roughening treatment, obtained by curing the resin sheet layer of the resin sheet with a support according to an embodiment of the present invention, together with the inner layer substrate 200. . 4 shows a cross section of the insulating layer 100 taken along a plane passing through the center 120C of the via bottom 120 of the via hole 110 and parallel to the thickness direction of the insulating layer 100.
As shown in FIG. 4, when the insulating layer 100 in which the via hole 110 is formed is roughened, a haloing phenomenon occurs, and the insulating layer 100 of the discoloration portion 140 is peeled off from the conductor layer 210 and the edge of the via bottom 120 is formed. A gap 160 continuous from 150 may be formed.

  By using the resin sheet layer in the present invention, the haloing phenomenon can be suppressed. Therefore, peeling of the insulating layer 100 from the conductor layer 210 can be suppressed, and the size of the gap 160 can be reduced.

  The edge 150 of the via bottom 120 corresponds to the inner peripheral edge of the gap 160. Therefore, the distance Wb from the edge 150 of the via bottom 120 to the outer peripheral end 170 of the gap 160 (that is, the end far from the center 120C of the via bottom 120) 170 is the size in the in-plane direction of the gap 160. Equivalent to. Here, the in-plane direction refers to a direction perpendicular to the thickness direction of the insulating layer 100. In the following description, the distance Wb may be referred to as a haloing distance Wb from the edge 150 of the via bottom 120 of the via hole 110. The degree of suppression of the haloing phenomenon can be evaluated from the haloing distance Wb from the edge 150 of the via bottom 120. Specifically, it can be evaluated that the haloing phenomenon can be effectively suppressed as the haloing distance Wb from the edge 150 of the via bottom 120 is smaller.

For example, the top diameter is obtained by irradiating the insulating layer 100 formed on the copper foil by heating and curing the resin sheet layer at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes to emit CO ₂ laser light. A via hole 110 having an Lt of about 50 μm is formed. Then, it is immersed in the swelling solution at 60 ° C. for 10 minutes, then immersed in the oxidant solution at 80 ° C. for 20 minutes, then immersed in the neutralizing solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 15 minutes. If the resin sheet with a support of the present invention is used, the haloing distance Wb from the edge 150 of the via bottom 120 of the via hole 110 of the insulating layer 100 thus obtained is preferably 10 μm or less, more preferably 8 μm or less, More preferably, it can be 5.5 μm or less, and particularly preferably 5 μm or less.

The irradiation conditions of the CO ₂ laser light are as follows: mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ / shot, shot number 2, burst mode (10 kHz).

  The haloing distance Wb from the edge 150 of the via bottom 120 is such that a cross section appears through the insulating layer 100 parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the via bottom 120 using FIB (focused ion beam). It can be measured by observing the cross section with an electron microscope.

  Moreover, since the shape of the via hole 110 of the insulating layer 100 before the roughening treatment can be easily controlled by using the resin sheet layer, the shape of the via hole 110 is usually easily formed even in the insulating layer 100 after the roughening treatment. It is possible to control. Therefore, the shape of the via hole 110 can be improved even after the roughening treatment, as in the case before the roughening treatment. Therefore, if the resin sheet with a support of the present invention is used, a via hole 110 having a taper ratio Lb / Lt close to 100% can be realized in the insulating layer after the roughening treatment.

  The taper rate Lb / Lt of the via hole 110 after the roughening process can be calculated from the bottom diameter Lb and the top diameter Lt of the via hole 110. Further, the bottom diameter Lb and the top diameter Lt of the via hole 110 have a cross section through the insulating layer 100 parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the via bottom 120 using FIB (focused ion beam). After cutting out, the cross section can be measured by observing it with an electron microscope.

  Further, according to the study of the present inventors, it has been found that the size of the gap 160 tends to increase as the via hole diameter increases. Therefore, the degree of suppression of the halo phenomenon can be evaluated by the ratio of the size of the gap 160 to the diameter of the via hole 110. For example, the evaluation can be performed based on the haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110. Here, the bottom radius Lb / 2 of the via hole 110 refers to the radius of the via bottom 120 of the via hole 110. The haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110 is a ratio obtained by dividing the haloing distance Wb from the edge 150 of the via bottom 120 by the bottom radius Lb / 2 of the via hole 110. The smaller the haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110, the more effectively the haloing phenomenon can be suppressed.

For example, the top diameter is obtained by irradiating the insulating layer 100 formed on the copper foil by heating and curing the resin sheet layer at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes to emit CO ₂ laser light. A via hole 110 having an Lt of about 50 μm is formed. Then, it is immersed in the swelling solution at 60 ° C. for 10 minutes, then immersed in the oxidant solution at 80 ° C. for 20 minutes, then immersed in the neutralizing solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 15 minutes. The halo ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110 formed in the insulating layer 100 thus obtained is preferably 35% or less, more preferably 30% or less, and even more preferably 25% or less. .

The irradiation conditions of the CO ₂ laser light are as follows: mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ / shot, shot number 2, burst mode (10 kHz).

  The haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110 can be calculated from the bottom diameter Lb of the via hole 110 and the haloing distance Wb from the edge 150 of the via bottom 120 of the via hole 110.

  Furthermore, normally, by using the resin sheet layer in the present invention, the formation of the discolored portion 140 during the formation of the via hole 110 can be suppressed. Therefore, as shown in FIG. 3, the size of the color changing portion 140 can be reduced, and ideally, the color changing portion 140 can be eliminated. The size of the color changing portion 140 can be evaluated by the haloing distance Wt from the edge 180 of the via top 130 of the via hole 110.

  The edge 180 of the via top 130 corresponds to an inner peripheral edge of the color changing portion 140. The haloing distance Wt from the edge 180 of the via top 130 represents the distance from the edge 180 of the via top 130 to the edge 190 on the outer peripheral side of the discoloration portion 140. It can be evaluated that the smaller the haloing distance Wt from the edge 180 of the via top 130, the more effectively the formation of the discolored portion 140 can be suppressed.

For example, the top diameter is obtained by irradiating the insulating layer 100 formed on the copper foil by heating and curing the resin sheet layer at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes to emit CO ₂ laser light. A via hole 110 having an Lt of about 50 μm is formed. Then, it is immersed in the swelling solution at 60 ° C. for 10 minutes, then immersed in the oxidant solution at 80 ° C. for 20 minutes, then immersed in the neutralizing solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 15 minutes. The haloing distance Wt from the edge 180 of the via top 130 of the insulating layer 100 thus obtained can be preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less.

The irradiation conditions of the CO ₂ laser light are as follows: mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ / shot, shot number 2, burst mode (10 kHz).

  The haloing distance Wt from the edge 180 of the via top 130 can be measured by observation with an optical microscope.

  Further, according to the study by the present inventor, it has been found that in general, the size of the discoloration portion 140 tends to increase as the diameter of the via hole 110 increases. Therefore, the degree of suppression of the formation of the color changing portion 140 can be evaluated by the ratio of the size of the color changing portion 140 to the diameter of the via hole 110. For example, the evaluation can be performed based on the halo ratio Ht with respect to the top radius Lt / 2 of the via hole 110. Here, the top radius Lt / 2 of the via hole 110 refers to the radius of the via top 130 of the via hole 110. The haloing ratio Ht with respect to the top radius Lt / 2 of the via hole 110 is a ratio obtained by dividing the haloing distance Wt from the edge 180 of the via top 130 by the top radius Lt / 2 of the via hole 110. The smaller the halo ratio Ht with respect to the top radius Lt / 2 of the via hole 110, the more effectively the formation of the discolored portion 140 can be suppressed.

For example, the top diameter is obtained by irradiating the insulating layer 100 formed on the copper foil by heating and curing the resin sheet layer at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes to emit CO ₂ laser light. A via hole 110 having an Lt of about 50 μm is formed. Thereafter, it is immersed in the swelling solution at 60 ° C. for 10 minutes, then immersed in the oxidant solution at 80 ° C. for 20 minutes, then immersed in the neutralizing solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 15 minutes. The halo ratio Ht with respect to the top radius Lt / 2 of the via hole 110 formed in the insulating layer 100 thus obtained can be preferably 35% or less, more preferably 30% or less, and even more preferably 28% or less. .

The irradiation conditions of the CO ₂ laser light are as follows: mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ / shot, shot number 2, burst mode (10 kHz).

  The haloing ratio Ht with respect to the top radius Lt / 2 of the via hole 110 can be calculated from the top diameter Lt of the via hole 110 and the haloing distance Wt from the edge 180 of the via top 130 of the via hole 110.

  In the process of manufacturing a printed wiring board, the via hole 110 is usually formed in a state where another conductor layer (not shown) is not provided on the surface 100U of the insulating layer 100 opposite to the conductor layer 210. Therefore, if the manufacturing process of the printed wiring board is known, the structure in which the via bottom 120 is on the conductor layer 210 side and the via top 130 is opened on the opposite side to the conductor layer 210 can be clearly recognized. However, in the completed printed wiring board, a conductor layer may be provided on both sides of the insulating layer 100. In this case, it may be difficult to distinguish the via bottom 120 and the via top 130 depending on the positional relationship with the conductor layer. However, the top diameter Lt of the via top 130 is usually larger than the bottom diameter Lb of the via bottom 120. Therefore, in the above case, it is possible to distinguish the via bottom 120 and the via top 130 according to the diameter.

  By using the resin sheet with a support of the present invention, an insulating layer having excellent flexibility can be obtained in addition to suppressing the haloing phenomenon.

  The cured product of the resin sheet layer obtained by thermally curing the resin sheet with a support at 190 ° C. for 90 minutes exhibits the property of being excellent in flexibility. Therefore, the said hardened | cured material brings about the insulating layer excellent in a softness | flexibility. The folding endurance of the MIT folding endurance test is 200 times or more. The evaluation of the flexibility can be measured according to a method described in Examples described later.

  The resin sheet with a support of the present invention is preferably used as a resin sheet with a support used to form the insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer. can do.

  In addition, in a multilayer printed wiring board described later, as a resin sheet with a support used for forming an insulating layer of a multilayer printed wiring board, a resin sheet with a support used to form an interlayer insulating layer of a printed wiring board It can be preferably used.

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin sheet with a support of the present invention is used for forming a rewiring as an insulating layer for forming a rewiring layer. The resin sheet with a support used for forming a layer and the resin sheet with a support used for sealing a semiconductor chip can also be suitably used. When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer.
(1) Laminating a temporary fixing film on a substrate;
(2) a step of temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) The process of peeling a base material and a temporary fixing film from a semiconductor chip,
(5) a step of forming a rewiring formation layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip are peeled; and (6) a rewiring layer as a conductor layer on the rewiring formation layer. Forming process

  Moreover, since the resin sheet layer in the resin sheet with a support of the present invention provides an insulating layer with good component embedding properties, it can be suitably used even when the printed wiring board is a component built-in circuit board.

[Cured product]
The cured product of the present invention is composed of a first cured product layer formed of a cured product of the first resin composition and a first resin composition formed on the first cured product layer. A second cured product layer formed of a cured product of a second resin composition different from each other, wherein the first resin composition and the second resin composition are each independently an epoxy resin, It contains a curing agent and an inorganic filler, the elastic modulus at 23 ° C. of the first cured product layer is 0.001 GPa to 0.1 GPa, and the elastic modulus at 23 ° C. of the second cured product layer is 3 GPa to 10 GPa. When the thickness of the first cured product layer is t3 (μm) and the thickness of the second cured product layer is t4 (μm), t3 / t4 is 5 or more and 10 or less.

  The first cured product layer is a cured product of the first resin composition, and the second cured product layer is a cured product of the second resin composition. The curing conditions for the first and second resin compositions can be the same as the thermosetting conditions for the resin sheet layer described below.

  The elastic modulus of the first and second cured product layers is 23 ° C. of the first and second cured product layers obtained by thermally curing the first and second resin composition layers at 180 ° C. for 90 minutes. It is the same as the elastic modulus in.

  The thickness (t3 (μm)) of the first cured product layer is the same as the thickness (t1 (μm)) of the first resin composition layer, and the thickness (t4 (μm)) of the second cured product layer. Is the same as the thickness (t2 (μm)) of the second resin composition layer. T3 / t4 is the same as the range of t1 / t2.

  This cured product is usually formed on the conductor layer as described above. Under the present circumstances, hardened | cured material is provided so that a 2nd hardened | cured material layer and a 1st hardened | cured material layer may be provided in this order from the conductor layer side. Therefore, since the 2nd hardened | cured material layer with a high elastic modulus joins to a conductor layer, peeling with a conductor layer and hardened | cured material can be suppressed, Therefore, a haloing phenomenon can be suppressed. Furthermore, since the cured product includes the first cured product layer having a low elastic modulus, the cured product has excellent flexibility as a whole. Therefore, this hardened | cured material can be used as an insulating layer provided with both suppression of a haloing phenomenon, and the outstanding softness | flexibility.

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer formed by the resin sheet layer of the resin sheet with a support of the present invention.

A printed wiring board can be manufactured by the method including the process of following (I) and (II), for example using the above-mentioned resin sheet with a support body.
(I) The process of laminating | stacking so that the 2nd resin composition layer of the resin sheet with a support body may join to an inner layer board | substrate on an inner layer board | substrate (II) The process of thermosetting a resin sheet layer and forming an insulating layer

  The “inner layer substrate” used in the step (I) is a member that becomes a printed wiring board substrate, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate. Etc. Moreover, this board | substrate may have a conductor layer in the single side | surface or both surfaces, and this conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an “inner layer circuit board”. Moreover, when manufacturing a printed wiring board, the intermediate product in which an insulating layer and / or a conductor layer should be further formed is also included in the “inner layer substrate” in the present invention. When the printed wiring board is a circuit board with a built-in component, an inner layer board with a built-in component can be used.

  Lamination | stacking of an inner layer board | substrate and the resin sheet with a support body can be performed by heat-pressing the 2nd resin composition layer of a resin sheet layer to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the resin sheet with a support to the inner layer substrate (hereinafter also referred to as “heat-pressing member”) include a heated metal plate (SUS mirror plate, etc.) or a metal roll (SUS roll). It is done. It is not necessary to press the thermocompression bonding member directly on the resin sheet with the support, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet with the support sufficiently follows the surface irregularities of the inner substrate. preferable.

  Lamination of the inner layer substrate and the resin sheet with the support may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurizing laminator.

  After lamination, the laminated resin sheet with the support may be smoothed by pressing the thermocompression bonding member from the support side under normal pressure (under atmospheric pressure), for example. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

  The support may be removed between step (I) and step (II), or may be removed after step (II).

  In step (II), the resin sheet layer is thermoset to form an insulating layer. The thermosetting conditions for the resin sheet layer are not particularly limited, and the conditions normally employed when forming the insulating layer of the printed wiring board may be used.

  For example, the thermosetting conditions of the resin sheet layer vary depending on the types of the first and second resin compositions, but the curing temperature is preferably 120 ° C to 240 ° C, more preferably 150 ° C to 220 ° C, and even more preferably. Is 170 ° C to 210 ° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

  Before the resin sheet layer is thermally cured, the resin sheet layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin sheet layer, the resin sheet layer is kept at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 115 ° C. or lower, more preferably 70 ° C. or higher and 110 ° 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, and further preferably 15 minutes to 100 minutes).

  When manufacturing a printed wiring board, you may further implement (III) the process of drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used for manufacturing printed wiring boards. In addition, when removing a support body after process (II), removal of this support body is performed between process (II) and process (III), between process (III) and process (IV), or process ( It may be carried out between IV) and step (V). Moreover, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

  Step (III) is a step of making a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the first and second resin compositions used for forming the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

  Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear is also removed. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 100 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan. Moreover, as a neutralization liquid used for a roughening process, acidic aqueous solution is preferable, As a commercial item, "Reduction Solution Securigant P" by Atotech Japan is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 1 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 120 nm or less, more preferably 110 nm or less, and further preferably 100 nm or less. Although it does not specifically limit about a minimum, Preferably it is 30 nm or more, More preferably, it is 40 nm or more, More preferably, it is 50 nm or more. The arithmetic average roughness (Ra) of the insulating layer surface can be measured using a non-contact type surface roughness meter.

  Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer 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. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

  The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer 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.

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, generally it is 3 micrometers-35 micrometers, Preferably it is 5 micrometers-30 micrometers.

  In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full additive method. It is preferable to form by a method. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

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

[Semiconductor device]
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

  Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction location” is a “location where an electrical signal is transmitted on a 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 is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the wire bonding mounting method, the flip chip mounting method, and the bumpless buildup layer are used. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. In the following description, “parts” and “%” representing amounts mean “parts by mass” and “% by mass”, respectively, unless otherwise specified. Further, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

<Measurement of average particle size of inorganic filler>
100 mg of the inorganic filler and 10 g of methyl ethyl ketone were weighed in a vial and dispersed with an ultrasonic wave for 10 minutes. Using a laser diffraction particle size distribution measuring device (“LA-960” manufactured by Horiba, Ltd.), the light source wavelengths used were blue and red, and the particle size distribution of the inorganic filler was measured on a volume basis by a flow cell method. From the obtained particle size distribution, the average particle size of the inorganic filler was calculated as the median diameter.

<Measurement of specific surface area of inorganic filler>
Using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.), the sample surface is adsorbed with nitrogen gas, and the specific surface area is calculated using the BET multipoint method. Was measured.

<Used inorganic filler>
Inorganic filler 1: N-phenyl-3-aminopropyltrimethoxysilane (100 parts by weight of spherical silica ("Advertex" SC2500SQ ", average particle size 0.5 µm, specific surface area 5.9 m ² / g)) Surface treated with 1 part KBM573) manufactured by Shin-Etsu Chemical Co., Ltd.

Inorganic filler 2: N-phenyl-3-aminopropyltri to 100 parts of spherical silica (“UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.1 μm, specific surface area 30.7 m ² / g) Surface treated with 2 parts of methoxysilane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.).

<Synthesis of Elastomer A>
In a reaction vessel, 50 g of G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average molecular weight = 5167 (GPC method), hydroxyl group equivalent = 1798 g / eq., Solid content: 100% by mass: Nippon Soda Co., Ltd.) and Ipsol 150 (Aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) 23.5 g and dibutyltin laurate 0.005 g were mixed and dissolved uniformly. When it became uniform, the temperature was raised to 50 ° C., and while further stirring, 7.4 g of isophorone diisocyanate (isocyanate group equivalent = 111.15 g / eq.) Was added, and the reaction was carried out for about 3 hours. Next, after cooling the reaction product to room temperature, 24.2 g of a cresol novolac type phenolic resin (hydroxyl equivalent 117, “KA-1160” manufactured by DIC) was added thereto, and the temperature was raised to 150 ° C. while stirring. The reaction was carried out for about 12 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. The confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a 100 mesh filter cloth to obtain elastomer A.
The properties of the elastomer A were as follows: the viscosity was 3.9 Pa · s (25 ° C., E-type viscometer), the solid content was 50% by mass, the number average molecular weight was 4890, and the content of the polybutadiene structure portion was 61.3% by mass. It was.

<Preparation of Resin Composition 1>
4 parts of dicyclopentadiene type epoxy resin (“HP-7200” manufactured by DIC, epoxy equivalent of about 285), 4 parts of bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation, about 238 of epoxy equivalent), 30 parts of elastomer A Was dissolved in a mixed solvent of 5 parts of solvent naphtha and 10 parts of methyl ethyl ketone with stirring. After cooling to room temperature, 5 parts of a reactive flame retardant (hydroxyl equivalent 249, “SPH-100” manufactured by Otsuka Chemical Co., Ltd., phosphorus content 12.5%), 12 parts of inorganic filler 1, imidazole series After mixing 0.15 part of a curing accelerator (Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole (1B2PZ)) and uniformly dispersing with a high-speed rotary mixer, use a cartridge filter ("SHP020" manufactured by ROKITECHNO). The resin composition 1 was prepared by filtration.

<Preparation of resin composition 2>
6 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 4 parts of bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation, about 238 equivalent of epoxy), phenoxy resin (Mitsubishi Chemical Corporation) 10 parts of “YX7553BH30” manufactured by Cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution having a solid content of 30% by mass was dissolved in a mixed solvent of 5 parts of solvent naphtha and 10 parts of methyl ethyl ketone with stirring. After cooling to room temperature, 5 parts of a triazine skeleton-containing phenol novolac-based curing agent (“LA-7054” manufactured by DIC, a hydroxyl group equivalent of about 125, a methyl ethyl ketone solution with a solid content of 60%), a naphthol-based curing agent (Nippon Steel) "SN395" manufactured by Sumikin Chemical Co., Ltd., 2 parts of hydroxyl equivalent 107), 18 parts of inorganic filler 1 and 0.1 part of amine curing accelerator (4-dimethylaminopyridine (DMAP)) are mixed and mixed with a high-speed rotary mixer. After being uniformly dispersed, a resin filter 2 was prepared by filtering with a cartridge filter (“SHP020” manufactured by ROKITECHNO).

<Preparation of resin composition 3>
In the resin composition 2, 5 parts of a triazine skeleton-containing phenol novolak-based curing agent (“LA-7054” manufactured by DIC, a methyl ethyl ketone solution having a hydroxyl group equivalent of about 125 and a solid content of 60%) was added to an active ester-based curing agent (manufactured by DIC). 5 parts of “HPC-8000L-65T”, an active group equivalent of about 223, a 65% by mass nonvolatile component MEK solution). Resin composition 3 was prepared in the same manner as resin composition 2 except for the above items.

<Preparation of resin composition 4>
In the resin composition 2, 18 parts of the inorganic filler 1 was changed to 10 parts of the inorganic filler 2. Resin composition 4 was prepared in the same manner as resin composition 2 except for the above items.

<Preparation of resin composition 5>
In resin composition 4, 5 parts of a triazine skeleton-containing phenol novolak-based curing agent (“LA-7054” manufactured by DIC, a methyl ethyl ketone solution having a hydroxyl group equivalent of about 125 and a solid content of 60%) was added to an active ester curing agent (manufactured by DIC). 5 parts of “HPC-8000L-65T”, an active group equivalent of about 220, and a 65% by mass nonvolatile component (MEK solution). A resin composition 5 was prepared in the same manner as the resin composition 4 except the above matters.

[Examples 1 to 4]
<Preparation of resin sheet with support>
As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., “release PET”) subjected to release treatment with an alkyd resin release agent (“AL-5” manufactured by Lintec) Prepared.

  Each second resin composition described in the following table was uniformly applied on a release PET with a die coater so that the thickness of the second resin composition layer after drying was 10 μm. A second resin composition layer was obtained on the release PET by drying at 2 ° C. for 2 minutes. Next, a rough surface of a polypropylene film (“Alphan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film is applied to the surface of the second resin composition layer that is not bonded to the release PET. The resin composition layer was laminated so as to be bonded. Thereby, the resin sheet A which consists of order of mold release PET (support body), the 2nd resin composition layer, and a protective film was obtained.

  Release PET was prepared as a support.

  Each first resin composition described in the following table was uniformly coated on a release PET with a die coater so that the thickness of the first resin composition layer after drying was 30 μm, and 70 ° C. to 95 ° C. The first resin composition layer was obtained on the release PET by drying at 0 ° C. for 2 minutes. Next, a rough surface of a polypropylene film (“Alphan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) is used as a protective film on the surface not bonded to the support of the first resin composition layer. It laminated | stacked so that it might join with the resin composition layer. Thereby, the resin sheet B which consists of order of mold release PET (support body), a 1st resin composition layer, and a protective film was obtained.

  The protective films of the resin sheet A and the resin sheet B were peeled off, laminated under the same conditions as the following lamination conditions, and the support of the resin sheet B was peeled off to produce a resin sheet with a support.

[Comparative Examples 1-2]
Resin sheets A and B prepared in Example 1 were prepared as resin sheets with a support in Comparative Examples 1 and 2, respectively.

<Measurement of thickness of first and second resin composition layers>
The thicknesses of the first and second resin composition layers are measured using a contact-type film thickness meter (MCD-25MJ, manufactured by Mitutoyo Corporation), and the thickness of the first resin composition layer (t1 (μm)) and The ratio (t1 / t2) to the thickness (t2 (μm)) of the second resin composition layer was measured.

<Measurement of elastic modulus and elongation>
(1) Preparation of cured product for evaluation The untreated surface of the release PET film (“501010” manufactured by Lintec Corporation, thickness 38 μm, 240 mm square) is a glass cloth base epoxy resin double-sided copper-clad laminate (Matsushita Electric Works “ R5715ES ”, 0.7mm thick, 255mm square) is placed on a glass cloth base epoxy resin double-sided copper-clad laminate, and the four sides of the release PET film are fixed with polyimide adhesive tape (width 10mm) did.

  Each of the resin sheets with a support (167 × 107 mm square) prepared in the examples and comparative examples is subjected to a second process using a batch-type vacuum pressurizing laminator (manufactured by Nikko Materials, 2-stage buildup laminator, CVP700). The resin composition layer was laminated at the center so as to contact the release surface of the release PET film. The laminating process was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

  Next, the support was peeled off, and the resin sheet layer was thermally cured at 180 ° C. for 90 minutes.

  After thermosetting, the polyimide adhesive tape was peeled off, and the cured product layer was removed from the glass cloth base epoxy resin double-sided copper-clad laminate. Further, the release PET film was peeled from the cured product layer to obtain a sheet-like cured product (evaluated cured product).

(2) Measurement of elastic modulus and elongation (breaking elongation) The cured product for evaluation was cut into dumbbell-shaped No. 1 to obtain a test piece. The test piece was subjected to a tensile test of the cured product for evaluation using a Tensilon universal testing machine (manufactured by A & D) in accordance with Japanese Industrial Standard (JIS K7127). The elongation at break was measured. This operation was performed 3 times, and the average value was shown in the table.

  The elastic modulus and elongation of the first cured product layer were measured by changing each of the resin sheets with a support to each resin sheet A. Further, the elastic modulus and elongation of the second cured product layer were measured by changing the resin sheet with each support to the resin sheet B.

<Measurement of via hole dimensions, haloing distance, and haloing ratio after roughening>
-Production of evaluation substrate A-
(1) Copper-clad laminate As a copper-clad laminate, a glass cloth base epoxy resin double-sided copper-clad laminate with copper foil layers laminated on both sides (copper foil thickness 3 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Company, Inc.) “HL832 NSF LCA” (255 × 340 mm size) was prepared.

(2) Lamination of resin sheet with support Each resin sheet with a support prepared in the examples (the comparative example is resin sheet A or resin sheet B) is a batch type vacuum pressure laminator (manufactured by Nikko Materials, Inc., 2 A stage buildup laminator (CVP700) was used to laminate on both sides of the copper clad laminate so that the second resin composition layer was in contact with the copper clad laminate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and pressing for 45 seconds at 130 ° C. and a pressure of 0.74 MPa. Next, hot pressing was performed at 120 ° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of resin sheet layer The copper-clad laminate on which the resin sheet layer is laminated is placed in an oven at 100 ° C for 30 minutes, then transferred to an oven at 180 ° C and then thermoset for 30 minutes for insulation. A layer was formed. This is a cured substrate A.

(4) Laser via processing (formation of via holes)
Using a CO ₂ laser processing machine “605GTWIII (-P)” manufactured by Mitsubishi Electric Corporation, a laser was irradiated from above the support to form a via hole having a top diameter (diameter) of 50 μm in the insulating layer. The laser irradiation conditions were a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ / shot, a shot number of 2, and a burst mode (10 kHz).

(5) Roughening treatment After peeling off the support of the cured substrate A in which a via hole was formed in the insulating layer, a desmear treatment as a roughening treatment was performed. In addition, as a desmear process, the following wet desmear process was implemented.

Wet desmear treatment Swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C for 10 minutes, then oxidizing solution ("Concentrate Compact CP ”, aqueous solution with potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80 ° C. for 20 minutes, and finally neutralization solution (“ Reduction Solution Securigant P ”manufactured by Atotech Japan Co., sulfuric acid In aqueous solution) at 40 ° C. for 5 minutes and then dried at 80 ° C. for 15 minutes. This is a roughened substrate A.

<Measurement of via diameter after desmear treatment>
The roughened substrate A was subjected to cross-sectional observation using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology). Specifically, the cross section of the laser via in the vertical direction was cut out by FIB (focused ion beam), and the via hole diameter after desmear treatment was measured from the cross-sectional SEM image. For each sample, the via top diameter after desmearing treatment was measured from five randomly selected cross-sectional SEM images, and the average value was defined as the via top diameter Lt (μm), which is shown in the table below. Similarly, the bottom diameter Lb of the via hole after the desmear treatment was measured.

<Measurement of halo distance after roughening>
In the image observed by SEM, a gap formed by peeling the insulating layer from the copper foil layer of the inner substrate was seen continuously from the edge of the via bottom. Therefore, from the observed image, the distance from the center of the via bottom to the edge of the via bottom (corresponding to the inner radius of the gap) r3, and the distance from the center of the via bottom to the far end of the gap (gap R4) was measured, and the difference r4-r3 between the distance r3 and the distance r4 was calculated as a haloing distance from the edge of the via bottom at the measurement point.

  The above measurements were made at 5 randomly selected via holes. And the average of the measured value of the measured haloing distance of five via holes was adopted as the haloing distance Wb from the edge of the via bottom of the sample.

  The roughened substrate A was observed with an optical microscope (“KH8700” manufactured by Hilox). Specifically, the insulating layer around the via hole was observed from above the roughened substrate A using an optical microscope (CCD). This observation was performed with the optical microscope focused on the via top. As a result of observation, a donut-shaped haloing portion in which the insulating layer was turned white was continuously observed around the via hole from the edge of the via top of the via hole. Therefore, from the observed image, the radius of the via top of the via hole (corresponding to the inner peripheral radius of the haloing portion) r1 and the outer peripheral radius r2 of the haloing portion are measured, and the difference r2 between the radius r1 and the radius r2 -R1 was calculated as the haloing distance from the edge of the via top of the measurement point.

  The above measurements were made at 5 randomly selected via holes. And the average of the measured value of the measured haloing distance of five via holes was adopted as the haloing distance Wt from the edge of the via top of the sample.

  In the table below, the haloing ratio Ht is the ratio of the haloing distance Wt from the edge of the via top after the roughening process to the radius (Lt / 2) of the via top of the via hole after the roughening process (“Wt / (Lt / 2) ”. If this haloing ratio Ht is 35% or less, it is determined as“ ◯ ”, and if the haloing ratio Ht is greater than 35%, it is determined as“ x ”.

  In the table below, the haloing ratio Hb is the ratio of the haloing distance Wb from the edge of the via top after the roughening process to the radius (Lb / 2) of the via top of the via hole after the roughening process ( It represents “Wb / (Lb / 2).” When this haloing ratio Hb was 35% or less, it was judged as “◯”, and when the haloing ratio Hb was larger than 35%, it was judged as “x”.

<Evaluation of flexibility (MIT folding resistance)>
The resin sheets with a support prepared in Examples and Comparative Examples were cured at 190 ° C. for 90 minutes, peeled off from the support, and then cut using a cutter to prepare five 110 mm × 15 mm samples for evaluation. . Using a MIT folding fatigue testing machine (“MIT-DA” manufactured by Toyo Seiki Seisakusho Co., Ltd.), in accordance with JIS C-5016, a load of 2.5 N, a bending angle of 135 degrees, a bending speed of 175 times / , The MIT folding resistance test was performed with the curvature radius set to 1 mm, and the number of foldings was measured. The average value of the folding endurance of five evaluation samples was determined. For MIT folding resistance, the case where the folding endurance was less than 200 was evaluated as “x”, and the case where it was 200 or more was evaluated as “◯”.

  In Examples 1 to 4, the ratio (t3 / t4) of the thickness t3 (μm) of the first cured product layer and the thickness t4 (μm) of the second cured product layer is <the first and second resin compositions. Measurement of the thickness of the layer> Measured in the same manner as in the column, it was the same as t1 / t2.

  In Examples 1 to 4, even if each resin composition layer does not contain the components (C) to (F), the results are the same as in the above examples, although there is a difference in the degree. I have confirmed.

DESCRIPTION OF SYMBOLS 1 Resin sheet | seat with support body 2 Resin sheet layer 3 Support body 10 1st resin composition layer 10 '1st hardened | cured material layer 20 2nd resin composition layer 20' 2nd hardened | cured material layer 100 Insulating layer 100U Conductor Surface of insulating layer opposite to layer 110 Via hole 120 Via bottom 120C Center of via bottom 130 Via top 140 Discolored portion 150 Edge of via bottom of via hole 160 Gap portion 170 Edge of outer periphery side of gap portion 180 Edge of via top 190 Color change portion 200 Inner layer substrate 210 Conductor layer Lb Bottom diameter of via hole Lt Top diameter of via hole Wb Haloing distance from edge of via bottom Wt Haloing distance from edge of via top

Claims (7)

A resin sheet with a support comprising a support and a resin sheet layer provided on the support,
The resin sheet layer includes a first resin composition layer formed from the first resin composition and a second resin composition formed from a second resin composition having a composition different from that of the first resin composition. Having a physical layer in this order from the support side,
The first resin composition and the second resin composition each independently contain a thermosetting resin and an inorganic filler,
The elastic modulus at 23 ° C. of the first cured product layer obtained by thermosetting the first resin composition layer at 180 ° C. for 90 minutes is 0.001 GPa or more and 0.1 GPa or less,
The elastic modulus at 23 ° C. of the second cured product layer obtained by thermosetting the second resin composition layer at 180 ° C. for 90 minutes is 3 GPa or more and 10 GPa or less,
Resin with support, wherein t1 / t2 is 1 or more and 10 or less, where t1 (μm) is the thickness of the first resin composition layer and t2 (μm) is the thickness of the second resin composition layer Sheet.   The resin sheet with a support according to claim 1, wherein the cured product obtained by thermally curing the resin sheet layer at 180 ° C for 90 minutes has an elastic modulus at 23 ° C of 0.01 GPa or more and 4 GPa or less.   The resin sheet with a support according to claim 1 or 2, wherein an elongation at 23 ° C of a cured product obtained by thermally curing the resin sheet layer at 180 ° C for 90 minutes is 10% or more and 50% or less.   The resin sheet with a support according to any one of claims 1 to 3, wherein the first resin composition contains an elastomer.   The resin sheet with a support according to any one of claims 1 to 4, wherein the elongation of the first cured product layer is 40% or more.   When the content (mass%) of the inorganic filler in the first resin composition is B1, and the content (mass%) of the inorganic filler in the second resin composition is B2, B2 / B1 is The resin sheet with a support according to any one of claims 1 to 5, which is 0.1 or more and 10 or less. The 1st hardened | cured material layer formed with the hardened | cured material of the 1st resin composition, and the 2nd resin composition in which a composition differs from the 1st resin composition formed on this 1st hardened | cured material layer A second cured product layer formed by a cured product of the product,
The first resin composition and the second resin composition each independently contain an epoxy resin, a curing agent and an inorganic filler,
The elastic modulus at 23 ° C. of the first cured product layer is 0.001 GPa or more and 0.1 GPa or less,
The elastic modulus at 23 ° C. of the second cured product layer is 3 GPa or more and 10 GPa or less,
Hardened | cured material whose t3 / t4 is 5-10, when the thickness of a 1st hardened | cured material layer is set to t3 (micrometer) and the thickness of a 2nd hardened | cured material layer is set to t4 (micrometer).

Images