JP2017179055A - Thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin that offers an insulating layer being bendable and having excellent dimensional accuracy and reflow resistance in the production of a wiring board comprising an embedded wire layer.SOLUTION: A thermosetting resin comprises (a) epoxy resin, (b) a compound having an optionally hydrogenated butadiene structure and a phenolic hydroxyl group, (c) phenoxy resin, and (d) inorganic filler. A part or all of the (a) epoxy resin and/or (c) phenoxy resin is a compound having a flexible structure selected from a C2 to 20 alkylene structure and a C2 to 20 alkylene structure having an ether linkage. The (d) inorganic filler is 30 mass% or more when a nonvolatile component of the resin composition is 100 mass%. The elastic modulus, breaking strength, and fracture elongation of the cured product at 23°C are 1 Gpa or more and 6 Gpa or less, 10 Mpa or more, and 6% or more, respectively.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin composition. Furthermore, the present invention relates to an adhesive film having a thermosetting resin composition layer, a method for manufacturing a wiring board using the adhesive film, a wiring board, and a semiconductor device.

  As a method of manufacturing a wiring board (printed wiring board), a build-up method in which circuit-formed conductor layers and insulating layers are alternately stacked is widely used, and the insulating layer is formed by curing a resin composition. It is known (see, for example, Patent Document 1).

JP2015-82535A

  In recent years, electronic devices have been made lighter, thinner, and smaller. Accordingly, there is a demand for a flexible wiring board that can be folded and stored in an electronic device. Further, in order to make the wiring board thinner, a wiring board having an embedded wiring layer is required.

  As an insulating layer used for a wiring board having an embedded wiring layer, the mismatch of the average linear thermal expansion coefficient (coefficient of thermal expansion: CTE) between wiring layers and components is reduced. Therefore, a hard material highly filled with an inorganic filler has been used. However, since it is a hard material, it could not be bent. On the other hand, when a soft material is used for bending, there are problems in dimensional accuracy and reflow resistance.

  An object of the present invention is to solve the above-described problems, and when manufacturing a wiring board having an embedded wiring layer, it is possible to provide a foldable insulating layer with good dimensional accuracy and reflow resistance. An object of the present invention is to provide a thermosetting thermosetting resin, an adhesive film, a method of manufacturing a wiring board using the same, a wiring board, and a semiconductor device.

That is, the present invention includes the following contents.
[1] A thermosetting resin composition comprising (a) an epoxy resin, (b) a compound having an optionally hydrogenated butadiene structure and a phenolic hydroxyl group, (c) a phenoxy resin, and (d) an inorganic filler. A thing,
(A) A part or all of the epoxy resin and / or (c) phenoxy resin has a flexible structure selected from an alkylene structure having 2 to 20 carbon atoms and an alkylene structure having an ether bond having 2 to 20 carbon atoms. A compound,
(D) The inorganic filler is 30% by mass or more when the nonvolatile component of the resin composition is 100% by mass,
Thermosetting resin composition having a modulus of elasticity, breaking strength, and breaking elongation at 23 ° C. of 1 Gpa or more and 6 Gpa or less, 10 Mpa or more, and 6% or more, respectively, at 23 ° C. of a cured product obtained by thermosetting a thermosetting resin composition. object.
[2] The thermosetting resin composition according to [1], wherein the compound having a flexible structure is a compound having an alkylene structure having an ether bond having 3 to 15 carbon atoms.
[3] The content of the compound having a flexible structure is 2% by mass to 50% by mass when the nonvolatile component in the thermosetting resin composition is 100% by mass, described in [1] or [2] Resin composition.
[4] (b) The content of the compound having a butadiene structure and a phenolic hydroxyl group which may be hydrogenated is 8% by mass to 50% when the nonvolatile component in the thermosetting resin composition is 100% by mass. The resin composition according to any one of [1] to [3], which is mass%.
[5] An adhesive film comprising a support and a layer of the thermosetting resin composition according to any one of [1] to [4].
[6] (1) A step of preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate;
(2) An adhesive film including a thermosetting resin composition layer is laminated on a substrate with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, and is thermally cured to form an insulating layer. The process of
(3) a step of interconnecting the wiring layers, and (4) a step of removing the substrate,
The adhesive film as described in [5] used for the manufacturing method of a wiring board containing this.
[7] Step (3) is at least one of a step of forming a via hole in the insulating layer to form a conductor layer and a step of polishing or grinding the insulating layer to expose the wiring layer. ] The adhesive film of description.
[8] Adhesive film [9] (1) Base material used for manufacture of a wiring board provided with an insulating layer and an embedded wiring layer embedded in the insulating layer, and the base material Preparing a substrate with a wiring layer having a wiring layer provided on at least one surface;
(2) The adhesive film according to any one of [5] to [8] is laminated on a substrate with a wiring layer and thermally cured so that the wiring layer is embedded in the thermosetting resin composition layer. Forming an insulating layer;
(3) a step of interconnecting the wiring layers; and
(4) removing the substrate;
A method for manufacturing a wiring board, comprising:
[10] Step (3) is at least one of a step of forming a via hole in the insulating layer to form a conductor layer, and a step of polishing or grinding the insulating layer to expose the wiring layer. ] Method.
[11] The method according to [9] or [10], wherein the step (3) is a step of forming a via hole in the insulating layer to form a conductor layer, and is performed by laser irradiation.
[12] The method according to [11], including a step of performing a roughening treatment before forming the conductor layer.
[13] The method according to any one of [9] to [12], wherein the wiring board is a flexible wiring board.
[14] The method according to any one of [9] to [13], wherein the minimum pitch of the wiring pattern is 40 μm or less.
[15] A wiring board comprising: an insulating layer that is a cured product of the thermosetting resin composition layer of the adhesive film according to any one of [5] to [8]; and an embedded wiring layer embedded in the insulating layer. .
[16] The wiring board according to [15], which is a flexible wiring board.
[17] The wiring board according to [15] or [16], wherein the insulating layer has a thickness of 2 μm or more.
[18] A semiconductor device comprising the wiring board according to any one of [15] to [17].

  According to the present invention, when manufacturing a wiring board having an embedded wiring layer, a thermosetting thermosetting resin, an adhesive film, and a foldable insulating layer that have good dimensional accuracy and reflow resistance and that can be bent. A wiring board manufacturing method, a wiring board, and a semiconductor device can be provided.

FIG. 1 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board. FIG. 2 is a schematic cross-sectional view for explaining a manufacturing process of the wiring board. FIG. 3 is a schematic cross-sectional view for explaining a manufacturing process of the wiring board. FIG. 4 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 5 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 6 is a schematic cross-sectional view for explaining a manufacturing process of the wiring board. FIG. 7 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 8 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 9 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 10 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 11 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 12 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 13 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 14 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 15 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 16 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 17 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 18 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 19 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 20 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 21 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 22 is a schematic cross-sectional view for explaining a wiring board. FIG. 23 is a schematic cross-sectional view for explaining a wiring board.

  Hereinafter, the thermosetting resin composition, the adhesive film, the method for producing a wiring board, the wiring board, and the semiconductor device of the present invention will be described in detail.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention comprises (a) an epoxy resin, (b) an optionally hydrogenated butadiene structure and a compound having a phenolic hydroxyl group, (c) a phenoxy resin, and (d) an inorganic filler. Including. The thermosetting resin composition may further contain additives such as (e) a curing agent, (f) a curing accelerator, (g) a flame retardant, and (h) an organic filler, as necessary. Although details will be described later, when the wiring board is manufactured, the wiring layer is embedded in the thermosetting resin composition layer, thereby forming an embedded wiring layer. Therefore, a part or all of (a) epoxy resin and / or (c) phenoxy resin is selected from an alkylene structure having 2 to 20 carbon atoms and an alkylene structure having an ether bond having 2 to 20 carbon atoms. (D) the inorganic filler is 30% by mass or more when the nonvolatile component of the resin composition is 100% by mass, and is a cured product obtained by thermosetting the thermosetting resin composition The elastic modulus, breaking strength, and breaking elongation at 23 ° C. are 1 Gpa or more and 6 Gpa or less, 10 Mpa or more, and 6% or more, respectively.

-(A) Epoxy resin-
The epoxy resin that can be used in the thermosetting resin composition of the present invention is not particularly limited as long as it is a compound having an epoxy group in the molecule. For example, a compound having a flexible structure selected from an alkylene structure having 2 to 20 carbon atoms and an alkylene structure having an ether bond having 2 to 20 carbon atoms (hereinafter also referred to as a flexible structure-containing compound), bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, 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, glycidyl amine type epoxy resin having aromatic structure, glycidyl ester having aromatic structure Type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having aromatic structure, epoxy resin having butadiene structure having aromatic structure, alicyclic epoxy resin having aromatic structure , Heterocyclic epoxy resin, spiro ring-containing epoxy resin having aromatic structure, cyclohexanedimethanol type epoxy resin having aromatic structure, naphthylene ether type epoxy resin, trimethylol type epoxy resin having aromatic structure, aromatic Examples thereof include a tetraphenylethane type epoxy resin having a structure. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it has two or more epoxy groups in one molecule, and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule, It is preferable to contain a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured product of the resin composition is also improved.

  Examples of 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 having an aromatic structure, and glycidyl amine type epoxy resins having an aromatic structure. Phenol novolac type epoxy resin, alicyclic epoxy resin having ester skeleton having aromatic structure, cyclohexanedimethanol type epoxy resin having aromatic structure and epoxy resin having butadiene structure having aromatic structure are preferable, and bisphenol A Type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin are more preferable, bisphenol A type epoxy resin, bisphenol F type epoxy Shi resin is more preferred. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US”, “jER828EL” (bisphenol A) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "630", "630LSD" (glycidylamine type epoxy) Resin), “ZX1059” (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “EX-721” (glycidyl ester type epoxy resin manufactured by Nagase ChemteX Corporation) ), Daicel Corporation "CELLOXIDE 2021P" (an alicyclic epoxy resin having an ester skeleton) of Nippon Steel Chemical Co., Ltd. "ZX1658", "ZX1658GS" (liquid 1,4 glycidyl cyclohexane) and the like. These may be used alone or in combination of two or more.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin having an aromatic structure, 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, tetraphenylethane type epoxy resin are preferable, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin More preferably, a naphthalene type tetrafunctional epoxy resin and a naphthylene ether type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” manufactured by DIC Corporation. "(Cresol novolac type epoxy resin)", "N-695" (Cresol novolac type epoxy resin), "HP-7200" (Dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA7311 ”,“ EXA7311-G3 ”,“ EXA7311-G4 ”,“ EXA7311-G4S ”,“ HP6000 ”(naphthylene ether type epoxy resin),“ EPPN-502H ”(trisphenol type epoxy) manufactured by Nippon Kayaku Co., Ltd. Resin), "NC7000L" (naphthol novolac type epoxy) Fat), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ESN485” (naphthol novolak type) Epoxy resin), “YX4000H”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin), Osaka Gas Chemical (manufactured by Mitsubishi Chemical Corporation) “PG-100”, “CG-500” manufactured by Mitsubishi Chemical Corporation, “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “jER1010” (solid bisphenol A type epoxy manufactured by Mitsubishi Chemical Corporation) Resin), "jER1031S" (tetraphenyl) Tan epoxy resin) and the like.

  The liquid epoxy resin is preferably an aromatic epoxy resin having two or more epoxy groups in one molecule and a liquid at a temperature of 20 ° C. The solid epoxy resin has three or more epoxy groups in one molecule. And an aromatic epoxy resin that is solid at a temperature of 20 ° C. is preferable. In addition, the aromatic epoxy resin as used in the field of this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator.

  When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:20 by mass ratio. preferable. By making the quantitative ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is provided when used in the form of an adhesive film, ii) when used in the form of an adhesive film Sufficient flexibility can be obtained, handling properties can be improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii), the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.3 to 1:10 by mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 9 is even more preferable.

  The content of the epoxy resin in the thermosetting resin composition is preferably 4% by mass or more, more preferably 5% by mass or more, and still more preferably, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. It is 6 mass% or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 50 mass% or less, More preferably, it is 40 mass% or less.

  In addition, in this invention, content of each component in a thermosetting resin composition is a value when the non-volatile component in a thermosetting resin composition is 100 mass% unless there is separate description.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

-Compound having a flexible structure selected from an alkylene structure having 2 to 20 carbon atoms and an alkylene structure having an ether bond having 2 to 20 carbon atoms-
In the thermosetting resin of the present invention, (a) the epoxy resin and / or (c) part or all of the phenoxy resin has an alkylene structure having 2 to 20 carbon atoms and an ether bond having 2 to 20 carbon atoms. It is a compound having a flexible structure selected from alkylene structures.

The alkylene structure having 2 to 20 carbon atoms is preferably an alkylene structure having 4 to 15 carbon atoms, and more preferably an alkylene structure having 4 to 10 carbon atoms. The alkylene group may be linear, branched or cyclic, but a linear or branched alkylene structure is preferred. Examples of such an alkylene structure include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, Examples include a tetradecylene group, a pentadecylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a decahydronaphthalene group, a norbornanylene group, an adamantanilene group, a methylene group, an ethylene group, a propylene group , Butylene group, pentylene group, hexylene group, halogen atom, alkyl group, alkoxy group, alkylidene group, amino group, silyl group, acyl group, acyloxy group, carboxy group, sulfo group, cyano group, nitro group, hydroxy Group, mercap Group, which may have a substituent such as an oxo group. Here, the number of carbon atoms does not include the number of carbon atoms of the substituent.

Examples of the alkylene structure having an ether bond having 2 to 20 carbon atoms include an oxyalkylene structure, an alkyleneoxy structure, an oxyalkyleneoxy structure, an alkyleneoxyalkylene structure, and an alkyleneoxyalkyleneoxyalkylene structure. The alkylene structure having an ether bond having 2 to 20 carbon atoms is preferably an alkylene structure having an ether bond having 2 to 15 carbon atoms, and more preferably an alkylene structure having an ether bond having 3 to 15 carbon atoms. The alkylene structure may be linear, branched or cyclic, but is preferably a linear or branched alkylene structure. Examples of the alkylene structure having an ether bond include oxymethylene group, oxyethylene group, oxypropylene group, oxybutylene group, oxypentylene group, oxyhexylene group, oxyheptylene group, oxyoctylene group, oxynonylene group, oxydecylene. Group, oxyundecylene group, oxide decylene group, oxytridecylene group, oxytetradecylene group, oxypentadecylene group, oxycyclopropylene group, oxycyclobutylene group, oxycyclopentylene group, oxycyclohexylene group, oxy Examples include decahydronaphthanylene group, oxynorbornanylene group, oxyadamantanylene group, oxymethylene group, oxyethylene group, oxypropylene group, oxybutylene group, oxypentylene group, oxyhexylene. Preferably, a halogen atom, alkyl group, alkoxy group, alkylidene group, amino group, silyl group, acyl group, acyloxy group, carboxy group, sulfo group, cyano group, nitro group, hydroxy group, mercapto group, oxo group, etc. It may have a group. Here, the number of carbon atoms does not include the number of carbon atoms of the substituent.

さらに例えば、以下の構造の樹脂（ｈはそれぞれ０〜２０の整数、好ましくは０〜５の整数であり、ｉ、ｊはそれぞれ１〜２０の整数、好ましくは１〜５の整数であり、好ましくは、ｉ＋ｊ＝２〜１０の整数）を挙げることができる。

及び

Specific examples of the flexible structure-containing compound that can be used in the present invention include an epoxy resin having the following structure (k is an integer of 1 to 20, preferably an integer of 1 to 5) or a phenoxy resin that is a polymer thereof. Can be mentioned.

Further, for example, a resin having the following structure (h is an integer of 0-20, preferably 0-5, i and j are each an integer of 1-20, preferably an integer of 1-5, preferably Is an integer of i + j = 2 to 10.

as well as

Further, for example, EXA-4850-150, EXA-4816, and EXA-4822 (epoxy resins containing an alkylene structure having an ether bond) manufactured by DIC Corporation; EP-4000S, EP-4000SS, EP-4003S manufactured by ADEKA; EP-4010S and EP-4011S (epoxy resins containing an alkylene structure having an ether bond); BEO-60E and BPO-20E (epoxy resins containing an alkylene structure having an ether bond); YX7105, YX7110, and YX7400 (epoxy resin containing an alkylene structure having an ether bond), YX7180 (phenoxy resin containing an alkylene structure having an ether bond), and the like are available.

  The content of the flexible structure-containing compound is preferably 2% by mass to 50% by mass when the nonvolatile component in the thermosetting resin composition is 100% by mass. 5 mass% or more is more preferable, 15 mass% or more is further more preferable, and 40 mass% or less is more preferable.

-(B) Compound having butadiene structure and phenolic hydroxyl group which may be hydrogenated-
The thermosetting resin composition of the present invention includes (b) a compound having a butadiene structure which may be hydrogenated and a phenolic hydroxyl group. By including a flexible structure such as a butadiene structure, the elastic modulus of the cured product of the thermosetting resin composition layer is lowered, and a wiring board that can be manufactured using the adhesive film of the present invention can be bent. Can do. A part or all of the butadiene structure may be hydrogenated.

  The component (b) has a phenolic hydroxyl group in order to react with the component (a). The phenolic hydroxyl group means a hydroxyl group present in a form in which a hydrogen atom of an aromatic ring structure is substituted with a hydroxyl group (hydroxy group). (B) The hydroxyl equivalent of a component becomes like this. Preferably it is 100-30000, More preferably, it is 250-20000. The functional group equivalent is the number of grams of resin containing 1 gram equivalent of functional group.

The component (b) is preferably a resin that is at least one selected from a resin having a glass transition temperature of 25 ° C. or lower and a resin that is liquid at 25 ° C.

  The glass transition temperature of the resin having a glass transition temperature (Tg) of 25 ° C. or lower is preferably 20 ° C. or lower, more preferably 15 ° C. or lower. Although the minimum of a glass transition temperature is not specifically limited, Usually, it can be set as -15 degreeC or more. The resin that is liquid at 25 ° C. is preferably a resin that is liquid at 20 ° C. or lower, more preferably a resin that is liquid at 15 ° C. or lower.

  The number average molecular weight (Mn) of the component (b) is preferably 500 to 100,000, more preferably 1000 to 50,000. Here, the number average molecular weight (Mn) of the resin is a number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

As the component (b) of the present invention, a compound using a hydroxy group-terminated polybutadiene, a diisocyanate compound, a tetrabasic acid anhydride and a polyfunctional phenol compound as raw materials can also be used.

The hydroxy group-terminated polybutadiene preferably has a number average molecular weight of 300 to 5,000. As specific examples, for example, G-1000, G-2000, G-3000, GI-1000, GI-2000 (above, manufactured by Nippon Soda Co., Ltd.), R-45EPI (produced by Idemitsu Petrochemical Co., Ltd.) ) And the like. A part or all of the butadiene structure may be hydrogenated.
The diisocyanate compound is a compound having two isocyanate groups in the molecule, and examples thereof include toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate. And diisocyanate.
Tetrabasic acid dianhydride is a compound having two acid anhydride groups in the molecule. For example, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, Naphthalenetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexene-1,2-dicarboxylic anhydride, 3,3′-4,4′-diphenylsulfonetetracarboxylic Acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione Etc.
Examples of the polyfunctional phenol compound include bisphenol A, bisphenol F, bisphenol S, bisphenol AF, biphenol, phenol novolac resin, alkylphenol novolac resin, bisphenol A type novolak resin, dicyclopentadiene structure-containing phenol novolak resin, and triazine structure-containing phenol. Examples include novolak resins, biphenyl skeleton-containing phenol novolak resins, phenyl group-containing phenol novolak resins, terpene-modified phenol resins, and polyvinylphenols. In particular, an alkylphenol novolac resin is preferable.
Details of the compound can be referred to the description of WO 2008/153208, the contents of which are incorporated herein.

  Although content of (b) component in a thermosetting resin composition is not specifically limited, Preferably it is 50 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 11 mass% or less. Further, the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 4% by mass or more.

-(C) Phenoxy resin-
The thermosetting resin composition of the present invention contains (c) a phenoxy resin.

  Examples of the phenoxy resin include, for example, the above-described flexible skeleton-containing compound, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol AF skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, and dicyclopentadiene. And a phenoxy resin having one or more skeletons selected from the group consisting of a skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Corporation, “YL7769BH30”, “YL6794”, “YL7213”, “YL7290”, “YL7482”, “YX7180” and the like.

  The weight average molecular weight in terms of polystyrene of the phenoxy resin is preferably in the range of 8,000 to 200,000, more preferably in the range of 10,000 to 100,000, and still more preferably in the range of 20,000 to 60,000. The polystyrene equivalent weight average molecular weight of the phenoxy resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-converted weight average molecular weight of the phenoxy resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L manufactured by Showa Denko KK as a column. / K-804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as the mobile phase.

  The epoxy equivalent of the phenoxy resin is preferably 6000 to 30000, more preferably 7000 to 20000, and still more preferably 9000 to 15000. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The content of the phenoxy resin is preferably 0.5% by mass to 60% by mass, more preferably 3% by mass to 50% by mass, and further preferably 5% by mass to 40% by mass.

-(D) Inorganic filler-
The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, 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. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle diameter of the inorganic filler is preferably 2 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, and more preferably 0.6 μm or less from the viewpoint of good embedding properties. Although the minimum of this average particle diameter is not specifically limited, Preferably it is 0.01 micrometer or more, More preferably, it is 0.05 micrometer or more, More preferably, it is 0.1 micrometer or more. Examples of commercially available inorganic fillers having such an average particle size include, for example, “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C” manufactured by Admatechs, manufactured by Denki Kagaku Kogyo Co., Ltd. “UFP-30”, “Silfil NSS-3N”, “Silfil NSS-4N”, “Silfil NSS-5N” manufactured by Tokuyama Corporation, “SOC4”, “SOC2”, “SOC1” manufactured by Admatechs Corporation, etc. Is mentioned.

  The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring apparatus, “LA-500” manufactured by Horiba, Ltd. or the like can be used.

  Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents from the viewpoint of improving moisture resistance and dispersibility. It is preferable that it is processed with 1 or more types of surface treating agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (hexamethyldisilazane) manufactured by KK, "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type) Silane coupling agent).

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 more preferable from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the sheet form. preferable.

  The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with 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.

  From the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion, the content of the inorganic filler in the thermosetting resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. It is. The upper limit of the content of the inorganic filler in the thermosetting resin composition is preferably 90% by mass or less, more preferably 75% by mass or less, from the viewpoint of mechanical strength of the insulating layer, particularly elongation.

-(E) Curing agent-
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and Examples thereof include carbodiimide curing agents. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together. The component (e) is preferably at least one selected from a phenolic curing agent, a naphthol curing agent, an active ester curing agent, and a cyanate ester curing agent.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the wiring layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the wiring layer.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495V”, “SN375”, “SN395” manufactured by Nippon Steel & Sumikin Co., Ltd. "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500" manufactured by DIC Corporation Etc.

  From the viewpoint of obtaining an insulating layer having excellent adhesion to the wiring layer, an active ester curing agent is also preferable. Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, 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.

  Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolac, and an active ester compound containing a benzoylated product of a phenol novolac are preferred, Of these, active ester compounds having a naphthalene structure and active ester compounds having a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. 65TM "," EXB-8000L-65TM "(manufactured by DIC Corporation)," EXB9416-70BK "(manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and as an active ester compound containing an acetylated product of phenol novolac “DC808” (manufactured by Mitsubishi Chemical Corporation), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, and “DC808” as an active ester curing agent which is an acetylated product of phenol novolac. "( "YLH1026" (Mitsubishi Chemical Corporation), "YLH1030" (Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi Chemical Corporation) as active ester-based curing agents that are benzoylated phenol novolaks Chemical Co., Ltd.).

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

  Examples of the cyanate ester curing agent 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-dimethyl) Bifunctional cyanate resins such as phenyl) 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, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolac polyfunctional cyanate ester resins), “BA230”, “BA230S75” (bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. For example, a prepolymer partially or wholly converted into a trimer).

  Specific examples of the carbodiimide curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

  The amount ratio of the epoxy resin and the curing agent is preferably a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] in the range of 1: 0.01 to 1: 2. 1: 0.015 to 1: 1.5 are more preferable, and 1: 0.02 to 1: 1 are more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.

  In one embodiment, the thermosetting resin composition includes the aforementioned (a) epoxy resin and (c) a curing agent. The thermosetting resin composition comprises (a) a mixture of a liquid epoxy resin and a solid epoxy resin as an epoxy resin (the mass ratio of liquid epoxy resin: solid epoxy resin is preferably 1: 0.1 to 1:20, More preferably 1: 0.3 to 1:10, and still more preferably 1: 0.6 to 1: 9), and (c) a phenolic curing agent, a naphthol curing agent, an active ester curing agent and It is preferable that each contains at least one selected from the group consisting of cyanate ester-based curing agents.

  Although content of the hardening | curing agent in a thermosetting resin composition is not specifically limited, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less. The lower limit is not particularly limited but is preferably 2% by mass or more.

-(F) Curing accelerator-
Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like. A 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 type.

  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, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

  Although content of the hardening accelerator in a thermosetting resin composition is not specifically limited, 0.01 mass%-3 mass% are preferable when the non-volatile component total amount of an epoxy resin and a hardening | curing agent is 100 mass%.

-(G) Flame retardant-
Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

  Commercially available products may be used as the flame retardant, and examples thereof include “HCA-HQ-HST” manufactured by Sanko Co., Ltd.

  When the thermosetting resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, More preferably, 0.5 mass%-10 mass% are further more preferable.

-(H) Organic filler-
As a thermosetting resin composition, you may use the arbitrary organic fillers which can be used when forming the insulating layer of a printed wiring board, For example, a rubber particle, polyamide microparticles | fine-particles, a silicone particle, etc. are mentioned.

  As the rubber particles, commercially available products may be used. Examples thereof include “EXL-2655” manufactured by Dow Chemical Japan Co., Ltd., “AC3816N” manufactured by Ganz Kasei Co., Ltd., and the like.

  When the thermosetting resin composition contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, and still more preferably. Is 0.3% by mass to 5% by mass, or 0.5% by mass to 3% by mass.

-Other ingredients-
The thermosetting resin composition may further contain other additives as necessary. Examples of such other additives include organic copper compounds, organic zinc compounds, and organic cobalt compounds. Examples thereof include resin compounds such as metal compounds, binders, thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and coloring agents.

  A cured product obtained by thermosetting the thermosetting resin composition layer of the present invention (for example, a cured product obtained by curing at 190 ° C. for 90 minutes (thermosetting resin composition after thermosetting)) is good. The elastic modulus (23 ° C.) is shown. That is, an insulating layer having a good elastic modulus is provided. The elastic modulus at 23 ° C. of the thermosetting resin composition after curing is 1 Gpa or more and 6 Gpa or less, preferably 5 GPa or less. The elastic modulus can be measured according to the method described in << Measurement of Elastic Modulus, Breaking Strength, and Breaking Elongation >> described later.

  A cured product obtained by thermosetting the thermosetting resin composition of the present invention (for example, a cured product obtained by curing at 190 ° C. for 90 minutes (thermosetting resin composition after thermosetting)) has good fracture. Indicates strength (23 ° C.). That is, an insulating layer exhibiting good breaking strength is provided. The breaking strength at 23 ° C. of the cured thermosetting resin composition is 10 MPa or more, preferably 20 MPa or more. The upper limit is not particularly limited, but is 500 MPa or less. The method for measuring the breaking strength can be measured according to the method described in << Measurement of Elastic Modulus, Breaking Strength, and Breaking Elongation> described later.

  A cured product obtained by thermosetting the thermosetting resin composition of the present invention (for example, a cured product obtained by curing at 190 ° C. for 90 minutes (thermosetting resin composition after thermosetting)) is excellently broken. Elongation (23 ° C.) is shown. That is, an insulating layer exhibiting good breaking elongation is provided. The fracture elongation at 23 ° C. of the cured thermosetting resin composition is 6% or more, and preferably 6.5% or more. Although it does not specifically limit about an upper limit, It is 30% mass or less. The method for measuring the breaking elongation can be measured according to the method described in << Measurement of Elastic Modulus, Breaking Strength, and Breaking Elongation> described later.

[Adhesive film]
The adhesive film of the present invention includes a support and a thermosetting resin composition layer. In one embodiment, the adhesive film includes a support and a thermosetting resin composition layer bonded to the support. The thermosetting resin composition layer is composed of a thermosetting resin composition. Hereinafter, each layer which comprises an adhesive film is demonstrated in detail.

<Support>
The adhesive film of the present invention includes a 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 metal foil may be a laminate of a plurality of metal foils.

  The support may be subjected to mat treatment, corona treatment, and antistatic treatment on the surface to be bonded to the thermosetting resin composition 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 thermosetting resin composition 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” 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 T6AM” manufactured by Toray Industries, Inc., 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 thickness of the thermosetting resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and even more preferably 40 μm or less or 20 μm or less from the viewpoint of thinning the wiring board. Although the minimum of the thickness of a thermosetting resin composition layer is not specifically limited, Preferably it is 2 micrometers or more, More preferably, it is 5 micrometers or more.

  The adhesive film may include other layers in addition to the support and the thermosetting resin composition layer. For example, the adhesive film may have a protective film layer to be described later on the outermost surface.

The adhesive film of the present invention comprises (1) a step of preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate, and (2) a thermosetting resin composition. A step of laminating an adhesive film including a layer on a substrate with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer and thermally curing to form an insulating layer; (3) a wiring layer; It is used for the manufacturing method of a wiring board including the process of connecting between layers, and the process of (4) removing a base material.

Moreover, the adhesive film of this invention is used for manufacture of a wiring board provided with an insulating layer and the embedded wiring layer embedded in the insulating layer as another aspect.
<Method for producing adhesive film>
The method for producing the adhesive film is not particularly limited as long as it includes a support and a thermosetting resin composition layer bonded to the support. For the adhesive film, for example, a resin varnish obtained by dissolving a resin composition in an organic solvent is prepared, and this resin varnish is applied onto a support using a die coater or the like, and further dried to form a resin composition layer. Can be manufactured.

  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, 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.

  Drying may be performed 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 thermosetting resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, it is cured by drying at 50 ° C. to 150 ° C. for 3 minutes to 15 minutes. A functional resin composition layer can be formed.

  In the adhesive film, a protective film according to the support can be further laminated on the surface of the thermosetting resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the thermosetting resin composition layer and scratches. The adhesive film can be stored in a roll. When an adhesive film has a protective film, it can be used by peeling off the protective film.

  As the protective film, a film made of a plastic material is preferable.

  Examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”), polyolefins such as polyethylene and polypropylene, Acrylic such as polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. It is done. Among these, polyethylene terephthalate, polyethylene naphthalate, and polypropylene are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  Moreover, as a protective film, you may use the support body with a release layer which has a release layer in the surface joined to a thermosetting resin composition 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” 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 T6AM” manufactured by Toray Industries, Inc., and the like.

  Although it does not specifically limit as thickness of a protective film, 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.

[Method of manufacturing a wiring board]
The method of manufacturing the wiring board of the present invention
(1) preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate;
(2) The step of laminating the adhesive film of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, and thermosetting to form an insulating layer;
(3) including a step of interconnecting wiring layers, and (4) a step of removing the base material.

  The step (3) is not particularly limited as long as the wiring layers can be connected to each other, but a step of forming a via hole in the insulating layer to form a conductor layer, and a step of polishing or grinding the insulating layer to expose the wiring layer It is preferable that it is at least one of these steps.

  Hereinafter, the case where the step (3) is a step of forming a via hole in the insulating layer to form a conductor layer is the first embodiment, and the step (3) is a step of polishing or grinding the insulating layer to expose the wiring layer. A case will be described as a second embodiment.

1. First Embodiment <Step (1)>
Step (1) is a step of preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate. As shown in FIG. 1, the substrate 10 with a wiring layer has a first metal layer 12 and a second metal layer 13 that are part of the substrate 11 on both surfaces of the substrate 11, respectively. The wiring layer 14 is provided on the surface opposite to the surface on the base material 11 side of the two metal layers 13.

  For the details of the step (1), a dry film (photosensitive resist film) is laminated on a substrate, and is exposed and developed under a predetermined condition using a photomask to form a pattern dry film. A wiring layer is formed by electroplating using the developed pattern dry film as a plating mask, and then the pattern dry film is peeled off.

  The material used for the first and second metal layers is not particularly limited. In a preferred embodiment, the first and second metal layers are preferably chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, from the viewpoints of cost, etching, ease of peeling, and the like. More preferred.

  The substrate is not particularly limited as long as the steps (1) to (4) can be performed. Examples of the base material include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate, and a metal layer such as a copper foil is formed on the substrate surface. May be.

  The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, and for example, a dry film such as a novolak resin or an acrylic resin can be used. A commercial item may be used for a dry film, for example, "ALPHO 20A263" by Nikko Materials Co., Ltd. which is a dry film with a PET film can be used. The dry film may be laminated on one surface of the substrate, or may be laminated on both surfaces of the substrate as in the second embodiment described later.

  The conditions for laminating the substrate and the dry film are the same as the conditions for laminating the adhesive film in step (2) described later so as to be embedded in the wiring layer, and the preferred range is also the same.

  After laminating the dry film on the substrate, exposure and development are performed under predetermined conditions using a photomask in order to form a desired pattern on the dry film.

  The line (circuit width) / space (inter-circuit width) ratio of the wiring layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 18/18 μm or less (pitch 36 μm or less), More preferably, it is 15/15 μm or less (pitch 30 μm or less). The lower limit of the line / space ratio of the wiring layer is not particularly limited, but is preferably 0.5 / 0.5 μm or more, more preferably 1/1 μm or more. The pitch need not be the same throughout the wiring layer.

  The minimum pitch of the wiring layer may be 40 μm or less, 36 μm or less, or 30 μm or less.

  After forming the dry film pattern, a wiring layer is formed, and the dry film is peeled off. Here, the wiring layer can be formed by a plating method using a dry film having a desired pattern as a plating mask.

  The conductor material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring 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 wiring 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 nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of wiring 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 thickness of the wiring layer is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 to 20 μm, or 15 μm, although it depends on the desired wiring board design.

  After forming the wiring layer, the dry film is peeled off. Peeling of the dry film can be performed using, for example, an alkaline peeling solution such as a sodium hydroxide solution. If necessary, an unnecessary wiring pattern can be removed by etching or the like to form a desired wiring pattern. The pitch of the wiring layer to be formed is as described above.

<Step (2)>
Step (2) is a step in which the adhesive film of the present invention is laminated on a substrate with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, and is thermally cured to form an insulating layer. is there. Since the thermosetting resin composition layer in the present invention exhibits good embedding properties, it can be laminated without voids when laminated on a substrate with a wiring layer. As shown in FIG. 2, the wiring layer 14 of the substrate with a wiring layer obtained in the above-described step (1) is laminated so as to be embedded in the thermosetting resin composition layer 21 of the adhesive film 20, The thermosetting resin composition layer 21 of the adhesive film 20 is thermoset. The adhesive film 20 is formed by laminating a thermosetting resin composition layer 21 and a support 22 in this order.

  First, as shown in FIG. 2, the thermosetting resin composition layer 21 of the adhesive film 20 is laminated on a substrate with a wiring layer so that the wiring layer 14 is embedded.

  Lamination | stacking of a wiring layer and an adhesive film can be performed by heat-pressing an adhesive film to a wiring layer from the support body side, for example after removing the protective film of an adhesive film. Examples of the member that heat-presses the adhesive film to the wiring layer (hereinafter also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll). In addition, it is preferable not to press the thermocompression bonding member directly on the adhesive film but to press it through an elastic material such as heat resistant rubber so that the adhesive film sufficiently follows the surface irregularities of the wiring layer.

  Lamination of the wiring layer and the adhesive film may be performed by a vacuum laminating method after removing the protective film of the adhesive film. 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 13 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Nikko Materials, a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like. It is done.

  After lamination, the laminated adhesive film may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. 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.

  After a thermosetting resin composition layer is laminated on a substrate with a wiring layer so that the wiring layer is embedded, the thermosetting resin composition layer is thermoset to form an insulating layer. The thermosetting conditions for the thermosetting resin composition layer are not particularly limited, and the conditions normally employed when forming the insulating layer of the wiring board may be used.

  For example, the thermosetting conditions of the thermosetting resin composition layer vary depending on the type of the thermosetting resin composition, but the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, More preferably, it is in the range of 170 ° C. to 200 ° C., and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

  Before thermosetting the thermosetting resin composition layer, the thermosetting resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the thermosetting resin composition layer, thermosetting at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). The conductive resin composition layer may be preheated for 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  The support for the adhesive film may be peeled off after the adhesive film is laminated on the substrate with the wiring layer and thermally cured, or the support may be peeled off before the adhesive film is laminated on the substrate with the wiring layer. Good. Moreover, you may peel a support body before the taxation process process mentioned later.

  The thickness of the insulating layer is the same as the thickness of the thermosetting resin composition layer, and the preferred range is also the same.

<Step (3)>
Step (3) in the first embodiment is a step of forming a via hole in the insulating layer and forming a conductor layer. The following description is divided into a step of forming a via hole in the insulating layer (hereinafter also referred to as “process (3-1)”) and a step of forming a conductor layer (hereinafter also referred to as “process (3-2)”). To do.

-Step (3-1)-
Although formation of a via hole is not specifically limited, Laser irradiation, an etching, mechanical drilling etc. are mentioned, However, It is preferable to carry out by laser irradiation. For details, as shown in an example in FIG. 3, in the step (3), after peeling off the support 22, laser irradiation is performed from the surface side of the adhesive film 20 to penetrate the support 22 and the insulating layer 21 ′. Then, a via hole 31 exposing the wiring layer 14 is formed.

This laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas laser, a YAG laser, an excimer laser or the like as a light source. The laser processing machine which may be used, for example, Via Mechanics Co. CO ₂ laser processing machine "LC-2k212 / 2C", Mitsubishi Electric Corporation of 605GTWIII (-P), manufactured by Panasonic Welding Systems Co., Laser processing machine.

  The conditions for laser irradiation are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.

  The shape of the via hole, that is, the shape of the outline of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular). Hereinafter, the “diameter” of the via hole refers to the diameter (diameter) of the outline of the opening when viewed in the extending direction. In this specification, the top diameter r1 refers to the contour diameter on the insulating layer 21 'side of the via hole, and the bottom diameter r2 refers to the contour diameter on the wiring layer 14 side of the via hole (see FIGS. 3 and 4). .

  The via hole is preferably formed so that the top diameter r1 of the via hole is 120 μm or less, preferably 90 μm or less.

  As shown in FIG. 3, the via hole 31 may be formed so that r1 is larger than r2. The top diameter r1 of the via hole is the same as the bottom diameter r2 of the via hole 31 as shown in FIG. The via hole 31 may be formed so that

  By doing so, the via hole filling property becomes good and the generation of voids can be suppressed, and as a result, the reliability of electrical connection by filled vias described later can be improved.

  After forming the via hole, a so-called desmear process, which is a smear removing process in the via hole, may be performed. When the step (3-2) to be described later is performed by a plating step, for example, wet desmear treatment may be performed on the via hole, and when the step (3-2) is performed by a sputtering step, For example, a dry desmear process such as a plasma treatment process may be performed. Moreover, the desmear process may serve as the roughening process.

  A step of performing a roughening treatment may be included before the step (3-2). The roughening treatment is performed on the via hole and the insulating layer, and the procedure and conditions of the roughening treatment are not particularly limited. For example, a known procedure and conditions usually used in forming an insulating layer of a multilayer printed wiring board are used. Can be adopted. Examples of dry roughening treatment include plasma treatment, etc., and examples of wet roughening treatment include a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order. Is mentioned.

  In the wet roughening treatment, for example, the swelling treatment with the swelling liquid, the roughening treatment with the oxidizing agent, and the neutralization treatment with the neutralization liquid can be performed in this order to roughen the insulating layer 21 ′. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include Swelling Dip Securigans P and Swelling Dip Securigans SBU manufactured by Atotech Japan.

  The swelling treatment with the swelling liquid is not particularly limited, and can be performed, for example, by immersing the insulating layer 21 ′ in a swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer 21 ′ to an appropriate level, it is preferable to immerse the insulating layer 21 ′ in a swelling liquid at 40 ° C. to 80 ° C. for 5 seconds to 15 minutes. Although it does not specifically limit as an oxidizing agent, 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 21 ′ in an oxidizing agent solution heated to 60 ° C. to 80 ° 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 oxidizing agents include alkaline permanganate solutions such as Concentrate Compact P and Dosing Solution Securigans P manufactured by Atotech Japan Co., Ltd. Moreover, as a neutralization liquid, acidic aqueous solution is preferable, As a commercial item, the reduction solution securigans P by Atotech Japan Co., Ltd. is mentioned, for example.

  The treatment with the neutralizing liquid can be performed by immersing the treated surface, which has been subjected to the roughening treatment with the oxidizing agent solution, in a neutralizing liquid at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidant solution in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

-Step (3-2)-
The conductor material which comprises a conductor layer is not specifically limited. In a preferred embodiment, it can be formed of the same material as the conductor material used for the wiring pattern, and copper is preferably used as the material.

  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.

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

  The conductor layer can be formed by any suitable method known in the art, such as plating, sputtering, or vapor deposition, and is preferably formed by plating. In a preferred embodiment, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Moreover, when the support body in an adhesive film is metal foil, the conductor layer which has a desired wiring pattern can be formed by conventionally well-known techniques, such as a subtractive method.

  Specifically, a plating seed layer is formed on the surface of the insulating layer 21 '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. An electroplating layer is formed on the exposed plating seed layer by electrolytic plating, 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.

  As shown in an example in FIG. 5, a plating seed layer 41 to be bonded to the exposed surface of the insulating layer 21 'is formed. First, cleaning of the surface of the insulating layer 21 'and alkali cleaning for charge adjustment are performed. Next, a soft etching process is performed for cleaning the inside of the via hole 31. Specifically, the treatment may be performed under any suitable conditions using an etchant such as an aqueous solution of sulfuric acid sodium peroxodisulfate. Next, a pre-dip process for adjusting the charge on the surface of the insulating layer 21 ′ for applying Pd (palladium) to the surface of the insulating layer 21 ′ is performed. Next, Pd which is an activator is applied to the surface, and Pd applied to the insulating layer 21 'is reduced. Next, copper (Cu) is deposited on the surface of the insulating layer 21 ′ to form a plating seed layer 41. At this time, the plating seed layer 41 is formed so as to cover the inside of the via hole 31, that is, the wiring layer 14 exposed from the side wall and the via hole 31.

  As shown in FIG. 6, after forming the plating seed layer 41, a mask pattern 50 that exposes a part of the plating seed layer 41 is formed. The mask pattern 50 can be formed, for example, by bonding a dry film to the plating seed layer 41 and performing exposure, development, and washing under predetermined conditions.

  As a dry film which can be used at a process (3-2), it is the same as that of the said dry film, and its preferable range is also the same.

  As shown in FIG. 7, an electroplating layer 42 is formed on the exposed plating seed layer 41 by electrolytic plating under the condition that the via hole 31 is filled, and the via hole is buried by electroplating to fill the filled via 61. Form.

  As shown in FIG. 8, the pattern conductor layer 40 is then formed by removing the mask pattern by peeling and performing flash etching under any suitable conditions that remove only the exposed plating seed layer 41.

  The conductor layer can include not only a linear wiring but also an electrode pad (land) on which an external terminal can be mounted, for example. The conductor layer may be composed only of electrode pads.

  The conductor layer may be formed by forming an electroplated layer and a filled via without using a mask pattern after the plating seed layer is formed, and then performing patterning by etching.

<Process (4)>
Step (4) is a step of removing the base material and forming the wiring board of the present invention as shown in FIG. The method for removing the substrate is not particularly limited. In a preferred embodiment, the substrate is peeled from the wiring board at the interface between the first and second metal layers, and the second metal layer is etched away with, for example, an aqueous copper chloride solution.

  As needed, you may peel a base material in the state which protected the conductor layer 40 with the protective film. The protective film is the same as the protective film used for the adhesive film, and the preferred range is also the same.

  By such a manufacturing method of the present invention, a wiring board in which the wiring layer 14 is embedded in the insulating layer 21 ′ can be manufactured. In addition, a flexible wiring board can be obtained by including at least one insulating layer 21 '. Moreover, if necessary, the formation of the insulating layer and the conductor layer in steps (2) to (3) may be repeated to form a multilayer wiring board. When producing a multilayer wiring board, at least one adhesive film of the present invention may be used. When performing a plurality of steps (3), in addition to forming via holes in the insulating layer and forming the conductor layer, a step of polishing or grinding the insulating layer to expose the wiring layer may be performed. The term “flexible” means that the wiring board can be bent at least once without causing a crack or a change in resistance value.

2. 2nd Embodiment 1st Embodiment is a case where a process (3) is a process of forming a via hole in an insulating layer, and forming a conductor layer, but 2nd Embodiment is a process (3) in which an insulating layer is formed. Except for the step of polishing or grinding to expose the wiring layer, it is the same as in the first embodiment. In each drawing used for the following description, the same components are denoted by the same reference numerals, and redundant description may be omitted.

  Step (1) is a step of preparing a base material with a wiring layer having a base material and wiring layers provided on both surfaces of the base material. The method for forming the wiring layer 14 is the same as in the first embodiment. In the step (1) in the second embodiment, as shown in FIG. 10, the thickness of each wiring layer 14 in the second embodiment is preferably different.

  Of each wiring layer, the thickness of the wiring layer (conductive pillar) having the greatest thickness depends on the design of the desired wiring board, but is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and even more preferably. Is 40 μm or less or 20 μm or less. Although a minimum is not specifically limited, Preferably it is 2 micrometers or more, More preferably, it is 5 micrometers or more. The thickness of the wiring layer other than the wiring layer having the greatest thickness is the same as the thickness of the wiring layer in the first embodiment, and the preferable range is also the same.

  In step (2), as shown in FIG. 11, the adhesive film of the present invention is laminated on a substrate with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, This is a step of forming an insulating layer by curing, which is the same as in the first embodiment, and the preferred range is also the same.

  Step (3) is a step of polishing or grinding the insulating layer to expose the wiring layer. Unlike the step (3) in the first embodiment, since the via hole is not formed, the cost of forming the via hole can be greatly reduced.

  As described above, as the wiring layer in the second embodiment, each wiring layer may have a uniform thickness as shown in FIG. 1, and each wiring layer as shown in FIG. 10 as an example. Layers 14 may have different thicknesses. In the step (3), it is not necessary to expose all the wiring layers. For example, a part of the wiring layer 14 may be exposed as shown in FIG.

  The insulating layer polishing method or grinding method is not particularly limited as long as the wiring layer can be exposed and the polishing or grinding surface is horizontal, and a conventionally known polishing method or grinding method can be applied. And a chemical mechanical polishing method using a chemical mechanical polishing apparatus.

  After the step (3), if necessary, a smear removing step and a roughening step may be performed as in the first embodiment. Moreover, you may form a conductor layer like the process (3-2) mentioned above as needed.

  Step (4) is a step of removing the base material and forming the wiring board of the present invention as shown in FIG. The method for removing the substrate is not particularly limited. In a preferred embodiment, the substrate is peeled from the wiring board at the interface between the first and second metal layers, and the second metal layer is etched away with, for example, an aqueous copper chloride solution.

3. 3rd Embodiment Although 1st Embodiment manufactured the wiring board from the base material with a wiring layer which has a wiring layer in one side, 3rd Embodiment is a base with a wiring layer which has a wiring layer on both surfaces of a base material. It is the same as that of 1st Embodiment except manufacturing a wiring board from a material. In each drawing used for the following description, the same components are denoted by the same reference numerals, and redundant description may be omitted.

  Step (1) is a step of preparing a base material with a wiring layer having a base material and wiring layers provided on both surfaces of the base material as shown in FIG. The method of forming the wiring layer 14 is the same as that of the first embodiment, and the wiring layers provided on both surfaces of the base material may be formed simultaneously to prepare a base material with a wiring layer. A wiring layer may be formed to prepare a substrate with a wiring layer. In addition, each wiring layer may have the same pattern or different patterns. Further, the thickness of each wiring layer may be different as shown in FIG.

  In the step (2), as shown in FIG. 15, the adhesive film is attached to both sides of the substrate with the wiring layer, and the wiring layer-based substrate is embedded in the thermosetting resin composition layer. It is a process of laminating and thermosetting each material. The two adhesive films used may be the same adhesive film or different adhesive films.

  In step (3), as shown in an example in FIG. 16, laser irradiation is performed on both surfaces of the substrate with a wiring layer from the thermally cured adhesive film side to form via holes in the thermally cured adhesive film. It is preferable. The via hole may be formed at the same time, or after forming one via hole, the other via hole may be formed.

  Before forming the conductor layer, a roughening process may be included on both surfaces of the substrate with the wiring layer, and the surfaces of the two insulating layers 21 ′ are roughened. The roughening treatment may be performed simultaneously, or the other roughening treatment may be performed after one roughening treatment.

  After the via hole is formed, a conductor layer is formed on both surfaces of the substrate with the wiring layer. As shown in FIG. 17, a plating seed layer 41 is formed on the roughened insulating layer 21 ′. After the plating seed layer 41 is formed, a mask pattern 50 that exposes a part of the plating seed layer 41 is formed as shown in FIG. 18, and the exposed plating seed layer 41 is formed as shown in FIG. 19 as an example. In addition, the electroplated layer 42 is formed, and the via hole is buried by electroplating to form the filled via 61. As shown in FIG. 20 as an example, the mask pattern is removed and the conductor layer 40 is formed. Details of the formation of the conductor layer 40 can be performed in the same manner as in the first embodiment. Moreover, the two conductor layers provided on both surfaces of the base material may be formed simultaneously, or the other conductor layer may be formed after forming one conductor layer.

  Although the case where the step (3) in the third embodiment is a step of forming a via hole in the insulating layer and forming a conductor layer has been described, the step of polishing or grinding the insulating layer and exposing the wiring layer is performed. Also good. Further, a via hole is formed in the insulating layer on one surface of the substrate with the wiring layer, and a conductor layer is formed. The insulating layer is polished or ground on the other surface, and the wiring layer is formed. You may perform the process to expose.

  Step (4) is a step of removing the base material and forming the wiring board of the present invention as shown in FIG. In the third embodiment, two types of wiring boards can be manufactured simultaneously.

[Wiring board]
The wiring board of the present invention includes an insulating layer that is a cured product of the thermosetting resin composition layer of the adhesive film of the present invention, and an embedded wiring layer embedded in the insulating layer. In addition, the description which overlaps with the content mentioned above may be abbreviate | omitted.

  The wiring board of this invention can be manufactured with the manufacturing method of the wiring board of this invention including the process of said (1)-(4), for example. As shown in FIG. 9, the wiring board 1 of the present invention is laminated in the order of the embedded wiring layer 14 and the insulating layer 21 ′. A conductor layer 40 is provided on the surface of the insulating layer 21 ′ that is not joined to the embedded wiring layer 14 (that is, on the surface opposite to the embedded wiring layer 14). The embedded wiring layer 14 is joined to the conductor layer 40 via the filled via 61.

  The embedded wiring layer refers to a wiring layer (wiring layer 14) embedded in the insulating layer 21 'as long as conductor connection with a component such as a semiconductor chip is possible. The embedded wiring layer is normally embedded in the insulating layer so that the protruding height is substantially 0 (zero), usually −1 μm to +1 μm, on the side opposite to the side where the adhesive film is laminated. It is.

  The wiring board of the present invention may be a multilayer wiring board as shown in FIG. 22 and FIG. The thermosetting resin composition constituting the thermosetting resin composition layer forming the insulating layer in the wiring board shown in FIG. 22 and FIG. 23 as an example may have the same composition or different compositions. Also good. Further, as shown in FIG. 22, the top diameter and the bottom diameter of the filled via 61 may be substantially the same, and as shown in FIG. 23, the top diameter of the filled via 61 is larger than the bottom diameter. Also good.

[Semiconductor device]
A semiconductor device of the present invention includes the wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the 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 of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). 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.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

<Preparation of evaluation substrate>
(1) Step of preparing a substrate with a wiring layer having a substrate and a wiring layer provided on one surface of the substrate (1-1) Lamination of a dry film on the substrate (core substrate) As a substrate, glass cloth base epoxy resin double-sided copper-clad laminate (layer structure: Micro thin MT-Ex copper foil (3 μm thick copper foil / 18 μm thick carrier foil) manufactured by Mitsui Mining & Smelting Co., Ltd.) / Panasonic ( “R1515A” substrate (thickness 0.2 mm) / Micro thin MT-Ex copper foil (18 μm thick carrier foil / 3 μm thick copper foil)) 170 × 125 mm prepared by Mitsui Kinzoku Mining Co., Ltd.) did. A dry film with a PET film (“ALHO 20A263” manufactured by Nikko Materials Co., Ltd., dry film thickness 20 μm) is bonded to the both sides of the 3 μm copper foil side of the laminated plate with the dry film and the copper foil. Thus, it laminated | stacked using the batch type vacuum pressurization laminator (Nikko Materials Co., Ltd. 2 stage buildup laminator "CVP700"). Lamination of the dry film was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the film at a temperature of 70 ° C. and a pressure of 0.1 MPa for 20 seconds.

(1-2) Formation of pattern A glass mask (photomask) on which the wiring pattern shown below is formed is placed on a PET film, which is a protective layer of a dry film, and UV is irradiated with a UV lamp at an irradiation intensity of 150 mJ / cm2. Irradiated. After UV irradiation, the PET film as a dry film was peeled off, and a 1% sodium carbonate aqueous solution at 30 ° C. was sprayed for 30 seconds at an injection pressure of 0.15 MPa. Then, it washed with water and the development (pattern formation) of the dry film was performed.

Glass mask wiring pattern:
L / S = 15 μm / 15 μm, that is, a comb-tooth pattern (wiring length 15 mm, 16 lines, 10 mm square conductor leads) with a wiring pitch of 30 μm is formed at intervals of 10 mm.

(1-3) Formation of wiring layer After development of the dry film, electrolytic copper plating was performed at a thickness of 15 μm to form a wiring layer. Next, a 3% sodium hydroxide solution at 50 ° C. was sprayed at an injection pressure of 0.2 MPa, the dry film was peeled off, washed with water and dried at 150 ° C. for 30 minutes.

(2) Step of laminating an adhesive film on a substrate with a wiring layer and forming an insulating layer by thermosetting so that the wiring layer is embedded in the thermosetting resin composition layer (2-1) Lamination of the adhesive film Using the resin varnishes prepared in Examples and Comparative Examples, the protective film of each adhesive film (167 mm × 122 mm) prepared as described in <Preparation of Adhesive Film> was peeled off, and a batch type vacuum pressure laminator ( Using a 2-stage build-up laminator “CVP700” manufactured by Nikko Materials Co., Ltd., the thermosetting resin composition layer was embedded and laminated on both surfaces of the wiring layer so as to be bonded to the wiring layer. Lamination was performed 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. Subsequently, the laminated adhesive film was smoothed by hot pressing at 100 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure.

(2-2) Thermosetting of thermosetting resin composition layer After laminating the adhesive film, the support (PET film) is peeled off and the thermosetting resin composition layer is thermoset at 190 ° C for 90 minutes. Insulating layers were formed on both sides of the wiring layer. After cooling to room temperature, heat treatment was performed at 130 ° C. for 30 minutes in order to relieve stress due to thermosetting.

(3) Step of forming a punching hole for length measurement on a substrate Four through holes (diameter of about 6 mm) are formed by punching in a 4 to 15 mm portion of the obtained substrate (170 × 125 mm) ( The holes are tentatively referred to as A, B, C, and D in a clockwise direction.) After peeling off the support of the adhesive film, the diagonal length L (L _AC , L _BD ) between the centers of the formed holes is a non-contact type. It was measured with an image measuring instrument (manufactured by Mitutoyo Corporation, Quick Vision model: QVH1X606-PRO III_BHU2G).

(4) Step of removing the base material Thereafter, a cutter blade was inserted into the interface between the 3 μm thick copper foil and the 18 μm thick carrier foil of the micro thin MT-Ex copper foil of the core substrate, and the core substrate was separated and separated. . Next, the 3 μm copper foil was removed by etching with an aqueous copper chloride solution, washed with water, and then dried at 110 ° C. for 30 minutes. The wiring board in which the L / S = 15/15 μm comb-teeth pattern thus obtained is embedded on one side is referred to as “evaluation board A”.

<Evaluation of dimensional accuracy>
Regarding the obtained two evaluation substrates A, the length L ′ (L ′ _AC , L ′ _BD ) between the centers of the holes formed in (3) is set to a non-contact type image in the same manner as L. Measured with a measuring instrument. Any one of the dimensional changes (L ′ _AC −L _AC ) and (L ′ _BD -L _BD ) exceeds 2 mm, ×, 1-2 mm is Δ, and all are 1 mm or less.

<Evaluation of reflow resistance>
The two evaluation boards A after the dimensional accuracy evaluation were passed three times through a reflow device (“HAS-6116” manufactured by Nippon Antom Co., Ltd.) that reproduces the solder reflow temperature with a peak temperature of 260 ° C. (reflow temperature profile is IPC) / JEDEC J-STD-020C). Thereafter, a case where there was an abnormality such as peeling even in a part of the conductor pattern was visually evaluated as x, and a case where there was no abnormality at all.

<Measurement of elastic modulus, breaking strength and breaking elongation>
The untreated surface of the release PET film (Lintec Co., Ltd. “501010”, thickness 38 μm, 240 mm square) is a glass cloth base epoxy resin double-sided copper-clad laminate (Matsushita Electric Works “R5715ES”, thickness) 0.7 mm, 250 mm square) was placed on a glass cloth base epoxy resin double-sided copper-clad laminate, and the four sides of the release film were fixed with polyimide adhesive tape (width 10 mm).

  Each adhesive film (230 mm square) prepared as described in <Preparation of adhesive film> using the resin varnishes prepared in Examples and Comparative Examples was used as a batch type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd.) 2 Using a stage buildup laminator CVP700), the laminate was processed in the center so that the thermosetting resin composition layer was in contact with 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 thermosetting resin composition layer was thermoset under curing conditions at 190 ° C. for 90 minutes.

  After thermosetting, the polyimide adhesive tape was peeled off, and the thermosetting resin composition layer was removed from the glass cloth base epoxy resin double-sided copper-clad laminate. Furthermore, the release PET film was peeled from the thermosetting resin composition layer to obtain a sheet-like cured product. The sheet-like cured product is referred to as an evaluation cured product. The obtained cured product for evaluation was cut into a dumbbell shape No. 1 to obtain a test piece. The test piece was subjected to tensile strength measurement using a tensile tester “RTC-1250A” manufactured by Orientec Co., Ltd., and the elastic modulus, breaking strength and breaking elongation at 23 ° C. were obtained. The measurement was performed according to JIS K7127. This operation was performed 5 times, and the average value of the top 3 points was shown in the table.

<Evaluation of resistance to seam fold>
At the center of the same dumbbell-shaped No. 1 as above, a 1 kg weight was placed for 5 seconds. Thereafter, the hull fold was returned to its original position, and a 1 kg weight was placed for 5 seconds. The above operation was repeated 5 times, and the presence or absence of cutting of the folded portion was visually observed. With regard to the three cured products for evaluation, all of the folded portions are resistant to being cut (◯), and even one of the cured materials is not resistant to being partially or entirely cut. (×) was evaluated.

<Measurement of resin layer melt viscosity>
Using the resin varnishes prepared in Examples and Comparative Examples, only the resin composition layer is peeled off from the release PET (support) of each adhesive film prepared as described in <Preparation of adhesive film>, and compressed with a mold. As a result, pellets for measurement (diameter 18 mm, 1.2 to 1.3 g) were produced. Then, using a dynamic viscoelasticity measuring apparatus ("Rheosol-G3000" manufactured by UBM Co., Ltd.) and using a parallel plate with a diameter of 18 mm for a sample resin composition layer 1 g, starting temperature from 60C The temperature was raised to 200 ° C. at a rate of temperature increase of 5 ° C./min, the dynamic viscoelastic modulus was measured under the measurement conditions of a measurement temperature interval of 2.5 ° C., a frequency of 1 Hz, and a strain of 1 deg, and the minimum melt viscosity (poise). Is shown in Table 1.

[Production of curing agent A having a butadiene structure and a phenolic hydroxyl group]
In a reaction vessel, 45 g of G-1000 (bifunctional hydroxy group-terminated polybutadiene, number average molecular weight = 1400, hydroxy group equivalent = 770 g / eq., Nippon Soda Co., Ltd.) and ipsol 150 (aromatic hydrocarbon-based mixed solvent) : Idemitsu Petrochemical Co., Ltd.) 40 g and dibutyltin laurate 0.005 g were mixed and dissolved uniformly. When the temperature became uniform, the temperature was raised to 50 ° C., and while further stirring, 15 g of isophorone diisocyanate (isocyanate group equivalent = 113 g / eq., IPDI manufactured by Evonik Degussa Japan Co., Ltd.) was added and reacted for about 3 hours. Next, the reaction product was cooled to room temperature, and then cresol novolak resin KA-1160 (hydroxyl equivalent = 117 g / eq., Manufactured by DIC Corporation) and ethyl diglycol acetate (produced by Daicel Corporation). 60g was added, it heated up to 80 degreeC, stirring, and reaction was performed for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. Upon confirming the disappearance of the NCO peak, the reaction 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 a curing agent A having a butadiene structure and a phenolic hydroxyl group (nonvolatile content: 50% by mass). Obtained.
Number average molecular weight: 2900

[Production of curing agent B having hydrogenated butadiene structure and phenolic hydroxyl group]
In a reaction vessel, GI-1000 (bifunctional hydroxy group terminal hydrogenated polybutadiene, number average molecular weight = 1500, hydroxy group equivalent = 830 g / eq., Nippon Soda Co., Ltd.) 46 g and Ipsol 150 (aromatic hydrocarbon type) Mixed solvent: Idemitsu Petrochemical Co., Ltd. 40 g and dibutyltin laurate 0.005 g were mixed and dissolved uniformly. When the temperature became uniform, the temperature was raised to 50 ° C., and with further stirring, 14 g of isophorone diisocyanate (isocyanate group equivalent = 113 g / eq., IPDI manufactured by Evonik Degussa Japan Co., Ltd.) was added, and the reaction was performed for about 3 hours. Next, the reaction product was cooled to room temperature, and then cresol novolak resin KA-1160 (hydroxyl equivalent = 117 g / eq., Manufactured by DIC Corporation) and ethyl diglycol acetate (produced by Daicel Corporation). 60g was added, it heated up to 80 degreeC, stirring, and reaction was performed for about 4 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 is regarded as the end point of the reaction, and the reaction product is cooled to room temperature and then filtered through a 100 mesh filter cloth to obtain a curing agent B having a hydrogenated butadiene structure and a phenolic hydroxyl group (non-volatile content: 50% by mass) )
Number average molecular weight: 3000

[Production of curing agent C having butadiene structure and phenolic hydroxyl group]
In a reaction vessel, 69 g of G-3000 (bifunctional hydroxy group-terminated polybutadiene, number average molecular weight = 3000, hydroxy group equivalent = 1800 g / eq., Nippon Soda Co., Ltd.) and Ipsol 150 (aromatic hydrocarbon-based mixed solvent) : Idemitsu Petrochemical Co., Ltd.) 40 g and dibutyltin laurate 0.005 g were mixed and dissolved uniformly. When the temperature became uniform, the temperature was raised to 50 ° C., and further with stirring, 8 g of isophorone diisocyanate (isocyanate group equivalent = 113 g / eq., IPDI manufactured by Evonik Degussa Japan Co., Ltd.) was added and reacted for about 3 hours. Next, the reaction product was cooled to room temperature, and 23 g of cresol novolak resin KA-1160 (hydroxyl equivalent = 117 g / eq., Manufactured by DIC Corporation) and ethyl diglycol acetate (manufactured by Daicel Corporation) were added thereto. 60g was added, it heated up to 80 degreeC, stirring, and reaction was performed for about 4 hours. The disappearance of the NCO peak at 2250 cm −1 was confirmed by FT-IR. Upon confirming the disappearance of the NCO peak, the reaction 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 a curing agent C having a butadiene structure and a phenolic hydroxyl group (non-volatile content: 50% by mass). Obtained.
Number average molecular weight: 5500

<Example 1>
5.1 parts of flexible structure-containing epoxy resin (DIC Corporation "EXA-4816", epoxy equivalent 406), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3100", epoxy equivalent 258) 1.5 Parts, flexible structure-containing phenoxy resin ("YX7180BH40" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 40% by mass), phenoxy resin (manufactured by Mitsubishi Chemical Corporation " YX6954BH30 ", 6 parts of cyclohexanone with a solid content of 30% by mass: 1: 1 MEK solution, and 1 part of Ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) were dissolved with heating. . What was heated and dissolved was cooled to room temperature, and into this, 10 parts of a curing agent A solution, a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., “1B2PZ-10M”, 1-benzyl-2-phenylimidazole, solid content 1 part of 10% by mass MEK solution) and spherical silica (average particle size 0.1 μm, manufactured by Denki Kagaku Kogyo Co., Ltd.) surface-treated with phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts of UFP-30 ”, carbon amount per unit surface area of 0.19 mg / m ² ), mixed uniformly with a high-speed rotary mixer, filtered through a cartridge filter (“ SHP020 ”manufactured by ROKITECHNO), and resin varnish 1 was produced.

<Example 2>
8.5 parts of flexible structure-containing epoxy resin (DIC Corporation "EXA-4816", epoxy equivalent 406), bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent 238) 3 parts, Flexible structure-containing phenoxy resin ("YX7180BH40" manufactured by Mitsubishi Chemical Corporation, 8 parts by weight of cyclohexanone: 1: 1 solution of MEK) 8 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation), solid content 10 parts of 30% by mass of cyclohexanone: MEK (1: 1 solution) and 1.5 parts of ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) were dissolved by heating with stirring. What was dissolved by heating was cooled to room temperature, and into this, 10 parts of a curing agent B solution, a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., “1B2PZ-10M”, 1-benzyl-2-phenylimidazole, solid content 10 parts by weight of MEK solution) 0.8 part, flame retardant (“HCA-HQ-HST” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phos Spherical silica surface-treated with phafenanthrene-10-oxide (average particle size 1.5 μm) 2.5 parts and aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Admatechs Ltd. "sO-C2", average particle size 0.5 [mu] m, mixing the carbon amount 0.38mg ^/ m 2) 20 parts per unit surface area, are uniformly dispersed in a high-speed rotary mixer, the cartridge Fi And filtered through a coater (ROKITECHNO manufactured "SHP050"), to prepare a resin varnish 2.

<Example 3>
1 part of a flexible structure-containing epoxy resin (Mitsubishi Chemical Corporation “YX7400”, epoxy equivalent 440), 6.8 parts of a flexible structure-containing epoxy resin (DIC Corporation “EXA-4816”, epoxy equivalent 406) , 12 parts of phenoxy resin (Mitsubishi Chemical Corporation “YX7553BH30”, 30% by mass of cyclohexanone: 1: 1 solution of MEK), Ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) ) 1.5 parts were heated and dissolved with stirring. What was dissolved by heating was cooled to room temperature, and into this, 10 parts of a curing agent B solution, a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., “1B2PZ-10M”, 1-benzyl-2-phenylimidazole, solid content 1 part of 10% by mass MEK solution) and spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.), average particle surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 24 parts of carbon having a diameter of 0.5 μm and a unit surface area of 0.38 mg / m ² ) are mixed, dispersed uniformly with a high-speed rotary mixer, filtered through a cartridge filter (“SHP050” manufactured by ROKITECHNO), and resin varnish 3 was produced.

<Example 4>
6 parts of bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent 238), 2 parts of dicyclopentadiene type epoxy resin DIC "HP-7200", epoxy equivalent 258), flexible structure 8 parts of phenoxy resin ("YX7180BH40" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: MEK having a solid content of 40% by mass) and 4 parts of MEK were heated and dissolved while stirring. What was dissolved by heating was cooled to room temperature, and into this, 20 parts of a curing agent C solution, a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., “1B2PZ-10M”, 1-benzyl-2-phenylimidazole, solid content 1 part of 10% by mass MEK solution), flame retardant (“HCA-HQ-HST” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphafe Spherical silica (average particle size 0.1 μm) surface-treated with 2.5 parts of nanthrene-10-oxide, average particle size 1.5 μm, and phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.) , Denki Kagaku Kogyo Co., Ltd. "UFP-30", carbon content 0.19 mg ^{/ m} 2) 8 parts per unit surface area, aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM573" In surface-treated spherical silica (Co. Admatechs Ltd., "SO-C2", average particle size 0.5 [mu] m, the carbon amount 0.38 mg ^{/ m} 2 per unit surface area) 8 parts were mixed, with a high-speed rotary mixer The resin varnish 4 was produced by uniformly dispersing and filtering with a cartridge filter (“SHP050” manufactured by ROKITETECHNO).

<Example 5>
2 parts of flexible structure-containing epoxy resin (Mitsubishi Chemical Corporation "YX7400", epoxy equivalent 440), flexible structure-containing epoxy resin (DIC Corporation "EXA-4816", epoxy equivalent 406) 10.2 parts , Flexible structure-containing phenoxy resin ("YX7180BH40" manufactured by Mitsubishi Chemical Corporation, cyclohexanone: 1: 1 solution of MEK having a solid content of 40% by mass), 8 parts, phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation), solid 8 parts of 30% by mass of cyclohexanone: 1: 1 MEK solution and 1.8 parts of ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) were heated and dissolved with stirring. What was dissolved by heating was cooled to room temperature, and into this, 12 parts of a curing agent A solution, a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., “1B2PZ-10M”, 1-benzyl-2-phenylimidazole, solid content 10 parts by mass of MEK solution) and spherical silica surface-treated with aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Admatex Co., Ltd.), average particle 15 parts in diameter of 0.5 μm, carbon amount per unit surface area of 0.38 mg / m ² ), mixed uniformly with a high-speed rotary mixer, filtered through a cartridge filter (“SHP050” manufactured by ROKITECHNO), and resin varnish 5 was produced.

<Comparative Example 1>
Bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation “YL7760”, epoxy equivalent 238) 8 parts, phenoxy resin (Mitsubishi Chemical Corporation “YX7553BH30”, solid content 30 mass% cyclohexanone: 1: 1 solution of MEK ) 10 parts, Ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) 1.5 parts was heated and dissolved with stirring. What was dissolved by heating was cooled to room temperature, and into this, 10 parts of a curing agent B solution, a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., “1B2PZ-10M”, 1-benzyl-2-phenylimidazole, solid content 10 parts by weight of MEK solution) 0.8 part, flame retardant (“HCA-HQ-HST” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phos Spherical silica surface-treated with phafenanthrene-10-oxide (average particle size 1.5 μm) 2.5 parts and aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Admatechs Ltd. "sO-C2", average particle size 0.5 [mu] m, mixing the carbon amount 0.38mg ^/ m 2) 20 parts per unit surface area, are uniformly dispersed in a high-speed rotary mixer, the cartridge Fi And filtered through a coater (ROKITECHNO manufactured "SHP050"), to prepare a resin varnish 6.

<Comparative example 2>
5.1 parts of flexible structure-containing epoxy resin (DIC Corporation "EXA-4816", epoxy equivalent 406), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3100", epoxy equivalent 258) 1.5 Parts, 1.5 parts of Ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) were heated and dissolved with stirring. What was heated and dissolved was cooled to room temperature, and into this, 10 parts of a curing agent A solution, a curing accelerator (manufactured by Shikoku Chemicals Co., Ltd., “1B2PZ-10M”, 1-benzyl-2-phenylimidazole, solid content 10 parts by weight of MEK solution) and spherical silica (average particle size 0.1 μm, manufactured by Denki Kagaku Kogyo Co., Ltd.) surface-treated with phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts of UFP-30 ”, carbon amount per unit surface area of 0.19 mg / m ² ), mixed uniformly with a high-speed rotary mixer, filtered through a cartridge filter (“ SHP020 ”manufactured by ROKITECHNO), and resin varnish 7 was produced.

<Comparative Example 3>
5.1 parts of flexible structure-containing epoxy resin (DIC Corporation "EXA-4816", epoxy equivalent 406), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3100", epoxy equivalent 258) 1.5 Parts, 15 parts of flexible structure-containing phenoxy resin ("YX7180BH40" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 40% by mass), ipsol 150 (aromatic hydrocarbon-based mixed solvent) 1 part of Idemitsu Petrochemical Co., Ltd.) was dissolved by heating with stirring. What was heated and dissolved was cooled to room temperature, and into this, 10 parts of a curing agent A solution, a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., “1B2PZ-10M”, 1-benzyl-2-phenylimidazole, solid content 10 parts by weight of MEK solution) and 1.5 parts of spherical silica (average particle size 0.1 μm, Denki Kagaku Kogyo Co., Ltd.) surface-treated with phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts of “UFP-30” manufactured by carbon, 0.19 mg / m ² of carbon per unit surface area are mixed and dispersed uniformly with a high-speed rotary mixer, and filtered with a cartridge filter (“SHP020” manufactured by ROKITECHNO) Resin varnish 8 was produced.

<Comparative Example 4>
6.8 parts of flexible structure-containing epoxy resin (DIC Corporation "EXA-4816", epoxy equivalent 406), flexible structure-containing phenoxy resin (Mitsubishi Chemical Corporation "YX7180BH40", solid content of 40% by mass 6 parts of cyclohexanone: MEK 1: 1 solution) and 10 parts of ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) were heated and dissolved with stirring. What was dissolved by heating was cooled to room temperature, and into this, 10 parts of a curing agent B solution, a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., “1B2PZ-10M”, 1-benzyl-2-phenylimidazole, solid content 10 parts by weight of MEK solution) and 0.8 parts of spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 50 parts of an average particle size of 0.5 μm and carbon amount per unit surface area of 0.38 mg / m ² ) are mixed, uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) Resin varnish 9 was produced.

<Preparation of adhesive film>
As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc.) having a release treatment with an alkyd resin release agent (“AL-5” manufactured by Lintec Corporation), a thickness of 38 μm, a softening point of 130 ° C. Type PET "). On the release surface, resin varnishes 1 to 9 are uniformly applied so that the thickness of the thermosetting resin composition layer after drying each resin varnish becomes 40 μm, and 80 to 120 ° C. (average 100 ° C.) After drying for 5 minutes, 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 bonded to join the thermosetting resin composition layer, An adhesive film was prepared.

1 Wiring Board 10 Substrate with Wiring Layer 11 Substrate (Core Substrate)
12 First metal layer 13 Second metal layer 14 Wiring layer (embedded wiring layer)
20 Adhesive Film 21 Thermosetting Resin Composition Layer 21 ′ Insulating Layer 22 Support 23 Protective Film 31 Via Hole 40 Conductor Layer 41 Plating Seed Layer 42 Electroplating Layer 50 Mask Pattern 61 Filled Via

Claims (18)

A thermosetting resin composition comprising (a) an epoxy resin, (b) a compound having an optionally hydrogenated butadiene structure and a phenolic hydroxyl group, (c) a phenoxy resin, and (d) an inorganic filler. And
(A) A part or all of the epoxy resin and / or (c) phenoxy resin has a flexible structure selected from an alkylene structure having 2 to 20 carbon atoms and an alkylene structure having an ether bond having 2 to 20 carbon atoms. A compound,
(D) The inorganic filler is 30% by mass or more when the nonvolatile component of the resin composition is 100% by mass,
Thermosetting resin composition having a modulus of elasticity, breaking strength, and breaking elongation at 23 ° C. of 1 Gpa or more and 6 Gpa or less, 10 Mpa or more, and 6% or more, respectively, at 23 ° C. of a cured product obtained by thermosetting a thermosetting resin composition. object. The thermosetting resin composition according to claim 1, wherein the compound having a flexible structure is a compound having an alkylene structure having an ether bond having 3 to 15 carbon atoms.   The resin composition according to claim 1 or 2, wherein the content of the compound having a flexible structure is 2% by mass to 50% by mass when the nonvolatile component in the thermosetting resin composition is 100% by mass. (B) The content of the compound having a butadiene structure and a phenolic hydroxyl group which may be hydrogenated is 8% by mass to 50% by mass when the nonvolatile component in the thermosetting resin composition is 100% by mass. The resin composition according to any one of claims 1 to 3. The adhesive film containing the support body and the layer of the thermosetting resin composition of any one of Claims 1-4. (1) preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate;
(2) An adhesive film including a thermosetting resin composition layer is laminated on a substrate with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, and is thermally cured to form an insulating layer. The process of
(3) a step of interconnecting the wiring layers, and (4) a step of removing the substrate,
The adhesive film of Claim 5 used for the manufacturing method of a wiring board containing this.   The step (3) is at least one of a step of forming a via hole in the insulating layer and forming a conductor layer, and a step of polishing or grinding the insulating layer and exposing the wiring layer. Adhesive film.   6. The adhesive film according to claim 5, wherein the adhesive film is used for manufacturing a wiring board comprising an insulating layer and an embedded wiring layer embedded in the insulating layer. (1) preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate;
(2) The adhesive film according to any one of claims 5 to 8 is laminated on a substrate with a wiring layer and thermally cured so that the wiring layer is embedded in the thermosetting resin composition layer. Forming an insulating layer;
(3) a step of interconnecting the wiring layers; and
(4) removing the substrate;
A method for manufacturing a wiring board, comprising:   The step (3) is at least one of a step of forming a via hole in the insulating layer and forming a conductor layer, and a step of polishing or grinding the insulating layer and exposing the wiring layer. the method of.   The method according to claim 9 or 10, wherein step (3) is a step of forming a via hole in the insulating layer to form a conductor layer, and is performed by laser irradiation.   The method of Claim 11 including the process of performing a roughening process before forming a conductor layer.   The method according to any one of claims 9 to 12, wherein the wiring board is a flexible wiring board.   The method according to claim 9, wherein the minimum pitch of the wiring pattern is 40 μm or less.   A wiring board provided with the insulating layer which is a hardened | cured material of the thermosetting resin composition layer of the adhesive film of any one of Claims 5-8, and the embedding type wiring layer embedded in the insulating layer.   The wiring board according to claim 15, which is a flexible wiring board.   The wiring board according to claim 15 or 16, wherein the insulating layer has a thickness of 2 µm or more. A semiconductor device provided with the wiring board of any one of Claims 15-17.

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