WO2022210598A1 - 回路基板の製造方法 - Google Patents
回路基板の製造方法 Download PDFInfo
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- WO2022210598A1 WO2022210598A1 PCT/JP2022/015174 JP2022015174W WO2022210598A1 WO 2022210598 A1 WO2022210598 A1 WO 2022210598A1 JP 2022015174 W JP2022015174 W JP 2022015174W WO 2022210598 A1 WO2022210598 A1 WO 2022210598A1
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- circuit
- metal layer
- resin composition
- circuit board
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- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical class O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- LTURHSAEWJPFAA-UHFFFAOYSA-N sulfuric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 LTURHSAEWJPFAA-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- GHPYAGKTTCKKDF-UHFFFAOYSA-M tetraphenylphosphanium;thiocyanate Chemical compound [S-]C#N.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 GHPYAGKTTCKKDF-UHFFFAOYSA-M 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
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- 239000013638 trimer Substances 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
- H05K3/4655—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern by using a laminate characterized by the insulating layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
- H05K3/064—Photoresists
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/107—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by filling grooves in the support with conductive material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
Definitions
- the present invention relates to a method of manufacturing a circuit board.
- circuit boards such as rewiring boards generally form an insulating layer by providing a curable resin material on a wafer or panel board and curing it. After that, a conductor layer is formed on the insulating layer, and this is repeated to form a multilayer structure (eg, Patent Document 1).
- Insulating layers used in circuit boards may contain inorganic fillers such as silica in order to achieve characteristics such as low coefficient of thermal expansion and low dielectric loss tangent. is.
- the present invention provides a novel method for manufacturing a circuit board, which can form a conductor circuit in a fine pattern even when the insulating layer contains an inorganic filler.
- the present invention includes the following contents.
- a method of manufacturing a circuit board comprising: A method for producing a circuit board, wherein the resin composition contains an epoxy resin, a curing agent and an inorganic filler.
- [2] The method according to [1], wherein the content of the inorganic filler in the resin composition is 20% by mass or more and 75% by mass or less when the non-volatile component in the resin composition is 100% by mass.
- [3] The method according to [1] or [2], wherein the inorganic filler has an average particle size of 0.6 ⁇ m or less.
- [4] The method according to any one of [1] to [3], wherein the inorganic filler is silica.
- [5] The method according to any one of [1] to [4], wherein the minimum melt viscosity of the resin composition is 5000 poise or less.
- [6] The method according to any one of [1] to [5], wherein the thickness of the metal layer is less than 0.5 ⁇ m.
- the arithmetic mean roughness Ra of the metal layer surface is 200 nm or less, and the difference TTV between the maximum and minimum heights of the metal layer surface measured in the thickness direction of the metal layer surface is 50 ⁇ m or less.
- the substrate with a metal layer is selected from a metal substrate, an inorganic substrate and an organic substrate having a composition different from that of the metal layer.
- step (Z) is performed by removing the metal layer after removing the substrate.
- Step (X) is (X-1) providing a photoresist on the metal layer, exposing and developing the photoresist to expose the metal layer corresponding to the circuit pattern of the first conductor circuit to be formed, and (X-2) ) The method of any one of [1] to [9], comprising forming a conductor layer on the exposed metal layer to form a first conductor circuit. [11] The method according to any one of [1] to [10], wherein the first conductor circuit includes a trench-type conductor circuit. [12] In step (Y), a resin sheet including a support film and a resin composition layer provided on the support film is attached to a base material so that the resin composition layer is bonded to the first conductor circuit.
- step (Y) After step (Y), (i) forming a second conductive circuit on the surface of the insulating layer; and (ii) forming a resin composition layer so as to embed the second conductive circuit, and curing the resin composition layer to form an insulating layer.
- a circuit board having a first main surface and a second main surface, including a trench-type conductor circuit on the first major surface;
- the trench-type conductor circuit has a minimum line/space ratio (L/S) of 2/2 ⁇ m or less, Angle difference between the direction y1 of the straight line defined by the side wall of the trench-type conductor circuit and the direction Y in the cross section in the direction Y perpendicular to the first main surface and also perpendicular to the extending direction of the trench-type conductor circuit is 20° or less,
- the insulating layer defining the first main surface together with the trench-type conductive circuit is made of a cured product of a resin composition containing an epoxy resin, a curing agent and an inorganic filler.
- the circuit board according to any one of [15] to [19], and a semiconductor provided on the first main surface so as to be electrically connected to the trench-type conductive circuit of the circuit board A semiconductor package, including a chip.
- the semiconductor package according to [20] which is a fan-out type package.
- the present invention it is possible to provide a novel method for manufacturing a circuit board, which can form a conductor circuit in a fine pattern even when the insulating layer contains an inorganic filler.
- FIG. 1 is a schematic diagram (1) for explaining a circuit board manufacturing method (hereinafter simply referred to as "circuit board manufacturing method") according to an embodiment of the present invention.
- FIG. 2 is a schematic diagram (2) for explaining the method of manufacturing the circuit board.
- FIG. 3 is a schematic diagram (3) for explaining the method of manufacturing the circuit board.
- FIG. 4 is a schematic diagram (4) for explaining the method of manufacturing the circuit board.
- FIG. 5 is a schematic diagram (5) for explaining the method of manufacturing the circuit board.
- FIG. 6 is a schematic diagram (6) for explaining the method of manufacturing the circuit board.
- FIG. 7 is a schematic diagram (7) for explaining the method of manufacturing the circuit board.
- FIG. 8 is a schematic diagram (8) for explaining the method of manufacturing the circuit board.
- FIG. 1 is a schematic diagram (1) for explaining a circuit board manufacturing method (hereinafter simply referred to as "circuit board manufacturing method”) according to an embodiment of the present invention.
- FIG. 2 is a schematic diagram (2) for explaining the method of
- FIG. 9 is a schematic diagram (9) for explaining the method of manufacturing the circuit board.
- FIG. 10 is a schematic diagram (10) for explaining the method of manufacturing the circuit board.
- FIG. 11 is a schematic diagram (11) for explaining the method of manufacturing the circuit board.
- FIG. 12 is a schematic diagram (12) for explaining the method of manufacturing the circuit board.
- FIG. 13 is a schematic diagram (13) for explaining the method of manufacturing the circuit board.
- FIG. 14 is a schematic diagram (14) for explaining the method of manufacturing the circuit board.
- FIG. 15 is a schematic diagram (15) for explaining the method of manufacturing the circuit board.
- FIG. 16 is a schematic diagram (16) for explaining the method of manufacturing the circuit board.
- FIG. 17 is a schematic diagram (17) for explaining the method of manufacturing the circuit board.
- FIG. 18 is a schematic diagram (18) for explaining the method of manufacturing the circuit board.
- FIG. 19 is a schematic diagram (19) for explaining the method of manufacturing the circuit board.
- FIG. 20 is a schematic diagram (20) for explaining the method of manufacturing the circuit board.
- FIG. 21 is a schematic diagram (21) for explaining the method of manufacturing the circuit board.
- FIG. 22 is a schematic diagram (22) for explaining the method of manufacturing the circuit board.
- FIG. 23 is a schematic diagram (23) for explaining the method of manufacturing the circuit board.
- FIG. 23 is also a schematic diagram of a circuit board in one embodiment of the present invention.
- FIG. 24 is a schematic diagram (1) for explaining a semiconductor package according to one embodiment of the present invention.
- FIG. 25 is a schematic diagram (2) for explaining the semiconductor package according to one embodiment of the present invention.
- FIG. 26 is a schematic diagram (3) for explaining the semiconductor package according to one embodiment of the present invention.
- a resin composition layer is formed so as to embed a conductive circuit, and the resin composition layer is cured to form an insulating layer.
- the resin composition layer is formed using a resin composition containing an epoxy resin, a curing agent, and an inorganic filler from the viewpoint of being able to be formed so as to embed a conductor circuit and exhibiting sufficient insulation after curing. be done.
- epoxy resins include bixylenol type epoxy resin, 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, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type Epoxy resin, naphthylene ether type epoxy resin, trimethylo
- the resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the epoxy resin.
- the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile components of the epoxy resin is preferably 50% by mass or more. More preferably 60% by mass or more, particularly preferably 70% by mass or more.
- Epoxy resins are classified into liquid epoxy resins at a temperature of 20°C (hereinafter referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20°C (hereinafter referred to as “solid epoxy resins").
- the epoxy resin the resin composition may contain only a liquid epoxy resin or only a solid epoxy resin. It is preferably included in combination with an epoxy resin.
- a liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.
- liquid epoxy resins examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, ester skeleton.
- An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are more preferable.
- liquid epoxy resins include "HP4032", “HP4032D”, and “HP4032SS” (naphthalene-type epoxy resins) manufactured by DIC; 828EL” (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation “jER807”, “1750” (bisphenol F type epoxy resin); Mitsubishi Chemical Corporation “jER152” (phenol novolac type epoxy resin); Mitsubishi Chemical Corporation “630", “630LSD” (glycidylamine type epoxy resin); Nippon Steel Chemical & Materials “ZX1059” (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX Co., Ltd.
- EX-721 (glycidyl ester type epoxy resin); "Celoxide 2021P” manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); “PB-3600” manufactured by Daicel (epoxy resin having a butadiene structure) "ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; These may be used individually by 1 type, and may be used in combination of 2 or more type.
- the solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.
- Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthylene Ether-type epoxy resins and bisphenol AF-type epoxy resins are more preferable.
- solid epoxy resins include DIC's "HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” ( cresol novolak type epoxy resin), “N-695" (cresol novolak type epoxy resin), "HP-7200”, “HP-7200HH”, “HP-7200H” (dicyclopentadiene type epoxy resin), "EXA-7311 “, “EXA-7311-G3", “EXA-7311-G4", “EXA-7311-G4S”, "HP6000", "HP6000L” (naphthylene ether type epoxy resin); “EPPN” manufactured by Nippon Kayaku Co., Ltd.
- ESN475V naphthalene type epoxy resin
- ESN485" naphthol novolac type epoxy resin
- YX8800 anthracene type epoxy resin
- PG-100 and "CG-500” manufactured by Osaka Gas Chemicals Co., Ltd.
- YX7760 bisphenol AF type epoxy resin
- YL7800 manufactured by Mitsubishi Chemical Co., Ltd.
- fluorene type epoxy resin "jER1010” (solid bisphenol A type epoxy resin), “jER1031S” (tetraphenylethane type epoxy resin) and the like.
- jER1010 solid bisphenol A type epoxy resin
- jER1031S tetraphenylethane type epoxy resin
- the ratio by mass is preferably 1:0.1 to 1:20, More preferably 1:0.3 to 1:15, particularly preferably 1:0.5 to 1:10.
- the desired effect of the present invention can be remarkably obtained by setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range.
- it usually provides moderate tackiness when used in the form of a resin sheet.
- sufficient flexibility is usually obtained, and handleability is improved.
- a cured product having sufficient breaking strength can be obtained.
- the epoxy equivalent of the epoxy resin is preferably 50 g/eq. ⁇ 5000g/eq. , more preferably 50 g/eq. ⁇ 3000g/eq. , more preferably 80 g/eq. ⁇ 2000 g/eq. , even more preferably 110 g/eq. ⁇ 1000 g/eq. is. By setting it within this range, a cured product of a resin composition having a sufficient cross-linking density can be obtained.
- Epoxy equivalent weight is the weight of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.
- the weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500, from the viewpoint of significantly obtaining the desired effects of the present invention.
- the weight average molecular weight of the epoxy resin is the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).
- the content of the epoxy resin is preferably 10% by mass or more, more preferably 15% by mass, when the non-volatile component in the resin composition is 100% by mass. It is at least 20% by mass, more preferably at least 20% by mass.
- the upper limit of the content of the epoxy resin is preferably 90% by mass or less, more preferably 85% by mass or less, particularly preferably 45% by mass or less, 40% by mass or less, or It is 35% by mass or less.
- the content of the epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably, when the resin component in the resin composition is 100% by mass. is 40% by mass or more or 50% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.
- the "resin component" referred to in the resin composition refers to a non-volatile component constituting the resin composition, excluding the inorganic filler described below.
- curing agents include active ester curing agents, phenolic curing agents and naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, amine curing agents, and acid anhydride curing agents. agents and the like.
- the curing agent may be used singly or in combination of two or more.
- a compound having one or more active ester groups in one molecule can be used as the active ester curing agent.
- active ester curing agents include phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, and the like, and have two or more ester groups per molecule with high reaction activity.
- Preferred are compounds having 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.
- an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. .
- carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
- phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like.
- dicyclopentadiene-type diphenol compound refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.
- the active ester curing agent examples include an active ester curing agent containing a dicyclopentadiene type diphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated phenol novolac, Examples include active ester curing agents containing benzoylated phenol novolacs. Among them, an active ester curing agent containing a naphthalene structure and an active ester curing agent containing a dicyclopentadiene type diphenol structure are more preferable.
- "Dicyclopentadiene-type diphenol structure” represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.
- active ester curing agents include "EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC- 8000H-65TM”, “EXB-8000L-65TM” (manufactured by DIC); “EXB9416-70BK”, “EXB-8100L-65T”, and “EXB-8150L-65T” as naphthalene type active ester curing agents containing a naphthalene structure.
- the content of the active ester curing agent is preferably 1% by mass or more, more preferably 2% by mass or more, based on 100% by mass of the non-volatile components in the resin composition. It is more preferably 4% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.
- the content of the active ester curing agent is preferably 5% by mass or more, more preferably 10% by mass or more, when the resin component in the resin composition is 100% by mass. , more preferably 15% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
- the phenol-based curing agent and naphthol-based curing agent preferably have a novolak structure.
- nitrogen-containing phenolic curing agents and nitrogen-containing naphthol curing agents are preferred, and triazine skeleton-containing phenolic curing agents and triazine skeleton-containing naphthol curing agents are more preferred.
- phenol-based curing agents and naphthol-based curing agents include “MEH-7700”, “MEH-7810” and “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., “NHN” manufactured by Nippon Kayaku Co., Ltd., “CBN”, “GPH”, Nippon Steel Chemical & Materials “SN170”, “SN180”, “SN190”, “SN475", “SN485", “SN495", “SN-495V”, “SN375”, “ SN395", DIC's "TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500” and the like.
- benzoxazine-based curing agents include "JBZ-OD100” (benzoxazine ring equivalent: 218 g/eq.), “JBZ-OP100D” (benzoxazine ring equivalent: 218 g/eq.), "ODA” manufactured by JFE Chemical Co., Ltd.
- cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4 '-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate compounds such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; phenol polyfunctional cyanate compounds derived from novolacs, cresol novolacs, etc.; prepolymers in which these cyanate compounds are partially triflu
- cyanate ester compounds include "PT30", “PT30S” and “PT60” (phenol novolac type polyfunctional cyanate ester) manufactured by Lonza Japan, “ULL-950S” (polyfunctional cyanate ester), and “BA230.” “, “BA230S75” (a prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer), and the like.
- carbodiimide-based curing agents include Carbodiimide (registered trademark) V-03 (carbodiimide group equivalent: 216 g/eq.), V-05 (carbodiimide group equivalent: 216 g/eq.), and V-07 manufactured by Nisshinbo Chemical Co., Ltd. (carbodiimide group equivalent: 200 g/eq.); V-09 (carbodiimide group equivalent: 200 g/eq.); Rhein Chemie Stabaxol (registered trademark) P (carbodiimide group equivalent: 302 g/eq.).
- Amine-based curing agents include resins having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like. Among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention.
- Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine-based curing agents include 4,4′-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 3,3′.
- acid anhydride-based curing agents include compounds having one or more acid anhydride groups in one molecule.
- Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid.
- the ratio of the epoxy resin to the curing agent is [total number of epoxy groups in the epoxy resin]:[total number of reactive groups in the curing agent], and is preferably in the range of 1:0.01 to 1:5. 1:0.05 to 1:3 is more preferred, and 1:0.1 to 1:2 is even more preferred.
- the number of epoxy groups in the epoxy resin is the sum of all the values obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent.
- the “number of active groups in the curing agent” is the sum of all the values obtained by dividing the mass of the non-volatile component of the curing agent present in the resin composition by the active group equivalent.
- the content of the curing agent is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 100% by mass of the nonvolatile components in the resin composition. It is 5% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
- the content of the curing agent is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably, when the resin component in the resin composition is 100% by mass. is 15% by mass or more or 20% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
- inorganic fillers examples include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and aluminum hydroxide.
- magnesium hydroxide calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, oxide Zirconium, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate.
- calcium carbonate and silica are preferred, and silica is particularly preferred.
- Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica.
- 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.
- Examples of commercially available inorganic fillers include “UFP-30” manufactured by Denka; “SP60-05”, “SP507-05” and “SPH516-05" manufactured by Nippon Steel Chemical &Materials; “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C” manufactured by Tokuyama; “SC2500SQ” etc. are mentioned.
- the average particle size of the inorganic filler is preferably 0.6 ⁇ m or less, more It is preferably 0.5 ⁇ m or less, more preferably 0.4 ⁇ m or less, more preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, still more preferably 0.03 ⁇ m or more.
- the specific surface area of the inorganic filler is preferably 1 m 2 /g or more, more preferably 2 m 2 /g or more, still more preferably 3 m 2 /g or more. Although there is no particular upper limit, it is preferably 60 m 2 /g or less, 50 m 2 /g or less, or 40 m 2 /g or less.
- the specific surface area can be calculated by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) to adsorb nitrogen gas on the surface of the sample according to the BET method, and using the BET multipoint method.
- the inorganic filler is preferably treated with a surface treatment agent.
- surface treatment agents include vinylsilane coupling agents, (meth)acrylic coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, Examples include silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, and the like.
- vinylsilane-based coupling agents, (meth)acrylic-based coupling agents, and aminosilane-based coupling agents are preferred, and aminosilane-based coupling agents are more preferred, from the viewpoint of significantly obtaining the effects of the present invention.
- one type of surface treatment agent may be used alone, or two or more types may be used in combination.
- surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd. "KBM1003” (vinyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM503” (3-methacryloxypropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM403” (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803” (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.
- the degree of surface treatment with the surface treatment agent is preferably within a predetermined range.
- 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2-5 parts by mass of a surface treatment agent, and is surface-treated with 0.2-3 parts by mass. preferably 0.3 parts by mass to 2 parts by mass of the surface treatment.
- the degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler.
- the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and more preferably 0.2 mg/m 2 from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable.
- it is preferably 1 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and further preferably 0.5 mg/m 2 or less. 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 (eg, 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 ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.
- EMIA-320V manufactured by Horiba Ltd.
- the content of the inorganic filler in the resin composition (and thus the content of the inorganic filler in the resin composition layer and the insulating layer) is determined from the viewpoint of sufficiently reducing the coefficient of thermal expansion and dielectric loss tangent of the insulating layer. It is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more when the non-volatile component in the product is 100% by mass. As will be described later, when the insulating layer contains an inorganic filler, it has been difficult to form a trench-type conductive circuit in a fine pattern.
- the method of the present invention it is possible to form trench-type conductive circuits in extremely fine patterns even when the content of the inorganic filler is even higher.
- the content of the inorganic filler in the resin composition may be increased to 45% by mass or more, 50% by mass or more, or 55% by mass or more.
- the upper limit of the content of the inorganic filler is preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.
- the resin composition may further contain other components.
- Such other components include, for example, curing accelerators, thermoplastic resins, and other additives. Each component will be described below.
- the resin composition may contain a curing accelerator.
- curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Curing accelerators are preferred, and amine-based curing accelerators are more preferred.
- a hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.
- Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.
- amine curing accelerators examples 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, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.
- trialkylamines such as triethylamine and tributylamine
- 4-dimethylaminopyridine such as triethylamine and tributylamine
- 4-dimethylaminopyridine such as triethylamine and tributylamine
- benzyldimethylamine 2,4,6-tris(dimethylaminomethyl)phenol
- 1,8-diazabicyclo (5,4,0)-undecene 1,8-diazabicyclo
- imidazole curing accelerators examples 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-d
- imidazole-based curing accelerator a commercially available product may be used, such as "P200-H50” manufactured by Mitsubishi Chemical Corporation.
- Guanidine curing accelerators include, for example, 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] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and
- metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
- organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
- organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate;
- organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
- the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.02% by mass, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention.
- % or more particularly preferably 0.03 mass % or more, preferably 3 mass % or less, more preferably 1 mass % or less, and particularly preferably 0.5 mass % or less.
- the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.05% by mass, when the resin component in the resin composition is 100% by mass. % or more, more preferably 0.1 mass % or more, preferably 3 mass % or less, more preferably 2 mass % or less, still more preferably 1 mass % or less.
- the resin composition may contain a thermoplastic resin.
- thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, and polyester resins. etc., and phenoxy resins are preferred.
- the thermoplastic resin may be used singly or in combination of two or more.
- the polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably 38,000 or more, more preferably 40,000 or more, and even more preferably 42,000 or more.
- the upper limit is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less.
- the polystyrene equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight-average molecular weight of the thermoplastic resin was measured using LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P/K-804L/K- manufactured by Showa Denko Co., Ltd. as a column. 804L can be measured at a column temperature of 40° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.
- phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, and terpene. and a phenoxy resin having one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton.
- the terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.
- a phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.
- Specific examples of phenoxy resins include Mitsubishi Chemical's "1256" and “4250” (both phenoxy resins containing bisphenol A skeleton), "YX8100” (phenoxy resin containing bisphenol S skeleton), and "YX6954” (bisphenolacetophenone).
- polyvinyl acetal resins examples include polyvinyl formal resins and polyvinyl butyral resins, with polyvinyl butyral resins being preferred.
- Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, Denka Butyral 6000-EP, and Sekisui.
- S-lec BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series manufactured by Kagaku Kogyo Co., Ltd. may be mentioned.
- polyimide resins include “Ricacoat SN20” and “Ricacoat PN20” manufactured by Shin Nippon Rika.
- polyimide resins also include linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, diisocyanate compounds and tetrabasic acid anhydrides (polyimides described in JP-A-2006-37083), and polysiloxane skeletons. Examples include modified polyimides such as polyimide containing (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).
- polyamide-imide resins include “Vylomax HR11NN” and “Vylomax HR16NN” manufactured by Toyobo.
- polyamideimide resins include modified polyamideimides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimides) manufactured by Hitachi Chemical Co., Ltd.
- polyethersulfone resin examples include "PES5003P” manufactured by Sumitomo Chemical Co., Ltd.
- polyphenylene ether resin include oligophenylene ether/styrene resin "OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Company.
- polyetheretherketone resin examples include "Sumiproy K” manufactured by Sumitomo Chemical Co., Ltd., and the like.
- polyetherimide resin include "Ultem” manufactured by GE.
- polysulfone resins include polysulfone "P1700” and “P3500” manufactured by Solvay Advanced Polymers.
- polyolefin resins include ethylene-based copolymers such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer.
- Resin polyolefin elastomers such as polypropylene and ethylene-propylene block copolymers.
- polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl terephthalate resin, and the like.
- the resin composition comprises one or more thermoplastic resins selected from the group consisting of phenoxy resins and polyvinyl acetal resins.
- a phenoxy resin is preferable as the thermoplastic resin, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferable.
- the content of the thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.3% by mass, when the non-volatile component in the resin composition is 100% by mass. % or more, more preferably 0.5 mass % or more.
- the upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
- the content of the thermoplastic resin is preferably 0.5% by mass or more, more preferably 1% by mass or more, when the resin component in the resin composition is 100% by mass. , more preferably 1.5% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.
- the resin composition may further contain other additives.
- additives include organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, and crystal violet.
- silicone leveling agents acrylic polymer leveling agents and other leveling agents; bentone, montmorillonite and other thickening agents; silicone antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents Antifoaming agents such as foaming agents and vinyl resin antifoaming agents; Adhesion improving agents such as urea silane; Adhesion imparting agents such as triazole adhesion imparting agents, tetrazole adhesion imparting agents, triazine adhesion imparting agents Antioxidants such as hindered phenol antioxidants; Fluorescent brighteners such as stilbene derivatives; Surfactants such as fluorine surfactants and silicone surfactants; , phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (e.g.
- melamine sulfate melamine sulfate
- halogen flame retardants e.g. antimony trioxide
- Dispersants such as oxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, cationic dispersants; borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers , isocyanate-based stabilizers, carboxylic acid-based stabilizers, carboxylic acid anhydride-based stabilizers, and the like.
- These additives may be used singly or in combination of two or more. The content of such additives may be determined according to the properties required for the insulating layer.
- the method of preparing the resin composition is not particularly limited, and examples thereof include a method of mixing and dispersing the compounding ingredients, if necessary, with a solvent or the like using a rotary mixer or the like.
- the minimum melt viscosity of the resin composition (and thus the resin composition layer) is preferably 5000 poise or less, more preferably 4500 poise or less, and still more preferably 4500 poise or less, from the viewpoint of embedding the conductor circuit and holding the conductor circuit without collapsing. It is 4000 poise or less. From the viewpoint of preventing exudation during formation of the resin composition layer and improving workability, the poise is preferably 100 poise or more, more preferably 200 poise or more, and even more preferably 300 poise or more.
- the minimum melt viscosity of the resin composition can be obtained by measuring the melt viscosity by a dynamic viscoelasticity method, as shown in ⁇ Measurement of Minimum Melt Viscosity> below.
- a method of manufacturing a circuit board according to the present invention (hereinafter also simply referred to as "method of the present invention") is characterized by including the following steps (X), (Y) and (Z). (X) forming a first conductor circuit on the metal layer of the base material with the metal layer; (Y) forming a resin composition layer with a resin composition so as to embed the first conductor circuit formed on the metal layer; and curing the resin composition layer to form an insulating layer (Z) removing the base material with the metal layer to form a circuit board having a first main surface where the first conductor circuit is exposed Further, the method for manufacturing a circuit board of the present invention is characterized in that the resin composition contains an epoxy resin, a curing agent and an inorganic filler.
- a conductive circuit is formed on the metal layer of a substrate with a metal layer, an insulating layer is formed so as to embed the conductive circuit, and then the substrate with the metal layer is removed to expose the conductive circuit.
- the method it is not necessary to selectively remove the metal layer (seed layer) of the part where the conductive circuit is not formed by etching, and it is possible to prevent the conductive circuit from being affected by the etching, and in turn, wiring can be performed in a fine pattern. (conductor circuit) can be formed, which is advantageous.
- the metal layer is removed by etching or the like, and the conductive circuit opening is formed into a concave shape, thereby improving the strength and reliability of the pad/wiring joint formed thereon. is also advantageous.
- an insulating layer is laser-processed to form a trench (groove), and the trench is filled with a conductor using a sputtering method or the like. A trench type conductor circuit was formed.
- the trench type conductor circuit can be formed with a minimum line/space ratio (L/S) of 2/2 ⁇ m or less. It is possible to form an extremely fine pattern such as Therefore, the present invention significantly contributes to finer wiring of circuit boards and further to higher functionality of semiconductor packages.
- step (X) a first conductor circuit is formed on the metal layer of the base material with the metal layer.
- the substrate with a metal layer used in step (X) is not particularly limited as long as it includes a substrate and a metal layer provided on the substrate.
- the metal layer functions as a seed layer for forming a conductive circuit
- the substrate functions as a support for the metal layer.
- the constituent material of the substrate is not particularly limited, and any substrate selected from metal substrates, inorganic substrates and organic substrates may be used.
- the substrate is selected from metallic, inorganic and organic substrates that differ in composition from the metallic layer.
- metal substrate that has a different composition from the metal layer
- its constituent material is not particularly limited as long as it has a different composition from the metal layer.
- Metal materials include, for example, copper, aluminum, and alloys thereof with other metals (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).
- the thickness of the metal substrate is not particularly limited, and may be, for example, in the range of 0.1 mm or more and 5 mm or less.
- inorganic substrates include glass substrates and ceramics substrates
- organic substrates include substrates made of plastic materials.
- the material of the glass substrate is not particularly limited, and various glass materials such as borosilicate glass, quartz glass, lead glass, and soda-lime glass may be used.
- the material of the ceramic substrate is not particularly limited, and various ceramic materials such as alumina and zirconia may be used.
- plastic materials include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), Examples include polyether sulfide (PES), polyether ketone, and polyimide. Composite materials such as fiber reinforced plastics may also be used.
- the thickness of these inorganic base materials and organic base materials is not particularly limited, and may be appropriately determined according to the type thereof.
- a substrate with a metal layer includes a metal layer provided on the substrate.
- the surface of the substrate on which such a metal layer is provided is preferably smooth and flat.
- the metal material constituting the metal layer is not particularly limited as long as it can form a conductor layer on the surface of the metal layer. , chromium, magnesium, nickel, zirconium, silicon, titanium, etc.).
- the metal layer can be formed on the substrate by, for example, sputtering, electroless plating, or application of an ultra-thin metal foil, and is preferably formed by sputtering.
- the thickness of the metal layer is preferably less than 0.5 ⁇ m from the viewpoint of improving the yield by forming a uniform concave shape in the conductive circuit opening after removing the metal layer by etching or the like. , less than 0.3 ⁇ m, less than 0.2 ⁇ m, or less than 0.1 ⁇ m.
- the lower limit of the thickness of the metal layer is not particularly limited, it may be, for example, 0.01 ⁇ m or more, 0.02 ⁇ m or more, or 0.03 ⁇ m or more from the viewpoint of facilitating the formation of the first conductive circuit described later.
- the metal layer "provided on the base material” means that the metal layer is provided (directly) by bonding to the base material, and the metal layer is provided on the base material other than the base material. The case where it is provided through a layer is also included.
- the other layer is not particularly limited as long as it does not impede the effects of the present invention.
- examples include a release layer that enables Any conventionally known adhesive layer or release layer may be used as long as it exhibits the desired function.
- the substrate with a metal layer has a peeling layer between the metal layer and the substrate, the substrate can be peeled off in the step (Z) described later, and the first conductor circuit (trench-type conductor It is preferable because a circuit board having a first main surface on which the circuit) is exposed can be easily formed. Therefore, in one preferred embodiment, the substrate with a metal layer includes a release layer between the substrate and the metal layer.
- the release layer is not particularly limited as long as it can release the base material from the metal layer.
- An organic film that evaporates (sublimes) and the like are included (International Publication No. 2018/025957).
- the arithmetic mean roughness Ra of the surface of the metal layer on which the conductor circuit is formed is preferably 200 nm or less, more preferably 150 nm or less, from the viewpoint that the first conductor circuit can be formed in a fine pattern. More preferably, it is 100 nm or less, 80 nm or less, 60 nm or less, 50 nm or less, 40 nm or less, or 20 nm or less.
- the lower limit of Ra is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, or 3 nm or more. Therefore, in one embodiment, the arithmetic mean roughness Ra of the metal layer surface is 200 nm or less.
- the difference TTV Total Thickness Variation
- the difference TTV between the maximum value and the minimum value of the height of the metal layer surface measured in the thickness direction of the substrate with the metal layer is the first conductor circuit in the fine pattern.
- the lower limit of the TTV is not particularly limited, and may be, for example, 1 ⁇ m or more, 2 ⁇ m or more, or 3 ⁇ m or more. Therefore, in one embodiment, the difference TTV between the maximum height and the minimum height of the metal layer surface measured in the thickness direction of the substrate with the metal layer is 50 ⁇ m or less.
- the first conductor circuit is formed on the metal layer of the base material with the metal layer.
- step (X) comprises (X-1) providing a photoresist on the metal layer, exposing and developing the photoresist to expose the metal layer corresponding to the circuit pattern of the first conductor circuit to be formed, and (X-2) ) forming a conductor layer over the exposed metal layer to form a first conductor circuit;
- the photoresist a conventionally known one that can be developed in a desired conductor circuit pattern may be used, and either a film photoresist (dry film photoresist) or a liquid photoresist may be used.
- the conductor layer is preferably formed by electroplating using the exposed metal layer as a plating seed layer.
- the metal layer (seed layer) of the circuit unformed portion is removed by etching performed by a normal semi-additive method. is not required.
- etching performed by a normal semi-additive method.
- a conductive circuit is formed on the metal layer of a substrate with a metal layer, and an insulating layer is formed so as to embed the conductive circuit, and then the substrate with the metal layer is removed. to expose the conductive circuit.
- the conductor circuit can be prevented from being affected by etching, and the first conductor circuit having a desired cross-sectional area can be formed with a fine pattern.
- the first conductor circuit with a fine pattern.
- a conductor circuit having a minimum line/space ratio (L/S) of preferably 5/5 ⁇ m or less, more preferably 3/3 ⁇ m or less, and even more preferably 2/2 ⁇ m or less can be formed. It is possible to form even a conductive circuit with S of 1.5/1.5 ⁇ m or less or 1/1 ⁇ m or less. Therefore, in one preferred embodiment, the minimum line/space ratio (L/S) of the first conductor circuit is 2/2 ⁇ m or less.
- the thickness of the conductor layer forming the first conductor circuit may be determined according to the specific design of the circuit board.
- the aspect ratio ratio T/W of the thickness T of the conductor layer to the line width W of the conductor layer
- a conductor circuit can be formed in a fine pattern.
- step (X) An example of step (X) will be described below with reference to FIGS.
- FIG. 1 shows an example in which a substrate 10 with a metal layer including a substrate 1 and a metal layer 2 provided on the substrate is prepared as such a substrate with a metal layer.
- the preferred range of the arithmetic mean roughness Ra of the surface 10a of the metal layer 2 is as described above.
- the surface roughness of the other major surface 10b facing this is not particularly limited.
- the preferred range of the difference TTV between the maximum and minimum heights of the metal layer surface measured in the thickness direction of the metal layer-attached substrate is also as described above.
- a first conductor circuit is formed on (the surface 10a of) the metal layer 2 of the substrate 10 with the metal layer.
- a photoresist 20 is provided on the metal layer 2 of the substrate 10 with a metal layer (FIG. 2), and the photoresist is exposed and developed to correspond to the circuit pattern of the first conductor circuit to be formed. Expose the metal layer (FIG. 3).
- a conductor layer 30 is formed on the exposed metal layer, and a first conductor circuit composed of these conductor layers 30 is formed (FIG. 4; hereinafter, the first conductor circuit is also denoted by 30 for convenience).
- the photoresist 20 is removed (FIG. 5).
- a desired circuit pattern or interlayer connection pattern may be formed by forming a conductor layer through a photoresist a plurality of times.
- a second photoresist 21 is provided on the metal layer provided with the first conductor circuit 30 (FIG. 6), the photoresist is exposed and developed, and the conductor layer 30 ( The first conductive circuit 30) is exposed (FIG. 7).
- a conductor layer is provided on the exposed first conductor circuit 30 to form an interlayer connection conductor (FIG. 8; in the drawing, the middle conductor layer 30 corresponds to the interlayer connection conductor).
- the second photoresist 21 is removed (FIG. 9).
- FIGS. 3 to 9 show an example in which the first conductor circuit is formed using the photoresist 20 and then the interlayer connection conductor is formed using the photoresist 21.
- the first conductor circuit is formed on the metal layer.
- the procedure is not particularly limited as long as it can be formed.
- the photoresist 20 may be exposed and developed to first expose the metal layer of the substrate corresponding to the interlayer connection pattern, and a conductor layer (interlayer connection conductor) may be formed on the exposed metal layer.
- the photoresist 20 is exposed and developed without removing the photoresist 20, and the metal layer of the substrate is formed corresponding to the circuit pattern of the first conductor circuit to be formed.
- a conductive layer may be formed on the exposed metal layer to form the first conductive circuit.
- step (Y) a resin composition layer is formed from a resin composition so as to embed the first conductor circuit, and the resin composition layer is cured to form an insulating layer.
- the resin composition layer contains a resin composition containing an epoxy resin, a curing agent, and an inorganic filler from the viewpoint of being able to be formed so as to embed the first conductive circuit and exhibiting sufficient insulation after curing. formed using The resin composition is as described in the ⁇ Resin composition> section above.
- the step (Y) may be carried out by applying the above resin composition in a varnish state, or by previously forming a resin composition layer containing the resin composition and laminating the resin composition layer. may be implemented by
- the step (Y) includes bonding a resin sheet including a support film and a resin composition layer provided on the support film such that the resin composition layer is bonded to the first conductor circuit. , laminating to a substrate with a metal layer provided with a first conductive circuit.
- the support film examples 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.
- a film made of a plastic material examples include polyesters such as PET and PEN, acrylics such as PC and PMMA, cyclic polyolefins, TAC, PES, polyetherketone, and polyimide.
- the metal foil examples include copper foil and aluminum foil, with copper foil being preferred.
- a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.
- the support film may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used.
- the resin sheet is prepared by, for example, using the above resin composition as it is, or preparing a resin varnish by dissolving the resin composition in an organic solvent, applying this to a support film using a die coater or the like, and drying it. It can be prepared by forming a resin composition layer.
- the thickness of the resin composition layer is not particularly limited as long as the first conductor circuit can be embedded therein, and may be appropriately determined according to the specific design.
- the lamination of the resin sheet is not particularly limited as long as the resin composition layer can be laminated so as to embed the first conductor circuit. can be done.
- the member for thermocompression bonding the resin sheet to the base material with the metal layer include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). be done.
- an elastic material such as heat-resistant rubber is used so that the resin sheet can sufficiently follow the unevenness of the surface of the base material with the metal layer based on the first conductor circuit and the interlayer connection conductor. It is preferable to press through
- Lamination of resin sheets may be carried out by a vacuum lamination method.
- the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C.
- the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa
- the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds.
- Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.
- Lamination may be performed by a vacuum laminator.
- Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.
- the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support film side. Pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Lamination and smoothing may be performed sequentially using a vacuum laminator.
- the resin composition layer is cured to form an insulating layer. Thereby, an insulating layer is formed so as to embed the first conductive circuit.
- the conditions for curing the resin composition layer are not particularly limited, and conditions that are normally employed when forming an insulating layer of a circuit board may be used.
- thermosetting conditions for the resin composition layer vary depending on the type of resin composition, but in one embodiment, the curing temperature is preferably 120°C to 250°C, more preferably 150°C to 240°C.
- the curing time can preferably be from 5 minutes to 240 minutes, more preferably from 10 minutes to 150 minutes.
- the support film may be removed before curing the resin composition layer, or may be removed after curing the resin composition layer.
- step (Y) An example of step (Y) will be described below with reference to FIGS.
- a resin composition layer 50 is formed so as to embed the first conductive circuit 30, and the resin composition layer is cured to form an insulating layer 51 (FIG. 10).
- the insulating layer 51 is formed thickly so as to bury the first conductor circuit and the interlayer connection conductor, and then the surplus insulating layer 51 is removed by polishing so that the interlayer connection conductor is exposed, and flattened and smoothed. is preferred (FIG. 11).
- the polishing method is not particularly limited, and for example, a chemical mechanical polishing method or a mechanical polishing method such as buffing, belt polishing, or roll polishing may be used.
- a circuit board with a multilayer structure can be manufactured by further forming a conductive circuit and forming an insulating layer.
- the method of the present invention comprises, after step (Y), (i) forming a second conductive circuit on the surface of the insulating layer; and (ii) forming a resin composition layer so as to embed the second conductive circuit, and curing the resin composition layer to form an insulating layer. Further comprising the step of forming.
- step (i)- a second conductive circuit is formed on the insulating layer surface.
- the formation of the second conductive circuit may be carried out according to a known circuit formation method such as a semi-additive method or a full-additive method.
- a metal layer is formed on the surface of the insulating layer, a photoresist is provided on the metal layer, and then the photoresist is exposed and developed to form a desired circuit pattern. to expose a portion of the metal layer corresponding to .
- the photoresist is removed. After that, unnecessary metal layers other than the conductor layer forming portion can be removed by etching or the like to form a second conductor circuit having a desired circuit pattern.
- the metal layer that functions as the plating seed layer may be formed by dry plating or wet plating.
- dry plating include physical vapor deposition (PVD) methods such as sputtering, ion plating, and vacuum deposition, and chemical vapor deposition (CVD) methods such as thermal CVD and plasma CVD.
- CVD chemical vapor deposition
- wet plating includes an electroless plating method.
- the thickness of the metal layer is preferably thin from the viewpoint of forming a thin second conductor circuit. It can be, for example, 2 ⁇ m or less.
- the lower limit of the thickness of the metal layer can be, for example, 0.01 ⁇ m or more, or 0.02 ⁇ m or more, from the viewpoint of suppressing the occurrence of plating burn when forming the conductor layer by electroplating.
- the line/space ratio (L/S) of the second conductor circuit and the thickness of the circuit conductor layer may be appropriately determined according to the specific design of the circuit board.
- step (i) An example of step (i) will be described below with reference to FIGS.
- the second conductor circuit is formed by a semi-additive method.
- a metal layer 31 is formed on the surface of the insulating layer obtained in step (Y) (FIG. 12).
- a photoresist 22 is provided on the metal layer 31 (FIG. 13), and the photoresist 22 is exposed and developed to expose the metal layer 31 corresponding to the circuit pattern of the second conductor circuit to be formed (FIG. 13). 14).
- a conductor layer 30 is formed on the exposed metal layer by electroplating (FIG. 15), and the photoresist 22 is removed (FIG. 16).
- the unnecessary metal layer 31 other than the conductor layer forming portion is removed by etching or the like (FIG. 17), and the second conductor circuit 30 can be formed on the surface of the insulating layer.
- step (ii)- a resin composition layer is formed so as to embed the second conductive circuit, and the resin composition layer is cured to form an insulating layer.
- Step (ii) may be carried out in the same manner as the aforementioned step (Y).
- the composition of the resin composition used to form the resin composition layer is as described in the section ⁇ Resin composition> above, and the configuration of the resin sheet is as described in step (Y).
- the resin composition used to form the resin composition layer in step (ii) may have the same composition as the resin composition used in step (Y), or may have a different composition.
- a circuit board having N+1 circuit layers can be manufactured.
- the steps of drilling the insulating layer and removing the insulating layer are performed.
- a step of desmearing may be performed.
- a resin composition layer 50 is formed so as to embed the second conductive circuit 30 provided on the insulating layer 51, and the resin composition layer is cured to form the insulating layer 51 (FIG. 18).
- the boundary between the insulating layer 51 formed in step (Y) and the resin composition layer 50 (insulating layer 51) formed in step (ii) is indicated by a dotted line.
- the insulating layer is integrated with the insulating layer formed in step (Y) to form the insulating layer 51 .
- the insulating layer is drilled to form via holes 51v (FIG. 19). After desmearing, a conductor can be formed in the via hole 51v to form the via conductor 30 (FIG. 20).
- step (i) and step (ii) are performed once, but as described above, by repeating step (i) and step (ii) N times, the circuit layer A number of N+1 circuit boards can be manufactured.
- step (Z) the substrate with the metal layer is removed to form a circuit board having a first main surface on which the first conductor circuit is exposed.
- Step (Z) can be performed by removing the metal layer and the base material at the same time, or by removing the metal layer after removing the base material, depending on the type of the metal layer and base material used.
- Step (Z) may be carried out, for example, by etching, chemical/mechanical polishing, or the like.
- the metal layer may be removed by etching or the like.
- the step (Z) includes removing the substrate by peeling, and then removing the metal layer by etching and chemical/mechanical polishing. You may remove by methods, such as.
- step (Z) An example of step (Z) will be described below with reference to FIGS.
- the procedure for removing the substrate when using a substrate with a metal layer having a release layer between the metal layer and the substrate is shown.
- the base material 1 is peeled off from the metal layer 2 (FIGS. 20 and 21; the peeling layer is not shown).
- the metal layer 2 derived from the substrate with a metal layer is removed by etching, chemical/mechanical polishing, or the like (FIGS. 22 and 23).
- the circuit board 100 having the first main surface 100a where the first conductive circuit 30 is exposed is formed.
- the circuit board 100 includes a first conductor circuit 30 as a trench-type conductor circuit on the first main surface 100a.
- a trench-type conductive circuit can be formed with an extremely fine structure such as a minimum line/space ratio (L/S) of 2/2 ⁇ m or less. It can be formed in a pattern. Therefore, the circuit board manufactured by the method of the present invention can be suitably used as a circuit board (circuit board for semiconductor packages) such as a rewiring board in the manufacture of semiconductor packages.
- circuit board By the method of the present invention, a circuit board having conductor circuits with extremely fine patterns can be manufactured.
- the invention also provides such a circuit board.
- the circuit board of the present invention comprises having a first principal surface and a second principal surface; including a trench-type conductor circuit on the first major surface;
- the trench-type conductor circuit has a minimum line/space ratio (L/S) of 2/2 ⁇ m or less
- the insulating layer defining the first main surface together with the trench-type conductive circuit is made of a cured resin composition containing an epoxy resin, a curing agent and an inorganic filler.
- circuit board of the present invention The features of the circuit board of the present invention will be described below with reference to FIG.
- a circuit board 100 has a first main surface 100a and a second main surface 100b, and the first conductor exposed on the first main surface.
- a circuit 30 is included.
- the circuit board 100 also includes an insulating layer 51 that defines a first major surface 100 a with the first conductor circuit 30 and is arranged to embed the first conductor circuit 30 . That is, the circuit board 100 according to one embodiment of the present invention includes trench-type conductive circuits 30 (first conductive circuits 30) on the first main surface 100a.
- the trench-type conductive circuit exposed on the first main surface extends from the front to the back of the paper (that is, in the Z direction when the paper is taken as the XY plane).
- the trench-type conductor circuit 30 (first conductor circuit 30) exposed on the first main surface 100a has an extremely fine pattern, and its minimum line/ The space ratio (L/S) is 2/2 ⁇ m or less, more preferably 1/1 ⁇ m or less.
- the insulating layer 51 defining the first main surface 100a together with the trench-type conductive circuit 30 (first conductive circuit 30) is made of epoxy resin, a curing agent and an inorganic filler. It consists of a cured product of a resin composition containing The resin composition is as described in the ⁇ Resin composition> section above, but from the viewpoint of achieving properties such as a low coefficient of thermal expansion and a low dielectric loss tangent, the insulating layer contains an inorganic filler. As described above, when the insulating layer contains an inorganic filler, it is difficult to form a trench-type conductive circuit in a fine pattern.
- the insulating layer contains inorganic fillers, and even when the content of inorganic fillers is high, trench-type conductor circuits can be produced extremely well. It can be formed in a fine pattern.
- the content of the inorganic filler in the insulating layer is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. It is also preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less. Therefore, in a preferred embodiment, the content of the inorganic filler in the insulating layer that defines the first main surface together with the trench-type conductor circuit is 20% by mass or more.
- All insulating layers may have the same configuration.
- the circuit board of the present invention preferably has a multi-layer structure with two or more circuit layers (including the first conductor circuit).
- the number of circuit layers may be determined according to the specific design of the circuit board, but is preferably 3 or more, 4 or more, or 5 or more.
- the upper limit of the number of circuit layers is not particularly limited, and may be, for example, 50 or less, 40 or less, or 30 or less.
- the method for manufacturing a circuit board having a multilayer structure is as described in the above [Method for manufacturing a circuit board].
- a trench-type conductive circuit having a good cross-sectional shape can be formed. Specifically, a cross section in a direction Y perpendicular to the first main surface 100a and also perpendicular to the extending direction of the trench-type conductive circuit 30 (that is, the cross section shown in FIG. 23; the direction Y is the vertical direction in FIG. 23) ), the angle difference between the direction y1 and the direction Y of the straight line defined by the side walls of the trench-type conductive circuit 30 is 20° or less.
- the angle difference between the direction y1 and the direction Y is preferably 15° or less, more preferably 10° or less, and still more preferably 8° or less, 6° or less, 5° or less, 4° or less, 2° or less, or 1°. It is possible to form even a trench-type conductor circuit in which the angle difference is substantially 0°.
- the circuit board manufactured by the method of the present invention even if the insulating layer contains an inorganic filler, or even if the content of the inorganic filler is high, as described above, A trench-type conductive circuit having a good cross-sectional shape can be formed.
- the circuit board manufactured by the method of the present invention has a width from the first main surface toward the depth direction of the circuit board. tend to result in reverse tapered conductor circuits with increasing .
- the trench-type conductive circuit has an inverse tapered shape with a width that increases from the first main surface toward the depth direction of the circuit board.
- the arithmetic mean roughness Ra of the first main surface is preferably 200 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less, 80 nm or less, 60 nm or less, 50 nm or less, 40 nm or less, or 20 nm. It is below.
- the lower limit of Ra is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, or 3 nm or more. Therefore, in one preferred embodiment, the arithmetic mean roughness Ra of the first main surface of the circuit board of the present invention is 200 nm or less.
- the difference TTV between the maximum value and the minimum value of the height of the first main surface measured in the thickness direction of the circuit board is preferably 50 ⁇ m or less, more preferably 50 ⁇ m or less, from the viewpoint that the first conductive circuit can be formed with a fine pattern. 40 ⁇ m or less, more preferably 30 ⁇ m or less, 20 ⁇ m or less, 15 ⁇ m or less, 10 ⁇ m or less, 7 ⁇ m or less, or 5 ⁇ m or less.
- the lower limit of the TTV is not particularly limited, and may be, for example, 1 ⁇ m or more, 2 ⁇ m or more, or 3 ⁇ m or more. Therefore, in one embodiment, the difference TTV between the maximum and minimum heights of the first main surface measured in the thickness direction of the circuit board is 50 ⁇ m or less.
- a semiconductor chip is electrically connected to a first main surface (specifically, a first conductive circuit (trench-type conductive circuit)) of a circuit board.
- a first main surface specifically, a first conductive circuit (trench-type conductive circuit)
- a circuit board of the present invention it is possible to connect the semiconductor chips easily and accurately.
- a trench-type conductor circuit having a high aspect ratio can be formed with a fine pattern.
- the trench-shaped conductive circuit The ratio of thickness T to width W (T/W) is preferably 1.5 or more, more preferably 2 or more, 2.5 or more, or 3 or more.
- the upper limit of the aspect ratio (T/W) can be, for example, 10 or less, 8 or less.
- the width W is calculated when calculating the aspect ratio (T/W). Take the maximum value.
- a portion of the first conductive circuit may be removed along with the substrate.
- the trench conductor The opening (exposed surface) of the circuit 30 is recessed by 0.05 W or more from the exposed surface of the insulating layer 51 that defines the first main surface together with the trench-type conductive circuit 30 .
- W represents the width W of the trench-type conductor circuit in the same cross section, as described above.
- the recess may be 0.06 W or more, 0.08 W or more, or 0.1 W or more, and the upper limit thereof may be, for example, 0.5 W or less, 0.4 W or less, or 0.3 W or less.
- the trench-type conductive circuit has a reverse tapered shape in which the width increases in the depth direction of the circuit board from the first main surface, and the width is narrower on the first main surface side. has a concave shape at
- the circuit board of the present invention can be suitably used as a circuit board (circuit board for semiconductor packages) such as a rewiring board in the manufacture of semiconductor packages.
- a circuit board circuit board for semiconductor packages
- a rewiring board in the manufacture of semiconductor packages.
- a first main surface specifically, a first conductive circuit (trench-type conductive circuit)
- Board connection terminals such as bumps are formed on the second main surface (100b in FIG. 23) of the circuit board.
- a semiconductor package can be manufactured using the circuit board of the present invention.
- the invention also provides such a semiconductor package.
- the semiconductor package of the present invention comprises a circuit board of the present invention and a trench-type conductive circuit (first conductive circuit) on the first main surface so as to be electrically connected to the circuit board. and a semiconductor chip provided.
- a semiconductor package according to one embodiment of the present invention has a semiconductor chip on a first main surface 100a so as to be electrically connected to a trench-type conductive circuit (first conductive circuit 30) of a circuit board 100 of the present invention. 110 (FIG. 24; conductor circuits such as the first conductor circuit are not shown). Then, a sealing layer 120 is provided on the first main surface 100a of the circuit board 100 so as to embed the semiconductor chip 110, and the semiconductor package 200 may be formed by appropriately dividing the semiconductor package 200 (FIGS. 25 and 26). ). The sealing layer 120 may be formed using a conventionally known sealing material (sealing resin composition) used in the manufacture of semiconductor packages.
- the semiconductor package of the present invention may be either a fan-in type package or a fan-out type package.
- 24 to 26 show a fan-out package having a circuit board 100 with a larger area than the semiconductor chip 110.
- FIG. When the semiconductor package of the present invention is a fan-out type package, combined with the inherent feature of the fan-out type package that a rewiring layer can be formed over a large area, a conductor circuit can be formed over a large area with a fine pattern. It is advantageous because it can be formed in Therefore, in one preferred embodiment, the semiconductor package of the present invention is a fan-out package.
- Inorganic filler 1 N-phenyl-3-aminopropyltri Surface-treated with 2 parts of methoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.).
- Preparation Example 2> (Preparation of Resin Composition 2) (1) A resin composition 2 was prepared in the same manner as in Preparation Example 1, except that the amount of the inorganic filler 1 was changed from 45 parts to 65 parts.
- Example 1 (1) Preparation of resin sheet As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc., thickness 38 ⁇ m, softening point 130 °C, “release PET”) was prepared. The resin composition 1 is uniformly coated on the release agent of the support with a die coater so that the thickness of the resin composition layer after drying is 20 ⁇ m, and dried at 70° C. to 95° C. for 4 minutes. Thus, a resin composition layer was provided on the release PET. Next, on the surface of the resin composition layer that is not bonded to the support, a rough surface of a polypropylene film (manufactured by Oji F-Tex Co., Ltd.
- a polypropylene film manufactured by Oji F-Tex Co., Ltd.
- circuit board for evaluation was manufactured by the following procedure.
- a metal layer (Cu layer) having a thickness of 200 nm was formed on the surface of the glass wafer using a sputtering apparatus (“E-400S” manufactured by Canon Anelva Corporation).
- substrate A was singulated by dicing and polished from the substrate (glass wafer) side. Although the exact thickness of the polished surface was not measured, it was confirmed that the polishing did not reach the metal layer (copper layer) and that some of the glass wafer remained.
- This substrate is referred to as substrate B.
- substrate C Etching Removal of Remaining Base Material
- Substrate B was immersed in an aqueous solution of hydrogen fluoride adjusted to 5% at 25° C. for 30 minutes to completely remove the base material (glass wafer) and remove the exposed metal layer from the substrate. Obtained. This substrate is referred to as substrate C.
- Example 2 A circuit board for evaluation A was produced in the same manner as in Example 1, except that the resin composition 2 was used instead of the resin composition 1.
- the melt viscosities of Resin Compositions 1 and 2 were measured using a dynamic viscoelasticity measuring device (“Rheosol-G3000” manufactured by UBM Co., Ltd.) to obtain the lowest melt viscosities. Specifically, 1 g of the sample resin composition was heated from a starting temperature of 60° C. to 200° C. at a rate of 5° C./min using a parallel plate with a diameter of 18 mm. The dynamic viscoelastic modulus was measured under the measurement conditions of vibration of 1 Hz and strain of 1 deg, and the minimum melt viscosity (poise) was obtained from the minimum value of the melt viscosity.
- a dynamic viscoelasticity measuring device (“Rheosol-G3000” manufactured by UBM Co., Ltd.)
- the resin sheets prepared using the resin compositions 1 and 2 were heated at 180° C. for 90 minutes to thermally cure the resin composition layers.
- Evaluation of embeddability The evaluation circuit board A was observed from the first conductor circuit side using a non-contact interference microscope (WYKO). Then, the embeddability was evaluated according to the following criteria. Evaluation criteria: ⁇ : Depression due to resin defect between wirings and defective embedding was observed ⁇ : The above defective embedding was not observed
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Abstract
Description
[1] 下記工程(X)、(Y)及び(Z):
(X)金属層付き基材の該金属層上に、第1導体回路を形成する工程
(Y)前記金属層上に形成された第1導体回路を埋め込むように樹脂組成物により樹脂組成物層を形成し、該樹脂組成物層を硬化させて絶縁層を形成する工程
(Z)金属層付き基材を除去して、第1導体回路が露出した第1の主面を有する回路基板を形成する工程
を含む、回路基板の製造方法であって、
樹脂組成物が、エポキシ樹脂、硬化剤及び無機充填材を含む、回路基板の製造方法。
[2] 樹脂組成物中の無機充填材の含有量が、樹脂組成物中の不揮発成分を100質量%とした場合、20質量%以上75質量%以下である、[1]に記載の方法。
[3] 無機充填材の平均粒子径が0.6μm以下である、[1]又は[2]に記載の方法。
[4] 無機充填材がシリカである、[1]~[3]のいずれかに記載の方法。
[5] 樹脂組成物の最低溶融粘度が5000poise以下である、[1]~[4]のいずれかに記載の方法。
[6] 金属層の厚みが0.5μm未満である、[1]~[5]のいずれかに記載の方法。
[7] 金属層表面の算術平均粗さRaが200nm以下であり、金属層付き基材の厚み方向に測定した該金属層表面の高さの最大値と最小値の差TTVが50μm以下である、[1]~[6]のいずれかに記載の方法。
[8] 金属層付き基材において、基材が、金属層とは組成が異なる金属基材、無機基材及び有機基材から選ばれる、[1]~[7]のいずれかに記載の方法。
[9] 工程(Z)が、基材を除去した後、金属層を除去することによって行われる、[1]~[8]のいずれかに記載の方法。
[10] 工程(X)が、
(X-1)金属層上にフォトレジストを設け、該フォトレジストを露光・現像して、形成すべき第1導体回路の回路パターンに対応して金属層を露出させること、及び
(X-2)露出した金属層上に導体層を形成し、第1導体回路を形成すること
を含む、[1]~[9]のいずれかに記載の方法。
[11] 第1導体回路が、トレンチ型の導体回路を含む、[1]~[10]のいずれかに記載の方法。
[12] 工程(Y)が、支持フィルムと該支持フィルム上に設けられた樹脂組成物層とを含む樹脂シートを、該樹脂組成物層が第1導体回路と接合するように、基材に積層することを含む、[1]~[11]のいずれかに記載の方法。
[13] 工程(Y)の後に、
(i)絶縁層表面上に、第2導体回路を形成する工程、及び
(ii)第2導体回路を埋め込むように樹脂組成物層を形成し、該樹脂組成物層を硬化させて絶縁層を形成する工程
を含む、[1]~[12]のいずれかに記載の方法。
[14] 回路基板が、半導体パッケージ用である、[1]~[13]のいずれかに記載の方法。
[15] 第1の主面及び第2の主面を有する回路基板であって、
第1の主面においてトレンチ型の導体回路を含み、
トレンチ型の導体回路の最小ライン/スペース比(L/S)が2/2μm以下であり、
第1の主面に垂直であり且つトレンチ型の導体回路の延在方向にも垂直な方向Yにおける断面において、トレンチ型の導体回路の側壁が画定する直線の方向y1と方向Yとの角度差が20°以下であり、
トレンチ型の導体回路と共に第1の主面を画定する絶縁層が、エポキシ樹脂、硬化剤及び無機充填材を含む樹脂組成物の硬化物からなる、回路基板。
[16] トレンチ型の導体回路が、第1の主面から回路基板の深さ方向に向かって幅が増大する逆テーパー形状を有する、[15]に記載の回路基板。
[17] 第1の主面に垂直であり且つトレンチ型の導体回路の延在方向にも垂直な方向Yにおける断面において、トレンチ型の導体回路の厚さTと幅Wの比(T/W)が1.5以上である、[15]又は[16]に記載の回路基板。
[18] 第1の主面に垂直であり且つトレンチ型の導体回路の延在方向にも垂直な方向Yにおける断面において、トレンチ型の導体回路の露出面が、トレンチ型の導体回路と共に第1の主面を画定する絶縁層の露出面より0.05W以上凹んでいる、[15]~[17]のいずれかに記載の回路基板。
[19] 回路層数が2以上の多層構造を有する、[15]~[18]のいずれかに記載の回路基板。
[20] [15]~[19]のいずれかに記載される回路基板と、該回路基板のトレンチ型の導体回路と電気的に接続されるように第1の主面上に設けられた半導体チップとを含む、半導体パッケージ。
[21] ファンアウト(Fan-Out)型パッケージである、[20]に記載の半導体パッケージ。
本発明の回路基板の製造方法においては、導体回路を埋め込むように樹脂組成物層を形成し、該樹脂組成物層を硬化させて絶縁層を形成する。ここで、樹脂組成物層は、導体回路を埋め込むように形成し得ると共に硬化後に十分な絶縁性を呈する等の観点から、エポキシ樹脂、硬化剤及び無機充填材を含む樹脂組成物を用いて形成される。
エポキシ樹脂としては、例えば、ビキシレノール型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ビスフェノールAF型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスフェノール型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、tert-ブチル-カテコール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフトール型エポキシ樹脂、アントラセン型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、線状脂肪族エポキシ樹脂、ブタジエン構造を有するエポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、スピロ環含有エポキシ樹脂、シクロヘキサン型エポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、トリメチロール型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂等が挙げられる。エポキシ樹脂は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
硬化剤としては、例えば、活性エステル系硬化剤、フェノール系硬化剤及びナフトール系硬化剤、ベンゾオキサジン系硬化剤、シアネートエステル系硬化剤、カルボジイミド系硬化剤、アミン系硬化剤、酸無水物系硬化剤等が挙げられる。硬化剤は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
無機充填材としては、例えば、シリカ、アルミナ、アルミノシリケート、ガラス、コーディエライト、シリコン酸化物、硫酸バリウム、炭酸バリウム、タルク、クレー、雲母粉、酸化亜鉛、ハイドロタルサイト、ベーマイト、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、窒化ホウ素、窒化アルミニウム、窒化マンガン、ホウ酸アルミニウム、炭酸ストロンチウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸ビスマス、酸化チタン、酸化ジルコニウム、チタン酸バリウム、チタン酸ジルコン酸バリウム、ジルコン酸バリウム、ジルコン酸カルシウム、リン酸ジルコニウム、及びリン酸タングステン酸ジルコニウム等が挙げられる。これらの中でも炭酸カルシウム、シリカが好適であり、シリカが特に好適である。シリカとしては、例えば、無定形シリカ、溶融シリカ、結晶シリカ、合成シリカ、中空シリカ等が挙げられる。また、シリカとしては、球状シリカが好ましい。無機充填材は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
樹脂組成物は、硬化促進剤を含有していてもよい。硬化促進剤としては、例えば、リン系硬化促進剤、アミン系硬化促進剤、イミダゾール系硬化促進剤、グアニジン系硬化促進剤、金属系硬化促進剤等が挙げられ、アミン系硬化促進剤、イミダゾール系硬化促進剤が好ましく、アミン系硬化促進剤がより好ましい。硬化促進剤は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
樹脂組成物は、熱可塑性樹脂を含有していてもよい。熱可塑性樹脂としては、例えば、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリオレフィン樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレンエーテル樹脂、ポリエーテルエーテルケトン樹脂、ポリエステル樹脂等が挙げられ、フェノキシ樹脂が好ましい。熱可塑性樹脂は、1種単独で用いてもよく、又は2種以上を組み合わせて用いてもよい。
樹脂組成物は、その他の添加剤をさらに含んでいてもよい。このような添加剤としては、例えば、ゴム粒子等の有機充填材;有機銅化合物、有機亜鉛化合物、有機コバルト化合物等の有機金属化合物;フタロシアニンブルー、フタロシアニングリーン、アイオディングリーン、ジアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック等の着色剤;シリコーン系レベリング剤、アクリルポリマー系レベリング剤等のレベリング剤;ベントン、モンモリロナイト等の増粘剤;シリコーン系消泡剤、アクリル系消泡剤、フッ素系消泡剤、ビニル樹脂系消泡剤等の消泡剤;尿素シラン等の接着性向上剤;トリアゾール系密着性付与剤、テトラゾール系密着性付与剤、トリアジン系密着性付与剤等の密着性付与剤;ヒンダードフェノール系酸化防止剤等の酸化防止剤;スチルベン誘導体等の蛍光増白剤;フッ素系界面活性剤、シリコーン系界面活性剤等の界面活性剤;リン系難燃剤(例えばリン酸エステル化合物、ホスファゼン化合物、ホスフィン酸化合物、赤リン)、窒素系難燃剤(例えば硫酸メラミン)、ハロゲン系難燃剤、無機系難燃剤(例えば三酸化アンチモン)等の難燃剤;リン酸エステル系分散剤、ポリオキシアルキレン系分散剤、アセチレン系分散剤、シリコーン系分散剤、アニオン性分散剤、カチオン性分散剤等の分散剤;ボレート系安定剤、チタネート系安定剤、アルミネート系安定剤、ジルコネート系安定剤、イソシアネート系安定剤、カルボン酸系安定剤、カルボン酸無水物系安定剤等の安定剤等が挙げられる。これらの添加剤は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。斯かる添加剤の含有量は、絶縁層に要求される特性に応じて決定してよい。
本発明の回路基板の製造方法(以下、単に「本発明の方法」ともいう。)は、下記工程(X)、(Y)及び(Z)を含むことを特徴とする。
(X)金属層付き基材の該金属層上に、第1導体回路を形成する工程
(Y)前記金属層上に形成された第1導体回路を埋め込むように樹脂組成物により樹脂組成物層を形成し、該樹脂組成物層を硬化させて絶縁層を形成する工程
(Z)金属層付き基材を除去して、第1導体回路が露出した第1の主面を有する回路基板を形成する工程
さらに、本発明の回路基板の製造方法は、樹脂組成物がエポキシ樹脂、硬化剤及び無機充填材を含むことも特徴とする。
工程(X)において、金属層付き基材の該金属層上に、第1導体回路を形成する。
工程(X)で用いる金属層付き基材は、基材と、該基材上に設けられた金属層とを含む限り特に限定されない。
本発明においては、金属層付き基材の該金属層上に、第1導体回路を形成する。
(X-1)金属層上にフォトレジストを設け、該フォトレジストを露光・現像して、形成すべき第1導体回路の回路パターンに対応して金属層を露出させること、及び
(X-2)露出した金属層上に導体層を形成し、第1導体回路を形成すること
を含む。
工程(Y)において、第1導体回路を埋め込むように樹脂組成物により樹脂組成物層を形成し、該樹脂組成物層を硬化させて絶縁層を形成する。
先述のとおり、樹脂組成物層は、第1導体回路を埋め込むように形成し得ると共に硬化後に十分な絶縁性を呈する等の観点から、エポキシ樹脂、硬化剤及び無機充填材を含む樹脂組成物を用いて形成される。該樹脂組成物は、上記<樹脂組成物>欄にて説明したとおりである。
樹脂組成物層を硬化させて絶縁層を形成する。これにより、第1導体回路を埋め込むように絶縁層が形成される。
(i)絶縁層表面上に、第2導体回路を形成する工程、及び
(ii)第2導体回路を埋め込むように樹脂組成物層を形成し、該樹脂組成物層を硬化させて絶縁層を形成する工程
をさらに含む。
工程(i)において、絶縁層表面上に、第2導体回路を形成する。
工程(ii)において、第2導体回路を埋め込むように樹脂組成物層を形成し、該樹脂組成物層を硬化させて絶縁層を形成する。
工程(Z)において、金属層付き基材を除去して、第1導体回路が露出した第1の主面を有する回路基板を形成する。
本発明の方法により、極めて微細なパターンを有する導体回路を備えた回路基板を製造することができる。本発明は、斯かる回路基板も提供する。
第1の主面及び第2の主面を有し、
第1の主面においてトレンチ型の導体回路を含み、
トレンチ型の導体回路の最小ライン/スペース比(L/S)が2/2μm以下であり、
トレンチ型の導体回路と共に第1の主面を画定する絶縁層が、エポキシ樹脂、硬化剤及び無機充填材を含む樹脂組成物の硬化物からなることを特徴とする。
本発明の方法によれば、断面形状が良好なトレンチ型の導体回路を形成することができる。詳細には、第1の主面100aに垂直であり且つトレンチ型の導体回路30の延在方向にも垂直な方向Yにおける断面(すなわち、図23に示す断面;方向Yは図23において上下方向である)において、トレンチ型の導体回路30の側壁が画定する直線の方向y1と方向Yとの角度差が20°以下であることを特徴とする。
本発明の回路基板において、第1の主面の算術平均粗さRaは、好ましくは200nm以下、より好ましくは150nm以下、さらに好ましくは100nm以下、80nm以下、60nm以下、50nm以下、40nm以下又は20nm以下である。該Raの下限は、特に限定されず、例えば1nm以上、2nm以上、3nm以上などとし得る。したがって好適な一実施形態において、本発明の回路基板の第1の主面の算術平均粗さRaは200nm以下である。
本発明の方法によれば、微細なパターンにてアスペクト比の高いトレンチ型の導体回路を形成することができる。詳細には、第1の主面100aに垂直であり且つトレンチ型の導体回路30の延在方向にも垂直な方向Yにおける断面(すなわち、図23に示す断面)において、トレンチ型の導体回路の厚さTと幅Wの比(T/W)は、好ましくは1.5以上、より好ましくは2以上、2.5以上又は3以上である。該アスペクト比(T/W)の上限は、例えば10以下、8以下などとし得る。ここで、トレンチ型の導体回路が先述のとおり逆テーパー形状を有するなど、方向Yにおける断面において深さ方向に幅Wが変化する場合、上記アスペクト比(T/W)の算出に際しては幅Wの最大値を採用する。
基材を除去して第1導体回路を露出させる本発明の方法によれば、基材と共に第1導体回路の一部が除去される場合がある。例えば、基材剥離後に金属層をエッチング等に除去することにより第1導体回路の一部を除去することが可能である。したがって一実施形態において、第1の主面100aに垂直であり且つトレンチ型の導体回路30の延在方向にも垂直な方向Yにおける断面(すなわち、図23に示す断面)において、トレンチ型の導体回路30の開口部(露出面)は、トレンチ型の導体回路30と共に第1の主面を画定する絶縁層51の露出面より0.05W以上凹んでいる。ここで、Wは、上記のとおり、同断面におけるトレンチ型の導体回路の幅Wを表す。該凹みは、0.06W以上、0.08W以上又は0.1W以上であってもよく、その上限は、例えば0.5W以下、0.4W以下、0.3W以下などとし得る。
本発明の回路基板を用いて半導体パッケージを製造することができる。本発明は、斯かる半導体パッケージも提供する。
無機充填材1:球状シリカ(電気化学工業社製「UFP-30」、平均粒径0.3μm、比表面積30.7m2/g)100部に対して、N-フェニル-3-アミノプロピルトリメトキシシラン(信越化学工業社製「KBM573」)2部で表面処理したもの。
ビキシレノール型エポキシ樹脂(三菱ケミカル社製「YX4000HK」、エポキシ当量約185)6部、ナフタレン型エポキシ樹脂(日鉄ケミカル&マテリアル社製「ESN475V」、エポキシ当量約332)5部、ビスフェノールAF型エポキシ樹脂(三菱ケミカル社製「YX7760」、エポキシ当量約238)15部、ナフチレンエーテル型エポキシ樹脂(DIC社製「HP6000L」、エポキシ当量約213)2部、シクロヘキサン型エポキシ樹脂(三菱ケミカル社製「ZX1658GS」、エポキシ当量約135)2部、フェノキシ樹脂(三菱ケミカル社製「YX7500BH30」、固形分30質量%のシクロヘキサノン:メチルエチルケトン(MEK)の1:1溶液、Mw=44000)2部を、ソルベントナフサ20部及びシクロヘキサノン10部の混合溶剤に撹拌しながら加熱溶解させた。室温にまで冷却した後、そこへ、トリアジン骨格含有クレゾールノボラック系硬化剤(DIC社製「LA-3018-50P」、水酸基当量約151、固形分50%の2-メトキシプロパノール溶液)4部、活性エステル系硬化剤(DIC社製「EXB-8000L-65TM」、活性基当量約220、不揮発成分65質量%のトルエン溶液)12部、無機充填材1を45部、アミン系硬化促進剤(4-ジメチルアミノピリジン(DMAP))0.05部を混合し、高速回転ミキサーで均一に分散した後に、カートリッジフィルター(ROKITECHNO社製「SHP020」)で濾過して、樹脂組成物1を調製した。
(1)無機充填材1の配合量を45部から65部に変更した点以外は、調製例1と同様にして、樹脂組成物2を調製した。
(1)樹脂シートの作製
支持体として、アルキド樹脂系離型剤(リンテック社製「AL-5」)で離型処理したPETフィルム(東レ社製「ルミラーR80」、厚さ38μm、軟化点130℃、「離型PET」)を用意した。樹脂組成物1を支持体の離型剤上に、乾燥後の樹脂組成物層の厚さが20μmとなるように、ダイコーターにて均一に塗布し、70℃から95℃で4分間乾燥することにより、離型PET上に樹脂組成物層を設けた。次いで、樹脂組成物層の支持体と接合していない面に、保護フィルムとしてポリプロピレンフィルム(王子エフテックス社製「アルファンMA-411」、厚さ15μm)の粗面を、樹脂組成物層と接合するように積層した。これにより、離型PET(支持体)\樹脂組成物層\保護フィルムの層構成を有する樹脂シートを得た。
下記手順で、評価用の回路基板を製造した。
基材として、ガラスウェハ(ウェハの厚さ0.8mm、8インチサイズ)を用意し、130℃のオーブンに投入して30分間乾燥した。
ガラスウェハの表面に金属層を形成した。詳細には、ガラスウェハの表面に、スパッタリング装置(キャノンアネルバ(株)製「E-400S」)を用いて、厚さ200nmの金属層(Cu層)を形成した。
セミアディティブ法に準じて第1導体回路を形成した。詳細には、金属層付き基材の金属層上にフォトレジストを設け、露光・現像してL/S=1.5/1.5μm(線幅1mm)の櫛刃パターンに対応して金属層を露出させた。次いで、硫酸銅電解メッキを行い、露出した金属層上に3μmの厚さで導体層(第1導体回路)を形成した後、フォトレジストを除去した。そして第1導体回路未形成部の金属層のエッチング(シードエッチング)を実施することなく、下記(2-4)の処理に付した。よって、この時点で、導体層は連続している。
樹脂シートから保護フィルムを剥離し、樹脂組成物層を露出させた。そして、バッチ式真空加圧ラミネーター(ニッコー・マテリアルズ社製2ステージビルドアップラミネーター「CVP700」)を用いて、樹脂組成物層が第1導体回路と接するように、金属層付き基材の片面に積層した。この積層は、30秒間減圧して気圧を13hPa以下とした後、130℃、圧力0.74MPaにて45秒間圧着することにより実施した。次いで、120℃、圧力0.5MPaにて75秒間熱プレスして平滑化した。その後、支持体を剥離して、露出した樹脂組成物層上に銅箔(三井金属製「3EC-III」(35μm))を上記と同様の条件で積層した。
上記(2-4)で得た積層体を、100℃のオーブンに投入して60分間加熱し、次いで180℃のオーブンに移し替えて90分間加熱し、樹脂組成物層を熱硬化した。こうして、第1導体回路を埋め込むように金属層付き基材の金属層上に樹脂組成物層の硬化物(絶縁層;厚さ20μm)が設けられた基板Aを得た。
基板Aをダイシングで個片化し、基材(ガラスウェハ)側から研磨した。研磨した正確な厚みは測定していないが、研磨は金属層(銅層)までは到達しておらず、一部のガラスウェハは残存していることを確認した。この基板を基板Bとする。
基板Bを25℃、5%に調整したフッ化水素水溶液に30分間浸けて基材(ガラスウェハ)を完全に除去し、金属層の露出した基板を得た。この基板を基板Cとする。
基板Cをエッチング液(三菱瓦斯化学製「WLC-C2」)を用いたエッチングに供し、金属層を除去して、第1導体回路が露出した回路基板を得た。得られた回路基板を評価用回路基板Aとする。
樹脂組成物1に代えて樹脂組成物2を使用した以外は、実施例1と同様の手順で評価用回路基板Aを作製した。
樹脂組成物1、2の最低溶融粘度や、該樹脂組成物1、2の硬化物の比誘電率・線熱膨張係数、評価用回路基板Aの特性は、以下のとおり、測定・評価した。
樹脂組成物1、2について、動的粘弾性測定装置((株)ユー・ビー・エム製「Rheosol-G3000」)を使用して溶融粘度を測定し、最低溶融粘度を求めた。詳細には、試料樹脂組成物1gについて、直径18mmのパラレルプレートを使用して、開始温度60℃から200℃まで昇温速度5℃/分にて昇温し、測定温度間隔2.5℃、振動1Hz、歪み1degの測定条件にて動的粘弾性率を測定し、溶融粘度の極小値から最低溶融粘度(poise)を求めた。
樹脂組成物1、2を用いて作製した樹脂シートを180℃、90分間加熱して、樹脂組成物層を熱硬化した。得られた樹脂組成物層の硬化物を、幅2mm、長さ80mmの試験片に切断し、空洞共振器摂動法誘電率測定装置(関東応用電子開発社製「CP521」)及びネットワークアナライザー(アジレントテクノロジー社製「E8362B」)を使用して、空洞共振法で測定周波数5.8GHz、23℃にて比誘電率の測定を行った。各硬化物について、2本の試験片について測定を行い(n=2)、平均値を算出した。
樹脂組成物1、2を用いて作製した樹脂シートを180℃、90分間加熱して、樹脂組成物層を熱硬化した。得られた樹脂組成物層の硬化物を、幅5mm、長さ15mmの試験片に切断し、(株)リガク製熱機械分析装置(Thermo Plus TMA8310)を使用して、引張加重法で熱機械分析を行った。試験片を前記装置に装着後、荷重1g、昇温速度5℃/分の測定条件にて連続して2回測定した。2回目の測定における25℃から150℃における平均の線熱膨張係数(ppm/℃)を算出した。
(1)埋め込み性の評価
評価用回路基板Aについて、非接触型干渉顕微鏡(WYKO)を用いて第1導体回路側から観察を行った。そして、以下の基準で埋め込み性を評価した。
評価基準:
×:配線間に樹脂欠損による凹みがあり埋め込み不良が観察されたもの
○:上記埋め込み不良が観察されなかったもの
評価用回路基板Aについて、絶縁信頼性試験を実施した。具体的にはHAST試験機(楠本化成製「PM422」)を用いて、温度130℃、湿度85%の環境下、電極の両端に3.3Vの電圧を印加した(bHAST)。200時間後、評価用回路基板Aを取り出し、その抵抗値を抵抗測定機(J-RAS製「ECM-100」)にて測定した。そして、以下の基準で絶縁性を評価した。
評価基準:
×:抵抗値が108Ω未満
○:抵抗値が108Ω以上
2 金属層
10 金属層付き基材
10a 金属層(第1の主面)
10b 第の2主面
20、21、22 フォトレジスト
30 導体層(導体回路)
31 金属層(めっきシード層)
50 樹脂組成物層
51 絶縁層
51v ビア
100 回路基板
100a 回路基板の第1の主面
100b 回路基板の第2の主面
110 半導体チップ
120 封止層
200 半導体パッケージ
Claims (21)
- 下記工程(X)、(Y)及び(Z):
(X)金属層付き基材の該金属層上に、第1導体回路を形成する工程
(Y)前記金属層上に形成された第1導体回路を埋め込むように樹脂組成物により樹脂組成物層を形成し、該樹脂組成物層を硬化させて絶縁層を形成する工程
(Z)金属層付き基材を除去して、第1導体回路が露出した第1の主面を有する回路基板を形成する工程
を含む、回路基板の製造方法であって、
樹脂組成物が、エポキシ樹脂、硬化剤及び無機充填材を含む、回路基板の製造方法。 - 樹脂組成物中の無機充填材の含有量が、樹脂組成物中の不揮発成分を100質量%とした場合、20質量%以上75質量%以下である、請求項1に記載の方法。
- 無機充填材の平均粒子径が0.6μm以下である、請求項1又は2に記載の方法。
- 無機充填材がシリカである、請求項1~3のいずれか1項に記載の方法。
- 樹脂組成物の最低溶融粘度が5000poise以下である、請求項1~4のいずれか1項に記載の方法。
- 金属層の厚みが0.5μm未満である、請求項1~5のいずれか1項に記載の方法。
- 金属層表面の算術平均粗さRaが200nm以下であり、金属層付き基材の厚み方向に測定した該金属層表面の高さの最大値と最小値の差TTVが50μm以下である、請求項1~6のいずれか1項に記載の方法。
- 金属層付き基材において、基材が、金属層とは組成が異なる金属基材、無機基材及び有機基材から選ばれる、請求項1~7のいずれか1項に記載の方法。
- 工程(Z)が、基材を除去した後、金属層を除去することによって行われる、請求項1~8のいずれか1項に記載の方法。
- 工程(X)が、
(X-1)金属層上にフォトレジストを設け、該フォトレジストを露光・現像して、形成すべき第1導体回路の回路パターンに対応して金属層を露出させること、及び
(X-2)露出した金属層上に導体層を形成し、第1導体回路を形成すること
を含む、請求項1~9のいずれか1項に記載の方法。 - 第1導体回路が、トレンチ型の導体回路を含む、請求項1~10のいずれか1項に記載の方法。
- 工程(Y)が、支持フィルムと該支持フィルム上に設けられた樹脂組成物層とを含む樹脂シートを、該樹脂組成物層が第1導体回路と接合するように、基材に積層することを含む、請求項1~11のいずれか1項に記載の方法。
- 工程(Y)の後に、
(i)絶縁層表面上に、第2導体回路を形成する工程、及び
(ii)第2導体回路を埋め込むように樹脂組成物層を形成し、該樹脂組成物層を硬化させて絶縁層を形成する工程
を含む、請求項1~12のいずれか1項に記載の方法。 - 回路基板が、半導体パッケージ用である、請求項1~13のいずれか1項に記載の方法。
- 第1の主面及び第2の主面を有する回路基板であって、
第1の主面においてトレンチ型の導体回路を含み、
トレンチ型の導体回路の最小ライン/スペース比(L/S)が2/2μm以下であり、
第1の主面に垂直であり且つトレンチ型の導体回路の延在方向にも垂直な方向Yにおける断面において、トレンチ型の導体回路の側壁が画定する直線の方向y1と方向Yとの角度差が20°以下であり、
トレンチ型の導体回路と共に第1の主面を画定する絶縁層が、エポキシ樹脂、硬化剤及び無機充填材を含む樹脂組成物の硬化物からなる、回路基板。 - トレンチ型の導体回路が、第1の主面から回路基板の深さ方向に向かって幅が増大する逆テーパー形状を有する、請求項15に記載の回路基板。
- 第1の主面に垂直であり且つトレンチ型の導体回路の延在方向にも垂直な方向Yにおける断面において、トレンチ型の導体回路の厚さTと幅Wの比(T/W)が1.5以上である、請求項15又は16に記載の回路基板。
- 第1の主面に垂直であり且つトレンチ型の導体回路の延在方向にも垂直な方向Yにおける断面において、トレンチ型の導体回路の露出面が、トレンチ型の導体回路と共に第1の主面を画定する絶縁層の露出面より0.05W以上凹んでいる、請求項15~17のいずれか1項に記載の回路基板。
- 回路層数が2以上の多層構造を有する、請求項15~18のいずれか1項に記載の回路基板。
- 請求項15~19のいずれか1項に記載される回路基板と、該回路基板のトレンチ型の導体回路と電気的に接続されるように第1の主面上に設けられた半導体チップとを含む、半導体パッケージ。
- ファンアウト(Fan-Out)型パッケージである、請求項20に記載の半導体パッケージ。
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