WO2023085184A1 - Feuille de résine multicouche - Google Patents

Feuille de résine multicouche Download PDF

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Publication number
WO2023085184A1
WO2023085184A1 PCT/JP2022/040994 JP2022040994W WO2023085184A1 WO 2023085184 A1 WO2023085184 A1 WO 2023085184A1 JP 2022040994 W JP2022040994 W JP 2022040994W WO 2023085184 A1 WO2023085184 A1 WO 2023085184A1
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WIPO (PCT)
Prior art keywords
resin
resin composition
layer
resin sheet
mass
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PCT/JP2022/040994
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English (en)
Japanese (ja)
Inventor
幸則 江戸
Original Assignee
味の素株式会社
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Application filed by 味の素株式会社 filed Critical 味の素株式会社
Priority to JP2023559589A priority Critical patent/JPWO2023085184A1/ja
Publication of WO2023085184A1 publication Critical patent/WO2023085184A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • 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 multilayer resin sheets. Furthermore, the present invention relates to a support-attached multilayer resin sheet, a printed wiring board, and a semiconductor device obtained by using the multilayer resin sheet. The present invention also relates to a method for producing a printed wiring board using the multilayer resin sheet.
  • the insulating layer is generally formed by laminating a resin composition layer on a circuit board using a resin sheet or the like containing a resin composition layer and curing the resin composition layer.
  • a resin composition layer is laminated on a circuit board using a resin sheet having a plurality of resin composition layers, and the resin composition layer is thermally cured to obtain a cured product, A technique for roughening the cured product to form a thin insulating layer having excellent mechanical strength is disclosed.
  • the surface of the cured product formed by curing the resin composition layer corresponds to the surface undulations of the underlying circuit board (due to the surface unevenness associated with the presence or absence of circuit wiring, etc.). In some cases, undulations occurred, and the flatness of the surface was sometimes poor. If the surface flatness is poor, when forming a conductor layer (wiring layer) on the cured product, the adhesion between the pattern-formed dry film and the insulating layer tends to decrease, resulting in poor formation of fine wiring.
  • the undulations on the surface of the cured product can be somewhat reduced by manipulating the lamination conditions of the resin composition layer. In some cases, the adhesiveness between the insulating layer and the conductive layer formed thereon is lowered.
  • the present invention provides a novel resin sheet that provides a cured product with good surface flatness and good adhesion to a conductor layer even when laminated on a lamination target member having an uneven surface.
  • a multilayer resin sheet comprising two or more resin composition layers, When performing dynamic viscoelasticity measurement at a frequency of 6.28 rad/sec, the elastic modulus (Pa) of the first resin composition layer, which is one of the outermost layers, is G' (A), and the first resin When the elastic modulus (Pa) of the layer excluding the composition layer is G′(B), (Log10(G′(B)) at 100° C.) ⁇ (Log10(G′(A)) at 100° C.) is -2 or more and less than 0.
  • D1 be the average particle size ( ⁇ m) of the inorganic filler in the first resin composition layer
  • D2 be the average particle size ( ⁇ m) of the inorganic filler in the layers other than the first resin composition layer.
  • T is the thickness ( ⁇ m) of the multilayer resin sheet and t is the thickness ( ⁇ m) of the first resin composition layer, t ⁇ (T ⁇ t) [1] to [ 3].
  • a multilayer resin sheet according to any one of [1] to [6] is placed on an inner layer substrate, and the surface of the multilayer resin sheet opposite to the first resin composition layer is bonded to the inner layer substrate.
  • a novel resin sheet that provides a cured product having good surface flatness and good adhesion to a conductor layer even when laminated on a member to be laminated having surface irregularities. can do.
  • the multilayer resin sheet of the present invention it is also possible to produce a cured product exhibiting low surface roughness after roughening treatment.
  • the multilayer resin sheet of the present invention comprises two or more resin composition layers, and when dynamic viscoelasticity measurement is performed at a frequency of 6.28 rad/sec, the first resin composition layer, which is one of the outermost layers, G'(A) is the elastic modulus (Pa) of the layer, and G'(B) is the elastic modulus (Pa) of the layer excluding the first resin composition layer. (B)))-(Log10(G'(A)) at 100°C) is -2 or more and less than 0.
  • the multilayer resin sheet of the present invention has a structure in which two or more resin composition layers are laminated together.
  • the first resin composition layer and the second resin composition layer Both are outermost layers.
  • the outermost layers are the first resin composition layer and the Nth resin composition layer when numbered in ascending order from Nth.
  • the multilayer resin sheet of the present invention is used by being laminated on a member to be laminated (for example, an inner layer substrate to be described later). At this time, the surface ( The other outermost layer; in a multilayer resin sheet consisting of two resin composition layers, the second resin composition layer, and in a multilayer resin sheet consisting of N resin composition layers, the Nth resin composition layer. applicable) is laminated and used so as to be joined to the member to be laminated. Therefore, when laminated on a member to be laminated, the first resin composition layer is on the outside (external environment side), so the first resin composition layer may be simply referred to as the "outer layer" below.
  • the layers other than the first resin composition layer are laminated with the first resin composition layer after being laminated on the member to be laminated. Since it is located between the target member, the layers other than the first resin composition layer may be simply referred to as "inner layer” below.
  • the number of resin composition layers may be two or more, and may be three or more.
  • the multilayer resin sheet of the present invention may be formed by making a difference in the content of each component in the resin sheet substantially in one resin sheet. In this case, the portion where the content of each component is different can be interpreted as the layer interface.
  • the elastic modulus (Pa) of the first resin composition layer which is one of the outermost layers, was G'( A) and the elastic modulus (Pa) of the layer excluding the first resin composition layer is G'(B), (Log10(G'(B)) at 100°C) - (at 100°C Log10(G'(A))) is -2 or more and less than 0.
  • the multilayer resin sheet of the present invention is laminated on a member to be laminated having an uneven surface, the surface flatness is good, and the adhesiveness (adhesive strength) to a conductor layer such as a plated conductor layer is improved. can also provide good cured products. Moreover, according to the multilayer resin sheet of the present invention, it is possible to provide a cured product with a low surface roughness after the roughening treatment.
  • the dynamic viscoelasticity measurement can be performed according to the method described in the section [Dynamic viscoelasticity measurement] below, using a Rheometer device ("AR-2000" manufactured by TA Instruments) at a frequency of 6 .28 rad/sec, 60° C. starting temperature, 5° C./min heating rate, and 0.75% strain.
  • AR-2000 manufactured by TA Instruments
  • the reason why the elastic modulus G′ at 100° C. is used is that the lamination processing temperature generally used when processing a resin sheet that does not contain a fiber base material such as glass cloth is taken into consideration.
  • the above dynamic viscoelasticity measurement is performed at a frequency of 6.28 rad/sec to simulate and reproduce the molding speed during lamination processing.
  • (Log10(G'(B)) at 100°C)-(Log10(G'(A)) at 100°C) is preferably -1. .9 or more, more preferably -1.8 or more, -1.7 or more, -1.6 or more or -1.5 or more, more preferably -1.4 or more, -1.3 or more, -1.2 greater than or equal to -1.1 or greater.
  • (Log 10 at 100 ° C. (G' (B) ))-(Log10(G'(A)) at 100°C) is preferably -0.05 or less, more preferably -0.1 or less, -0.15 or less or -0.2 or less, more preferably -0.25 or less, -0.3 or less, -0.35 or less, -0.4 or less, -0.45 or less, or -0.5 or less.
  • (A) is preferably more than 500 Pa, more preferably 600 Pa or more or 800 Pa or more, more preferably 1,000 Pa or more, 1,500 Pa or more, 2,000 Pa or more, 2,500 Pa or more, 3,000 Pa or more, 3,500 Pa or 4,000 Pa or more, and the upper limit is preferably 100,000 Pa or less, more preferably 95,000 Pa or less, 90,000 Pa or less, 85,000 Pa or less, or 80,000 Pa or less. A range is preferred. Therefore, in a preferred embodiment, the elastic modulus G'(A) at 100°C of the first resin composition layer is 1,000 Pa or more and 100,000 Pa or less.
  • G′(B) at 100° C. is preferably 10 Pa or more, 20 Pa or more, 50 Pa or more, or 100 Pa or more from the viewpoint of handleability when forming a laminate by laminating a multilayer resin sheet on a member to be laminated.
  • the upper limit is preferably 50,000 Pa or less, 40,000 Pa or less, 30,000 Pa or less, 20,000 Pa or less, 15,000 Pa or less, 14,000 Pa or less, 12,000 Pa or less, or 10,000 Pa or less.
  • the layers other than the first resin composition layer are from the viewpoint of obtaining a cured product with a low coefficient of linear thermal expansion, and also from the viewpoint of obtaining a cured product with a low dielectric loss tangent. From the viewpoint of providing a cured product with low loss, it is preferable to contain an inorganic filler. Details of the inorganic filler will be described later.
  • the first resin composition layer also preferably contains an inorganic filler from the viewpoint of providing a cured product with a low coefficient of linear thermal expansion and a low dielectric loss tangent.
  • the first resin composition layer The inorganic filler contained preferably has a smaller average particle diameter than the inorganic filler contained in the layers other than the first resin composition layer.
  • the average particle diameter ( ⁇ m) of the inorganic filler in the first resin composition layer is D1
  • the average particle diameter of the inorganic filler in the layers other than the first resin composition layer is When ( ⁇ m) is D2, D1 ⁇ D2.
  • D1 and D2 are preferably D1 ⁇ 0.9D2, more preferably D1 ⁇ 0.8D2, D1 ⁇ 0.7D2, D1 ⁇ 0.6D2, D1 ⁇ It satisfies the relationship of 0.55D2 or D1 ⁇ 0.5D2. A method for measuring the average particle size of the inorganic filler will be described later.
  • the multilayer resin sheet of the present invention includes the first resin composition.
  • the layers other than the layer are preferably thicker than the first resin composition layer. Therefore, in a preferred embodiment, t ⁇ (T ⁇ t), where T is the thickness ( ⁇ m) of the multilayer resin sheet and t is the thickness ( ⁇ m) of the first resin composition layer.
  • t and T are preferably t ⁇ 0.2T, more preferably t ⁇ 0.15T, t ⁇ 0.1T, t ⁇ 0.08T, t It satisfies the relationship ⁇ 0.06T or t ⁇ 0.05T.
  • t and T are preferably 0.005 T from the viewpoint of realizing better flatness and adhesion to the conductor layer, and from the viewpoint of being able to provide a cured product with a lower surface roughness after roughening treatment. It satisfies the relationship ⁇ t, 0.01T ⁇ t, or 0.02T ⁇ t.
  • the thickness T of the multilayer resin sheet of the present invention differs depending on the application, and may be determined appropriately according to the application.
  • the thickness T of the multilayer resin sheet is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, 120 ⁇ m or less, 100 ⁇ m or less, 80 ⁇ m or less, 60 ⁇ m or less, or 50 ⁇ m or less from the viewpoint of thinning the printed wiring board.
  • the lower limit of the thickness T is not particularly limited, it can be usually 5 ⁇ m or more, 10 ⁇ m or more, or the like.
  • the ingredients and amounts of the first resin composition layer may be applied by replacing the "resin composition layer” described later with the "first resin composition layer”.
  • the "resin composition layer” described later may be read as "the layer other than the first resin composition layer”.
  • the resin composition layer preferably contains an inorganic filler as described above.
  • inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum silicate, 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, oxide
  • examples include titanium, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate.
  • silica is particularly suitable.
  • 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 “SP60-05” and “SP507-05” manufactured by Nippon Steel Chemical &Materials; “SC2500SQ”, “SO-C4" and “SO-C2” manufactured by Admatechs. ”, “SO-C1”, “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C”; Denka “UFP-30”, “DAW-03”, “FB-105FD”; Tokuyama "SILFIL NSS-3N”, “SILFIL NSS-4N”, “SILFIL NSS-5N” manufactured by Taiheiyo Cement Co., Ltd.; “MGH-005" manufactured by Taiheiyo Cement Co., Ltd.;
  • the average particle size of the inorganic filler is not particularly limited, but is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and still more preferably 3 ⁇ m or less, 2 ⁇ m or less, 1 ⁇ m or less, 0.8 ⁇ m or less, or 0.7 ⁇ m or less. is.
  • the lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and still more preferably 0.07 ⁇ m or more, 0.1 ⁇ m or more, or 0.2 ⁇ m or more. be.
  • the average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory.
  • the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement.
  • a measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes.
  • a measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle diameter was calculated as the median diameter.
  • the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.
  • D1 is the average particle size ( ⁇ m) of the inorganic filler in the first resin composition layer
  • D2 is the average particle size ( ⁇ m) of the inorganic filler in the layers other than the first resin composition layer.
  • D1 ⁇ D2 it is preferable that D1 ⁇ D2.
  • a suitable relationship between D1 and D2 is as described above.
  • D1 is preferably 1 ⁇ m or less, more It is preferably 0.8 ⁇ m or less, 0.7 ⁇ m or less, or 0.6 ⁇ m or less, more preferably 0.5 ⁇ m or less, 0.4 ⁇ m or less, 0.3 ⁇ m or less, or 0.2 ⁇ m or less.
  • the lower limit of D1 is as described above, and can be, for example, 0.01 ⁇ m or more, 0.02 ⁇ m or more.
  • the inorganic filler is preferably surface-treated with an appropriate surface treatment agent.
  • the surface treatment can enhance the moisture resistance and dispersibility of the inorganic filler.
  • surface treatment agents include vinyl-based silane coupling agents, epoxy-based silane coupling agents, styryl-based silane coupling agents, (meth)acrylic-based silane coupling agents, amino-based silane coupling agents, and isocyanurate-based silanes.
  • Silane coupling agents such as coupling agents, ureido-based silane coupling agents, mercapto-based silane coupling agents, isocyanate-based silane coupling agents, and acid anhydride-based silane coupling agents; methyltrimethoxysilane, phenyltrimethoxysilane, etc. non-silane coupling-alkoxysilane compounds; silazane compounds;
  • the surface treatment agents may be used singly or in combination of two or more.
  • Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBE903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573” (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31” ( hexamethyldisilazane) and the like.
  • the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2 to 5% by mass of a surface treatment agent.
  • 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 1.0 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and 0.5 mg/m 2 or less .
  • the amount of carbon per unit surface area of component (D) 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 layer may be determined according to the properties required for the multilayer resin sheet. ) is 100% by mass, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, 46% by mass or more, or 48% by mass or more, more preferably 50% by mass or more , 55% by mass or more, 60% by mass or more, 65% by mass or more, or 70% by mass or more.
  • the upper limit of the content of the inorganic filler is not particularly limited, but may be, for example, 90% by mass or less, or 80% by mass or less.
  • the content C1 of the inorganic filler in the first resin composition layer is preferably 45% by mass or more, more preferably 50% by mass or more, 52% by mass or more, It is 54% by mass or more, or 55% by mass or more, and the content C1 may be increased to, for example, 56% by mass or more, 58% by mass or more, or 60% by mass or more.
  • the upper limit of the content C1 is as described above, it is preferably 80% by mass or less, 75% by mass or less, or 70% by mass or less.
  • the content C2 of the inorganic filler in the layers other than the first resin composition layer is preferably 45% by mass or more, more preferably 50% by mass or more, and 55% by mass. or 60% by mass or more, more preferably 65% by mass or more, 66% by mass or more, 68% by mass or more, 70% by mass or more, 72% by mass or more, or 74% by mass.
  • the upper limit of the content C2 is as described above, it is preferably 80% by mass or less, 75% by mass or less, or 70% by mass or less.
  • the content C1 (% by mass) of the inorganic filler in the first resin composition layer and the content C2 (% by mass) of the inorganic filler in the layers other than the first resin composition layer are the above As long as (Log10(G'(B)) at 100°C) - (Log10(G'(A)) at 100°C) is within the specific range of the present invention, C1 may be higher than C2, and C2 is C1 It may be higher and C1 and C2 may be the same.
  • the content C1 (% by mass) of the inorganic filler in the first resin composition layer and the content C2 (% by mass) of the inorganic filler in the layers excluding the first resin composition layer satisfies the relationship C1 ⁇ C2.
  • Preferred ranges for C1 and C2 are as described above.
  • the content C1 (% by mass) of the inorganic filler in the first resin composition layer and the content C2 (mass %) of the inorganic filler in the layers other than the first resin composition layer %) satisfies the relationship C1 ⁇ C2.
  • the preferred ranges of C1 and C2 are as described above, but the difference between C1 and C2 (C1-C2) is preferably 20% by mass or less, more preferably 15% by mass or less, and 14% by mass. % or less, 12 mass % or less, or 11 mass % or less.
  • the resin composition layer preferably contains a thermosetting resin.
  • thermosetting resins examples include epoxy resins, benzocyclobutene resins, epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, polyimide resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, and silicone resins. resins, phenoxy resins, and the like. Thermosetting resins may be used singly or in combination of two or more.
  • thermosetting resin preferably contains an epoxy resin from the viewpoint of realizing the properties and further from the viewpoint of being able to provide a cured product with a lower surface roughness after the roughening treatment.
  • epoxy resins include bisphenol 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, and 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 formula epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin. .
  • Bisphenol-type epoxy resins refer to epoxy resins having a bisphenol structure, and include, for example, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, and bisphenol AF-type epoxy resins.
  • a biphenyl-type epoxy resin refers to an epoxy resin having a biphenyl structure, where the biphenyl structure may have a substituent such as an alkyl group, an alkoxy group, or an aryl group. Therefore, bixylenol type epoxy resins and biphenyl aralkyl type epoxy resins are also included in biphenyl type epoxy resins. Epoxy resins may be used singly or in combination of two or more.
  • an aromatic epoxy resin is preferable.
  • the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.
  • the epoxy resin preferably has two or more epoxy groups in one molecule.
  • the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass. % by mass or more.
  • Epoxy resins include 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").
  • 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 novolac type epoxy resin, and an ester skeleton.
  • cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure are preferable.
  • liquid epoxy resins include "HP-4032", “HP-4032D”, and “HP-4032SS” (naphthalene-type epoxy resins) manufactured by DIC Corporation; “828US” and “jER828EL” manufactured by Mitsubishi Chemical Corporation; “825", “Epikote 828EL” (bisphenol A type epoxy resin); “jER807”, “1750” (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “jER152” manufactured by Mitsubishi Chemical Corporation (phenol novolak type epoxy resin ); "630” and “630LSD” manufactured by Mitsubishi Chemical Corporation (p-aminophenol type epoxy resin, glycidylamine type epoxy resin); “ZX1059” manufactured by Nippon Steel Chemical & Materials Co., Ltd.
  • 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, and tetraphenylethane type epoxy resin.
  • solid epoxy resins include "HP-4032H” (naphthalene type epoxy resin) manufactured by DIC; "HP-4700” and “HP-4710” manufactured by DIC (naphthalene type tetrafunctional epoxy resin); DIC's "N-690” (cresol novolak type epoxy resin); DIC's "N-695" (cresol novolac type epoxy resin); DIC's "HP-7200HH”, “HP-7200H”, “HP-7200” (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", “EXA-7311-G3", “EXA-7311-G4", "EXA-7311-G4S”, "HP6000” " (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.
  • the resin composition layer may contain only a liquid epoxy resin as an epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. It's okay. From the viewpoint that the above (Log10(G'(B)) at 100°C) - (Log10(G'(A)) at 100°C) can be easily adjusted to a suitable range, the resin composition layer contains a solid epoxy resin. is preferably included. When a liquid epoxy resin and a solid epoxy resin are used in combination, the weight ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.5 to 1:50, more preferably 1:0.5 to 1:50. 1:1 to 1:30, more preferably 1:2 to 1:20.
  • 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. ⁇ 2000g/eq. , even more preferably 110 g/eq. ⁇ 1000 g/eq. is.
  • 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 100-5000, more preferably 250-3000, and even more preferably 400-1500.
  • the Mw of the epoxy resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
  • the above (Log10 (G' (B)) at 100 ° C.) - (Log10 (G' (A)) at 100 ° C.) can be easily adjusted to a suitable range, and even better flatness and adhesion to the conductor layer can be achieved.
  • the content of the thermosetting resin in the resin composition layer is the resin component in the resin composition layer is 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 12% by mass or more, 14% by mass or more, or 15% by mass or more.
  • the upper limit of the content is not particularly limited, and may be determined according to the properties required for the resin composition. and so on.
  • the "resin component" referred to in the resin composition layer refers to a solid content (non-volatile component) constituting the resin composition layer, excluding the inorganic filler described below.
  • the resin composition layer in the multilayer resin sheet of the present invention contains a thermosetting resin and an inorganic filler.
  • the resin composition layer contains at least one selected from a curing agent, a thermoplastic resin, a radically polymerizable resin and a curing accelerator, in addition to the above thermosetting resin and inorganic filler. may contain.
  • the resin composition layer preferably contains a curing agent.
  • the curing agent usually has the function of curing the resin composition layer by reacting with the thermosetting resin.
  • curing agents examples include active ester curing agents, phenol curing agents, naphthol curing agents, acid anhydride curing agents, cyanate ester curing agents, carbodiimide curing agents, and amine curing agents.
  • the curing agent may be used singly or in combination of two or more.
  • the curing agent consists of an active ester-based curing agent, a phenol-based curing agent, and a naphthol-based curing agent, from the viewpoint of realizing the properties and further from the viewpoint of being able to provide a cured product with even lower surface roughness after roughening treatment. It preferably contains one or more selected from the group, and particularly preferably contains an active ester curing agent from the viewpoint that a cured product exhibiting excellent dielectric properties can be obtained. Therefore, in one embodiment, component (B) contains one or more selected from the group consisting of an active ester curing agent, a phenolic curing agent, and a naphthol curing agent, more preferably an active ester curing agent. include.
  • 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”, “EXB-8000L”, and “EXB-8000L-” as active ester curing agents containing a dicyclopentadiene type diphenol structure.
  • the phenol-based curing agent and naphthol-based curing agent preferably have a novolac 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, for example, “MEH-7700”, “MEH-7810”, “MEH-7851” and “MEH-8000H” manufactured by Meiwa Kasei; Nippon Kayaku Co., Ltd. "NHN”, “CBN”, “GPH” manufactured by Nippon Steel Chemical & Materials Co., Ltd.
  • acid anhydride-based curing agents include curing agents 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.
  • 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 resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc.; prepolymers obtained by partially triazinizing these cyanate
  • cyanate ester curing agents include “PT30” and “PT60” (phenol novolac type polyfunctional cyanate ester resins), “ULL-950S” (polyfunctional cyanate ester resins) and “BA230” manufactured by Lonza Japan. , “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 Nisshinbo Chemical Co., Ltd. Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216 g/eq.), V-05 (carbodiimide group equivalent: 262 g/eq.), V- 07 (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 curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. mentioned. Specific examples of amine-based curing agents include 4,4′-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 3,3′.
  • the content of the curing agent in the resin composition is 100% by mass of the resin component in the resin composition. , it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more.
  • the upper limit of the content is not particularly limited, and may be determined according to the properties required for the resin composition. and so on.
  • the curing agent preferably contains an active ester curing agent from the viewpoint of providing a cured product exhibiting good dielectric properties.
  • the content of the active ester-based curing agent in the curing agent is such that a cured product exhibiting outstanding dielectric properties is obtained.
  • the non-volatile component of the curing agent is 100% by mass, it is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, 75% by mass or more, or 80% by mass or more. be.
  • the upper limit of the content of the active ester curing agent in the curing agent is not particularly limited, and may be 100% by mass, but may be, for example, 95% by mass or less, or 90% by mass or less.
  • the mass ratio of the active ester curing agent to the thermosetting resin is , preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0.8 or more, 1 or more, 1.1 or more, 1.2 or more, 1.5 or more, more preferably 0.6 or more, further preferably 0.8 or more, 1 or more, 1.1 or more, 1.2 or more. 3 or more, 1.4 or more, or 1.5 or more.
  • the upper limit of the mass ratio (active ester curing agent/thermosetting resin) may be, for example, 3 or less, 2.8 or less, 2.6 or less, or 2.5 or less.
  • the resin composition layer may contain a thermoplastic resin.
  • thermoplastic resins include phenoxy resins, polyimide resins, polyvinyl acetal resins, acrylic resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetherimide resins, and polycarbonate resins. , polyether ether ketone resins, and polyester resins, among which resins selected from phenoxy resins, polyimide resins, acrylic resins, polyphenylene ether resins, and polycarbonate resins are preferred.
  • the thermoplastic resin may be used singly or in combination of two or more.
  • 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.
  • 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).
  • a resin having an imide structure can be used as the polyimide resin.
  • a polyimide resin can generally be obtained by an imidization reaction between a diamine compound and an acid anhydride.
  • Specific examples of the polyimide resin include, for example, a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), polysiloxane.
  • Modified polyimides such as skeleton-containing polyimides (polyimides described in JP-A-2002-12667, JP-A-2000-319386, etc.) can be mentioned.
  • a commercially available polyimide resin may be used, and examples thereof include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika Co., Ltd.
  • the polyimide resin contains a structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit (1)").
  • structural unit (1) The number of structural units (1) contained per polyimide resin molecule is 1 or more, and is not particularly limited, but may be 100 or less, 50 or less, or 30 or less.
  • R 1 is a tetravalent group represented by the following formula (1-1)
  • R 2 is a divalent group represented by the following formula (1-2).
  • Ar 11 , Ar 12 , Ar 13 and Ar 14 each independently represent an aromatic ring optionally having a substituent, L 11 , L 12 and L 13 each independently represent a divalent linking group, nc1 represents an integer of 0 or more.
  • Ar 21 , Ar 22 , Ar 23 and Ar 24 each independently represent an aromatic ring optionally having a substituent, L 21 , L 22 and L 23 each independently represent a divalent linking group, nc2 represents an integer of 1 or more. )]
  • aromatic ring C the aromatic ring represented by Ar 11 , Ar 12 , Ar 13 and Ar 14 (hereinafter also referred to as “aromatic ring C”) preferably has 6 to 100 carbon atoms, more preferably 6 to 50 aromatic rings, more preferably 6 to 100 carbon atoms, still more preferably 6 to 50 carbon atoms.
  • Ar 11 , Ar 12 , Ar 13 and Ar 14 are each independently an optionally substituted aromatic having 6 to 14 carbon atoms It is carbocyclic.
  • aromatic ring as used herein means a ring according to Hückel's rule in which the number of electrons contained in the ⁇ -electron system on the ring is 4n+2 (n is a natural number), and is a monocyclic aromatic ring. rings, and fused aromatic rings in which two or more monocyclic aromatic rings are fused. Aromatic rings may be carbocyclic or heterocyclic.
  • aromatic rings include monocyclic rings such as benzene ring, furan ring, thiophene ring, pyrrole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, and pyrazine ring.
  • Aromatic ring of formula naphthalene ring, anthracene ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzimidazole ring, indazole ring, benzoxazole ring, benzoisoxazole ring, benzothiazole ring, quinoline condensed ring in which two or more monocyclic aromatic rings such as ring, isoquinoline ring, quinoxaline ring, acridine ring, quinazoline ring, cinnoline ring, and phthalazine ring are condensed; one or more of indane ring, fluorene ring, tetralin ring, etc.
  • a condensed ring in which one or more monocyclic non-aromatic rings are condensed to a monocyclic aromatic ring.
  • an aromatic carbocyclic ring having 6 to 14 carbon atoms is preferred, and a benzene ring is more preferred.
  • substituent S include, independently of each other, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, an aryloxy group, arylalkyl group, arylalkoxy group, monovalent heterocyclic group, alkylidene group, amino group, silyl group, acyl group, acyloxy group, carboxy group, sulfo group, cyano group, nitro group, hydroxy group, mercapto group and oxo group is mentioned.
  • the divalent linking groups represented by L 11 , L 12 and L 13 are preferably one or more selected from carbon, oxygen, nitrogen, sulfur and silicon atoms (for example 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeletal atoms.
  • the number of carbon atoms in the alkylene group is preferably 1-10, more preferably 1-6, still more preferably 1-5 or 1-4.
  • the alkenylene group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 5 carbon atoms.
  • the number of carbon atoms in the arylene group is preferably 6 to 20, more preferably 6 to 10, and the number of carbon atoms in the heteroarylene group is preferably 2 to 20, more preferably 3 to 10, 4 to 10 or 5 to 10. is.
  • the alkyl group, alkylene group, alkenylene group, alkynylene group, arylene group, and heteroarylene group described above may further have a substituent.
  • substituent include the substituent S described above.
  • the divalent linking groups represented by L 11 , L 12 and L 13 preferably do not contain an aromatic ring. In one embodiment, the divalent linking group represented by L 11 and the divalent linking group represented by L 13 are the same, and the divalent linking group represented by L 11 and the divalent linking group represented by L 12 are the same. are different from each other.
  • L 11 and L 13 are —O—, and L 12 is an optionally substituted alkylene group
  • Ar 11 , Ar 12 , Ar 13 and Ar 14 are each independently an optionally substituted aromatic carbocyclic ring having 6 to 14 carbon atoms
  • L 11 and L 13 are —O—
  • L 12 is an optionally substituted alkylene group.
  • L 11 and L 13 are —O— and L 12 is a dimethylmethylene group.
  • examples of the aromatic rings represented by Ar 21 , Ar 22 , Ar 23 and Ar 24 and the substituents that the aromatic rings may have are, respectively, the aromatic ring C and the substituent S and are the same. Therefore, in a preferred embodiment, in formula (1-2), Ar 21 , Ar 22 , Ar 23 and Ar 24 are each independently It is an aromatic carbocycle. Further, in a preferred embodiment, in formula (1-2), L 21 and L 23 are —O—, and L 22 is an optionally substituted alkylene group; In an embodiment, in formula (1-2), Ar 21 , Ar 22 , Ar 23 and Ar 24 are each independently an optionally substituted aromatic carbocyclic ring having 6 to 14 carbon atoms. and L 21 and L 23 are —O—, and L 22 is an optionally substituted alkylene group. In a further preferred embodiment, in formula (1-2), L 21 and L 23 are —O— and L 22 is a dimethylmethylene group.
  • Ar 11 , Ar 12 , Ar 13 and Ar 14 are each independently an optionally substituted aromatic having 6 to 14 carbon atoms. a group carbocyclic ring, and in formula (1-2), Ar 21 , Ar 22 , Ar 23 and Ar 24 are each independently an optionally substituted aromatic having 6 to 14 carbon atoms; is a group carbocycle.
  • L 11 and L 13 are —O—
  • L 12 is an optionally substituted alkylene group
  • L 21 and L 23 are —O—
  • L 22 is an optionally substituted alkylene group.
  • nc1 preferably represents an integer of 1 or more.
  • the upper limit of the integer represented by nc1 is not particularly limited, but may be 50, 40, 30 or 20, for example.
  • nc2 preferably represents an integer of 2 or more.
  • the upper limit of the integer represented by nc2 is not particularly limited, but may be 60, 50, 40 or 30, for example.
  • Structural unit (1) is produced by, for example, a known method for producing a polyimide resin, typically a method of imidating by polymerizing a monomer composition containing a tetracarboxylic dianhydride and a diamine compound, or a tetracarboxylic dianhydride. It can be obtained according to a method of polymerizing and imidating a monomer composition containing a compound and a diisocyanate compound.
  • the polyimide resin is allowed to partially contain a polyamic acid structure that may be generated during the process of imidization.
  • Structural unit (1) is, for example, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (a compound represented by the following formula (I); hereinafter also referred to as “BPADA” ) and 4,4′-[1,4-phenylenebis[(1-methylethylidene)-4,1-phenyleneoxy]]bisbenzenamine (a compound represented by the following formula (II); hereinafter, (also referred to as “BPPAN”). That is, R 1 in structural unit (1) is a skeleton derived from BPADA, and R 2 is a skeleton derived from BPPAN.
  • BPADA 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride
  • BPPAN 4,4′-[1,4-phenylenebis[(1-methylethylidene)-4,1-phenyleneoxy]]bisbenzenamine
  • the polyimide resin may further contain a structural unit represented by the following formula (2) (hereinafter also referred to as "structural unit (2)"). Therefore, in one embodiment, the polyimide resin further contains a structural unit represented by the following formula (2).
  • the number of structural units (2) contained per polyimide resin molecule is 0 or more and is not particularly limited, but may be 100 or less, 50 or less, or 30 or less.
  • R 3 represents an optionally substituted tetravalent aliphatic group or an optionally substituted tetravalent aromatic group
  • R 4 represents an optionally substituted divalent aliphatic group or an optionally substituted divalent aromatic group.
  • R3 is the same as R1
  • R4 is different from R2
  • R4 is the same as R2
  • R3 is different from R1 .
  • the tetravalent aliphatic group represented by R 3 contains at least carbon atoms, preferably one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms and silicon atoms (e.g., 1 It is a tetravalent group consisting of skeletal atoms of up to 3000, 1 to 1000, 1 to 100, 1 to 50).
  • the tetravalent aliphatic group represented by R 3 is more preferably a tetravalent aliphatic group having 1 to 100 carbon atoms, more preferably 1 to 50 carbon atoms.
  • R 3 represents a tetravalent aliphatic group having a substituent
  • examples of the substituent are the same as those of the substituent S.
  • the tetravalent aromatic group represented by R 3 is preferably a tetravalent aromatic group having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms.
  • An aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the aromatic rings represented by Ar 11 , Ar 12 , Ar 13 and Ar 14 in formula (1-1).
  • R 3 represents a tetravalent aromatic group having a substituent
  • examples of the substituent are the same as those of the substituent S.
  • Examples of the tetravalent aromatic group represented by R 3 include a group obtained by removing two acid anhydride groups from a tetracarboxylic dianhydride having an optionally substituted aromatic group.
  • Specific examples of tetracarboxylic dianhydrides having an optionally substituted aromatic group include BPADA, pyromellitic dianhydride, and 3,3′,4,4′-biphenyltetracarboxylic acid.
  • dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride is mentioned.
  • the divalent aliphatic group represented by R 4 contains at least carbon atoms, preferably one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms and silicon atoms (e.g., 1 3000, 1 to 1000, 1 to 100, 1 to 50) skeletal atoms.
  • the divalent aliphatic group represented by R 4 is more preferably a divalent aliphatic group having 1 to 100 carbon atoms, more preferably 1 to 50 carbon atoms.
  • R 4 represents a divalent aliphatic group having a substituent
  • examples of the substituent are the same as examples of the substituent S, for example, an alkyl group having 1 to 6 carbon atoms is.
  • R 4 is an optionally substituted divalent aliphatic group, one of which is an alkyl group having 1 to 6 carbon atoms. In one embodiment, R 4 is an optionally substituted divalent aliphatic group and is a divalent group obtained by removing two amino groups from isophoronediamine.
  • R 4 represents an optionally substituted divalent aliphatic group, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, selected from 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine or a group obtained by removing two amino groups from a diamine compound having a linear aliphatic group which may have a substituent.
  • 1,2-diaminoethane 1,3-diaminopropane
  • 1,4-diaminobutane 1,5-diaminopentane, selected from 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine
  • R 4 represents an optionally substituted divalent aliphatic group, 1,2-diaminopropane, 1,2-diamino-2-methylpropane, 1,3-diamino-2-methylpropane , 1,3-diamino-2,2-dimethylpropane, 1,3-diaminopentane, 1,5-diamino-2-methylpentane, an optionally substituted branched aliphatic group It may be a group obtained by removing two amino groups from a diamine compound having
  • R 4 represents an optionally substituted divalent aliphatic group, 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine), 1,4-diaminocyclohexane, 1, 3-diaminocyclohexane, 1,4-cyclohexanebis(methylamine), 1,3-cyclohexanebis(methylamine), 4,4'-diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, 3 (4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 2,6 ]decane, 2,5(6)-bis(aminomethyl)bicyclo[2.2.1]heptane , 1,3-diaminoadamantane, 3,3′-diamino-1,1′-biadamantyl and 1,6-diaminoadamantane, a diamine compound having an optionally substituted
  • the divalent aromatic group represented by R 4 is preferably a divalent aromatic group having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms.
  • An aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the examples of the aromatic ring C.
  • R 4 represents a divalent aromatic group having a substituent, examples of the substituent are the same as those of the substituent S.
  • R 4 represents an optionally substituted divalent aromatic group
  • 4,4'-diaminodiphenyl ether, 1,4-phenylenediamine, 2,2-bis[4-(4-amino It may be a group obtained by removing two amino groups from a diamine compound having an optionally substituted aromatic group selected from phenoxy)phenyl]propane.
  • R3 is the same as R1 , then R4 is different from R2 , and if R4 is the same as R2 , then R3 is different from R1 . In one embodiment, R3 is the same as R1 .
  • Structural unit (2) described above can be obtained, for example, according to a known method for producing a polyimide resin.
  • Structural unit (2) can be obtained, for example, by reacting BPADA with isophorone diamine. That is, R3 in the structural unit (2) is a skeleton derived from BPADA, and R4 is a skeleton derived from isophoronediamine. When R 3 is the same as R 1 , R 3 and R 1 are skeletons derived from BPADA.
  • the terminal structure of the polyimide resin is not particularly limited.
  • the terminal structure of the polyimide resin may be an acid anhydride group, a carboxyl group, or an amino group derived from the raw material compound (for example, an acid such as BPADA or an amine compound such as BPPAN).
  • the raw material compound further contains maleic anhydride
  • the terminal structure of the polyimide resin may be a maleimide group.
  • the glass transition temperature Tg (°C) of the polyimide resin is preferably 140°C or higher, more preferably 145°C or higher, and still more preferably 150°C or higher, 160°C or higher, or 170°C or higher. Although the upper limit is not particularly limited, it may be 300° C. or less.
  • the glass transition temperature Tg (°C) of the polyimide resin can be measured by a thermomechanical analysis (TMA) method.
  • the content of the structural unit (1) in the polyimide resin is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more, 30% by mass or more, or 40% by mass or more.
  • the upper limit of the content can be, for example, 98% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less.
  • the content ratio (mass percentage) of the structural unit (1) can be calculated from the ratio of the charged amount (parts by mass) of each material used in the synthesis of the polyimide resin.
  • the molecular weight and the formula weight of the structural unit (1) may be specified, and the ratio of the formula weight of the structural unit (1) to the molecular weight may be calculated.
  • the content of the structural unit (1) estimated from the degree of polymerization is preferably within the above range.
  • the content of the structural unit (2) may be 0% by mass (that is, the structural unit (2) is not included), and the effect of the present invention is obtained.
  • the upper limit is not limited as long as it does not interfere.
  • the content of the structural unit (2) in the polyimide resin is, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more, 95% by mass or less, 90% by mass or less, It can be 80% by mass or less, 70% by mass or less, or 60% by mass or less.
  • the content of structural unit (2) is calculated in the same manner as the content of structural unit (1).
  • the weight average molecular weight (Mw) of the polyimide resin is 1,000 or more, preferably 1,00 to 10,000, more preferably 1,000 to 5,000.
  • the weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
  • polyvinyl acetal resin-- examples include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are 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.
  • acrylic resin-- An acrylic resin means a polymer obtained by polymerizing a monomer component including a (meth)acrylic acid ester-based monomer.
  • the monomer component constituting the acrylic resin may contain (meth)acrylamide-based monomers, styrene-based monomers, functional group-containing monomers, etc. as copolymerization components in addition to (meth)acrylic acid ester-based monomers.
  • Specific examples of acrylic resins include "ARUFON UP-1000", “ARUFON UP-1010", “ARUFON UP-1020", “ARUFON UP-1021", “ARUFON UP-1061” and "ARUFON” manufactured by Toagosei Co., Ltd.
  • polyolefin resin examples 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.
  • Polybutadiene resins include, for example, hydrogenated polybutadiene skeleton-containing resins, hydroxyl group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxyl group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, and isocyanate group-containing resins.
  • Examples include polybutadiene resin, urethane group-containing polybutadiene resin, polyphenylene ether-polybutadiene resin, and the like.
  • polyamide-imide resin-- Specific examples of polyamide-imide resins include "VYLOMAX HR11NN” and “VYLOMAX HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins include modified polyamideimides such as "KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimides) manufactured by Hitachi Chemical Co., Ltd.
  • polyethersulfone resin-- Specific examples of the polyethersulfone resin include "PES5003P” manufactured by Sumitomo Chemical Co., Ltd., and the like.
  • polysulfone resin-- Specific examples of the polysulfone resin include polysulfone "P1700” and “P3500” manufactured by Solvay Advanced Polymers.
  • polyphenylene ether resin-- Specific examples of the polyphenylene ether resin include "Noryl (registered trademark) SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include “Ultem” manufactured by GE.
  • polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxy group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins.
  • polycarbonate resins include "FPC0220” manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and “T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, "C-1090” and “C-2090” manufactured by Kuraray Co., Ltd. , “C-3090” (polycarbonate diol) and the like.
  • Specific examples of the polyetheretherketone resin include "Sumiproy K” manufactured by Sumitomo Chemical Co., Ltd., and the like.
  • Polyester resins include, for example, polyethylene terephthalate resins.
  • the weight average molecular weight of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, 15,000 or more, or 20,000 or more, It is preferably 200,000 or less, more preferably 150,000 or less or 100,000 or less, still more preferably 80,000 or less or 60,000 or less.
  • the weight average molecular weight of the thermoplastic resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
  • the content of the thermoplastic resin in the resin composition layer is the above when the resin component in the resin composition layer is 100% by mass. (Log10(G′(B)) at 100° C.) ⁇ (Log10(G′(A)) at 100° C.) is easily adjusted to a suitable range, preferably 0.1% by mass or more, 0.1% by mass or more, It is 3% by mass or more, or 0.5% by mass or more.
  • the upper limit of the thermoplastic resin content is not particularly limited, but is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6% by mass or less or 5% by mass or less.
  • the resin composition layer may contain a radically polymerizable resin.
  • the type of the radically polymerizable resin is not particularly limited as long as it has one or more (preferably two or more) radically polymerizable unsaturated groups in one molecule.
  • the radically polymerizable resin for example, one selected from a maleimide group, a vinyl group, an allyl group, a styryl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, a fumaroyl group, and a maleoyl group as a radically polymerizable unsaturated group. Resins having the above are mentioned.
  • the above (Log10 (G' (B)) at 100 ° C.) - (Log10 (G' (A)) at 100 ° C.) can be easily adjusted to a suitable range, and even better flatness and adhesion to the conductor layer
  • the radically polymerizable resin is a maleimide resin. , (meth)acrylic resin and styryl resin.
  • maleimide resin As the maleimide resin, as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule, is not particularly limited.
  • maleimide resins include (1) “BMI-3000J”, “BMI-5000", “BMI-1400", “BMI-1500”, “BMI-1700”, and “BMI-689” (all of which are Maleimide resins containing an aliphatic skeleton (preferably an aliphatic skeleton having 36 carbon atoms derived from dimer diamine) such as “SLK6895-T90" (manufactured by Shin-Etsu Chemical Co., Ltd.); (3) “MIR-3000-70MT” (manufactured by Nippon Kayaku Co., Ltd.), “BMI-4000” (Daiwa Kasei Co., Ltd.). (manufactured by Kei Kasei Co., Ltd
  • the type of the (meth)acrylic resin is not particularly limited as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule, and may be a monomer or an oligomer.
  • the term "(meth)acryloyl group” is a generic term for acryloyl group and methacryloyl group.
  • methacrylic resins in addition to (meth)acrylate monomers, for example, “A-DOG” (manufactured by Shin-Nakamura Chemical Co., Ltd.), “DCP-A” (manufactured by Kyoeisha Chemical Co., Ltd.), “NPDGA”, “FM-400”. , “R-687”, “THE-330”, “PET-30”, and “DPHA” (all manufactured by Nippon Kayaku Co., Ltd.).
  • styryl resin is not particularly limited as long as it has one or more (preferably two or more) styryl groups or vinylphenyl groups in one molecule, and it may be a monomer or an oligomer.
  • styryl resins include styrene monomers as well as styryl resins such as "OPE-2St”, “OPE-2St 1200", and “OPE-2St 2200” (all manufactured by Mitsubishi Gas Chemical Company).
  • the content of the radically polymerizable resin in the resin composition layer is From the viewpoint of easily adjusting the above (Log10(G'(B)) at 100°C) - (Log10(G'(A)) at 100°C) to a suitable range, it is preferably 2% by mass or more, more preferably 4% by mass or more, more preferably 5% by mass or more, 6% by mass or more, 8% by mass or more, or 10% by mass or more, for example, 12% by mass or more, 14% by mass or more, or 15% by mass or more. .
  • the upper limit of the content is not particularly limited, and may be determined depending on the properties required of the resin composition.
  • the first resin composition layer preferably contains a radically polymerizable resin. Therefore, in one preferred embodiment, the first resin composition layer contains a radically polymerizable resin.
  • the resin composition layer may contain a curing accelerator.
  • a curing accelerator By including a curing accelerator, the curing time and curing temperature can be adjusted efficiently.
  • curing accelerators examples include organic phosphine compounds such as “TPP”, “TPP-K”, “TPP-S”, and “TPTP-S” (manufactured by Hokko Chemical Industry Co., Ltd.); , “2E4MZ”, “Cl1Z”, “Cl1Z-CN”, “Cl1Z-CNS”, “Cl1Z-A”, “2MZ-OK”, “2MA-OK”, “2PHZ” (manufactured by Shikoku Kasei Co., Ltd.), etc.
  • imidazole compounds such as Novacure (manufactured by Asahi Chemical Industry Co., Ltd.) and Fujicure (manufactured by Fuji Chemical Industry Co., Ltd.); 1,8-diazabicyclo[5,4,0]undecene-7,4-dimethylaminopyridine, benzyldimethyl amines, 2,4,6-tris(dimethylaminomethyl)phenol, 4-dimethylaminopyridine and other amine compounds; organic metal complexes or salts of cobalt, copper, zinc, iron, nickel, manganese, tin, etc.; mentioned.
  • the content of the curing accelerator in the resin composition layer is the above when the resin component in the resin composition is 100% by mass.
  • (Log10(G'(B)) at 100°C)-(Log10(G'(A)) at 100°C) is preferably adjusted to a suitable range, preferably 10% by mass or less, more preferably 8 mass % or less, 6 mass % or less, or 5 mass % or less, and the lower limit may be 0.001 mass % or more, 0.01 mass % or more, or 0.05 mass % or more.
  • the resin composition layer may further contain optional additives.
  • additives include, for example, organic fillers such as rubber particles; radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; organic copper compounds, organic zinc compounds, and organic cobalt compounds.
  • organometallic compounds such as compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine; silicone-based leveling agents , leveling agents such as acrylic polymer leveling agents; thickeners such as bentone and montmorillonite; UV absorbers such as benzotriazole UV absorbers; adhesion improvers such as urea silane; Antioxidants such as phenolic antioxidants; Fluorescent brighteners such as stilbene derivatives; Surfactants such as fluorosurfactants and silicone surfactants; , phosphinic acid compounds, red phosphorus), nitrogen flame retardants (e.g.
  • melamine sulfate melamine sulfate
  • halogen flame retardants e.g. antimony trioxide
  • Dispersants such as dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, cationic dispersants; borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers
  • Stabilizers such as stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers are included. The content of such additives may be determined according to the properties required for the multilayer resin sheet.
  • the method for producing the multilayer resin sheet of the present invention is not particularly limited as long as a structure in which two or more resin composition layers are laminated together can be realized, and methods known to those skilled in the art may be used.
  • the resin composition is melt-kneaded and extruded, and then by a T-die or a circular die or the like, an extrusion molding method in which the resin composition is dissolved or dispersed in a solvent to form a film, A casting molding method in which a film is formed by casting, and other conventionally known film molding methods can be used.
  • the extrusion molding method and the casting molding method are preferable because they can be used for thinning.
  • the multilayer resin sheet of the present invention includes two or more resin composition layers laminated together.
  • a method for forming a multilayer resin sheet by laminating two or more resin composition layers for example, two or more separately prepared resin composition layers are laminated together using a hot roll laminator or the like to form a multilayer resin sheet.
  • a method of forming a resin composition layer simultaneously or sequentially during coating or extrusion to form a multilayer resin sheet, a method of making a difference in the content of each component in the resin sheet during casting molding, and substantially Examples include a method of forming a resin sheet having a multilayer structure in one resin sheet, and other conventionally known methods of forming a multilayer resin sheet.
  • a preferred example of a method for producing a multilayer resin sheet having two resin composition layers, that is, a first resin composition layer and a second resin composition layer is shown below.
  • the method for producing a multilayer resin sheet comprises: (A1) a step of preparing a support-attached resin sheet comprising a support and a first resin composition layer bonded to the support; and (B1) a second resin composition layer on the first resin composition layer; and drying the coating film to provide a second resin composition layer (hereinafter, an embodiment of lamination by such coating is also referred to as “first embodiment”).
  • step (A1) a support-attached resin sheet including a support and a first resin composition layer bonded to the support is prepared.
  • the support will be described later in the section [Multilayer resin sheet with support].
  • the support-attached resin sheet can be produced, for example, by coating the support with the first resin composition and drying the coating film to form the first resin composition layer.
  • a resin varnish is prepared by dissolving the first resin composition in an organic solvent, the resin varnish is applied onto a support using a die coater or the like, and the coated film is dried. can be done.
  • organic solvents examples include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol; acetic acid 2- Ether ester solvents such as ethoxyethyl, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, ⁇ -butyrolactone, and methyl methoxypropionate; Ester alcohol solvent; ether alcohol solvent such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol
  • the coating film may be dried by a known drying method such as heating or blowing hot air.
  • a drying method such as heating or blowing hot air.
  • drying at 80° C. to 180° C. for 2 minutes to 10 minutes gives the support.
  • a first resin composition layer can be formed thereon.
  • the second resin composition is applied onto the first resin composition layer, and the coating film is dried to provide the second resin composition layer.
  • a multilayer resin sheet with a support is formed, in which the multilayer resin sheet is formed on the support.
  • the application of the second resin composition and drying of the coating film may be carried out in the same manner as the application of the first resin composition and drying of the coating film in step (A1).
  • the drying temperature of the coating film in the step (A1) (° C.) is T1
  • the drying temperature (° C.) of the coating film in step (A2) is T2, preferably T1>T2, more preferably T1 ⁇ (T2+20), still more preferably T1 ⁇ (T2+40), or It is preferable to satisfy the relationship T1 ⁇ (T2+50).
  • the support-attached multilayer resin sheet may further include a protective film conforming to the support on the surface of the multilayer resin sheet that is not bonded to the support (that is, the surface opposite to the support).
  • a protective film conforming to the support on the surface of the multilayer resin sheet that is not bonded to the support (that is, the surface opposite to the support).
  • the method for producing a multilayer resin sheet comprises: (A2a) a step of preparing a first support-attached resin sheet comprising a first support and a first resin composition layer bonded to the first support; (A2b) a step of preparing a second support-attached resin sheet comprising a second support and a second resin composition layer bonded to the second support; and (B2) a first (hereinafter referred to as " An embodiment of stacking by lamination is also referred to as a “second embodiment”.).
  • step (A2a) and step (A2b) may each be performed in the same manner as step (A1) in the first embodiment.
  • the coating film in the step (A2a) When the drying temperature (° C.) of the step (A2b) is Ta, and the drying temperature (° C.) of the coating film in the step (A2b) is Tb, preferably Ta>Tb, more preferably Ta ⁇ (Tb+20), still more preferably Ta ⁇ ( Tb+40) or Ta ⁇ (Tb+50).
  • step (B2) the first resin sheet with support and the second resin sheet with support are laminated such that the first resin composition layer and the second resin composition layer are bonded. .
  • a multilayer resin sheet is thus formed between the first support and the second support.
  • the second support can function as the protective film in the first embodiment.
  • the support-attached multilayer resin sheet manufactured according to the second embodiment can be used by peeling off the second support (protective film) when laminating on a member to be laminated.
  • the lamination temperature preferably ranges from 60° C. to 160° C., more preferably 80° C. to 140° C.
  • the lamination pressure preferably ranges from 0.098 MPa to 1.77 MPa, more preferably It is in the range of 0.29 MPa to 1.47 MPa
  • the lamination time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds.
  • Lamination can be carried out under reduced pressure conditions, preferably at a pressure of 26.7 hPa or less.
  • Lamination can be done with a commercially available 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-type vacuum pressurized laminator, and the like.
  • the multilayer resin sheet of the present invention can provide a cured product with good surface flatness and good adhesion to the conductor layer even when laminated on a member to be laminated having an uneven surface. According to the multilayer resin sheet of the present invention, it is also possible to produce a cured product exhibiting low surface roughness after roughening treatment. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for an insulating layer of a printed wiring board), and can be used for interlayer insulation of a printed wiring board. It can be used more preferably as a resin composition for forming a layer (resin composition for insulating interlayers of printed wiring boards).
  • the resin composition of the present invention can also be suitably used when the printed wiring board is a component built-in circuit board.
  • the resin composition of the present invention is also a resin composition for forming an insulating layer on which a conductor layer (including a rewiring layer) is formed (resin for insulating layer for forming a conductor layer). composition).
  • the present invention also provides a support-attached multilayer resin sheet in which the multilayer resin sheet of the present invention is provided on a support.
  • the support-attached multilayer resin sheet of the present invention comprises: a multilayer resin sheet of the present invention; and a support bonded to the first resin composition layer of the multilayer resin sheet.
  • the multilayer resin sheet of the present invention is as described in the above [Multilayer resin sheet] section.
  • the first resin composition layer of the multilayer resin sheet of the present invention is bonded to the support.
  • the support examples include thermoplastic resin films, metal foils, and release papers, with thermoplastic resin films and metal foils being preferred.
  • the support is therefore a thermoplastic film or a metal foil.
  • thermoplastic resin film When a thermoplastic resin film is used as the support, examples of the thermoplastic resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA). , cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA).
  • cyclic polyolefin triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like.
  • TAC triacetyl
  • examples of the metal foil 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. may be used.
  • the support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the first resin composition layer.
  • a support with a release layer having a release layer on the surface to be bonded to the first resin composition layer may be used.
  • the release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. .
  • SK-1 manufactured by Lintec Co., Ltd., "SK-1", “ AL-5”, “AL-7”, Toray's "Lumirror T60”, Teijin's "Purex”, and Unitika's "Unipeel”.
  • the thickness of the support is not particularly limited, it is preferably in the range of 5 ⁇ m to 75 ⁇ m, more preferably in the range of 10 ⁇ m to 60 ⁇ m.
  • the thickness of the release layer-attached support as a whole is preferably within the above range.
  • a metal foil with a supporting base which is a thin metal foil laminated with a supporting base that can be peeled off, may be used.
  • the metal foil with a supporting substrate includes a supporting substrate, a release layer provided on the supporting substrate, and a metal foil provided on the releasing layer.
  • the multilayer resin sheet is provided on the metal foil so that the first resin composition layer of the multilayer resin sheet is bonded to the metal foil.
  • the material of the supporting base material is not particularly limited, but examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil and the like.
  • copper foil When copper foil is used as the supporting substrate, it may be an electrolytic copper foil or a rolled copper foil.
  • the release layer is not particularly limited as long as it can release the metal foil from the support base material, for example, Cr, Ni, Co, Fe, Mo, Ti, W, an alloy layer of an element selected from the group consisting of P; organic A film etc. are mentioned.
  • metal foil with a supporting base material for example, copper foil and copper alloy foil are preferable as the material of the metal foil.
  • the thickness of the supporting substrate is not particularly limited, but is preferably in the range of 10 ⁇ m to 150 ⁇ m, more preferably in the range of 10 ⁇ m to 100 ⁇ m. Also, the thickness of the metal foil may be, for example, in the range of 0.1 ⁇ m to 10 ⁇ m.
  • the support-attached multilayer resin sheet may further contain optional layers as necessary.
  • optional layers include a protective film provided on the surface of the multilayer resin sheet that is not bonded to the support (that is, the surface opposite to the support).
  • the thickness of the protective film is not particularly limited, it is, for example, 1 ⁇ m to 40 ⁇ m.
  • the manufacturing method of the support-attached multilayer resin sheet is as described in the above [Multilayer resin sheet] section.
  • the multi-layered resin sheet with support can be rolled up and stored.
  • the support-attached resin sheet has a protective film, it can be used by peeling off the protective film.
  • the adhesive strength between the support and the multilayer resin sheet is S1
  • the protective film and the multilayer resin sheet are opposite to each other. and the outermost layer on the side
  • the relationship S1>S2 is satisfied.
  • the protective film can be peeled off from the multilayer resin sheet before the support, and the surface of the multilayer resin sheet opposite to the first resin composition layer can be exposed. can be used by laminating so that the surface opposite to the first resin composition layer of is bonded to the member to be laminated.
  • the support-attached multilayer resin sheet of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board. (For insulating interlayers of printed wiring boards).
  • the sheet-like laminated material of the present invention also includes a resin composition for forming an insulating layer on which a conductor layer (including a rewiring layer) is formed (insulating layer for forming a conductor layer). resin composition).
  • the printed wiring board of the present invention includes an insulating layer made of a cured multilayer resin sheet of the present invention.
  • a printed wiring board can be produced, for example, using the multilayer resin sheet of the present invention by a method including the following steps (I) and (II).
  • (II) Multilayer resin The process of curing (e.g. thermosetting) the sheet to form an insulating layer
  • the “inner layer substrate” used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc.
  • the substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned.
  • An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board.”
  • an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" as used in the present invention.
  • an inner layer board with built-in components may be used.
  • Lamination of the inner layer substrate and the multilayer resin sheet can be performed, for example, by using the support-attached multilayer resin sheet of the present invention and thermocompression bonding the multilayer resin sheet to the inner layer substrate from the support side.
  • the member for thermocompression bonding the multilayer resin sheet to the inner layer substrate include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls).
  • the thermocompression bonding member may be directly pressed onto the support-attached multilayer resin sheet, or may be pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the uneven surface of the inner layer substrate.
  • Lamination of the inner layer substrate and the multilayer resin sheet may be performed 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 can be carried out under reduced pressure conditions, preferably at a pressure of 26.7 hPa or less.
  • Lamination can be done with a commercially available 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 multilayer resin sheet may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. Pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.
  • the support may be removed between step (I) and step (II), or may be removed after step (II).
  • the conductor layer may be formed using the metal foil without peeling off the support.
  • the supporting substrate and the release layer
  • a conductor layer can be formed using metal foil.
  • step (II) the multilayer resin sheet is cured (for example, thermally cured) to form an insulating layer made of the cured multilayer resin sheet.
  • Curing conditions for the multilayer resin sheet are not particularly limited, and conditions commonly used for forming insulating layers of printed wiring boards may be used.
  • the thermosetting conditions for the multilayer resin sheet vary depending on the composition of the resin composition layer, etc., but in one embodiment, the curing temperature is preferably 120° C. to 250° C., more preferably 150° C. to 240° C., and further preferably 150° C. to 240° C. It is preferably 170°C to 230°C.
  • the curing time can be preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, even more preferably 15 minutes to 120 minutes.
  • the multilayer resin sheet Before thermosetting the multilayer resin sheet, the multilayer resin sheet may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the multilayer resin sheet, the multilayer resin sheet is cured at a temperature of 50° C. to 120° C., preferably 60° C. to 115° C., more preferably 70° C. to 110° C. for 5 minutes or more, preferably Preheating may be performed for 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.
  • steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards.
  • the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step ( It may be carried out between IV) and step (V). If necessary, the steps (I) to (V) of forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board.
  • the step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer.
  • Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.
  • Step (IV) is a step of roughening the insulating layer.
  • removal of smear (desmear) is also performed in this step (IV).
  • the procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed.
  • the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order.
  • the swelling liquid used for the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable.
  • Examples of commercially available swelling liquids include "Swelling Dip Securigant P" and "Swelling Dip Securigant SBU” manufactured by Atotech Japan.
  • the swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. C. for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.
  • the oxidizing agent used for the roughening treatment is not particularly limited, but examples include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide.
  • the roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 to 30 minutes.
  • the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass.
  • Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.
  • an acidic aqueous solution is preferable, and a commercially available product includes, for example, "Reduction Securigant P" manufactured by Atotech Japan.
  • the treatment with the neutralizing solution can be performed by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.
  • the step (V) is a step of forming a conductor layer, and forms the conductor layer on the insulating layer.
  • the conductor material used for the conductor layer is not particularly limited.
  • the conductor layer contains one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal.
  • the conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys).
  • single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred.
  • a metal layer is more preferred.
  • the conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated.
  • the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.
  • the thickness of the conductor layer is generally 3 ⁇ m to 35 ⁇ m, preferably 5 ⁇ m to 30 ⁇ m, depending on the desired printed wiring board design.
  • the conductor layer may be formed by plating.
  • a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method.
  • a semi-additive method is shown below.
  • a plating seed layer is formed on the surface of the insulating layer by electroless plating.
  • a mask pattern (dry resist) is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern.
  • the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.
  • the conductor layer may be formed using metal foil.
  • step (V) is preferably performed between step (I) and step (II).
  • step (I) the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer.
  • Lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I).
  • step (II) is performed to form an insulating layer.
  • a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.
  • a metal foil can be produced by a known method such as an electrolysis method or a rolling method.
  • Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd., and the like.
  • the metal foil may be used to form the conductor layer.
  • a semiconductor chip package can be manufactured using the multilayer resin sheet of the present invention.
  • the present invention also provides such a semiconductor chip package.
  • the semiconductor chip package of the present invention includes an insulating layer (rewiring forming layer) for forming a rewiring layer, which is made of a cured product of the multilayer resin sheet of the present invention.
  • a semiconductor chip package can be manufactured, for example, using the multilayer resin sheet of the present invention by a method including the following steps (1) to (6).
  • the multilayer resin sheet of the present invention may be used to form the rewiring formation layer in step (5).
  • An example of forming a rewiring layer using a multilayer resin sheet will be described below. Techniques for forming a rewiring layer of a semiconductor chip package are well known, and those skilled in the art will be able to use the multilayer resin sheet of the present invention. can be used to manufacture semiconductor packages according to known techniques.
  • the material used for the base material is not particularly limited. Glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel plates (SPCC); 4 substrate); and a substrate made of bismaleimide triazine resin (BT resin).
  • the material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in step (4) and can temporarily fix the semiconductor chip.
  • a commercially available product can be used as the temporary fixing film.
  • Commercially available products include Riva Alpha manufactured by Nitto Denko Corporation.
  • Temporarily fixing the semiconductor chip can be performed using a known device such as a flip chip bonder and a die bonder.
  • the layout and the number of arrangement of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production number of the target semiconductor package, etc. For example, a matrix of multiple rows and multiple columns can be aligned and temporarily fixed.
  • Step (3)- A sealing resin sheet having a sealing resin composition layer provided on a support is laminated on a semiconductor chip, or a sealing resin composition is applied onto a semiconductor chip and cured (for example, thermally cured). forming a sealing layer;
  • lamination of a semiconductor chip and a sealing resin sheet can be performed by heat-pressing the sealing resin sheet to the semiconductor chip from the support side.
  • the lamination of the semiconductor chip and the encapsulating resin sheet may be performed by a vacuum lamination method, and the lamination conditions are the same as the lamination conditions described in relation to the printed wiring board manufacturing method, and the preferred ranges are also the same. be.
  • the sealing resin composition layer is thermally cured to form a sealing layer.
  • the heat curing conditions are the same as the heat curing conditions described in relation to the printed wiring board manufacturing method.
  • the support of the encapsulating resin sheet may be peeled off after the encapsulating resin sheet is laminated on the semiconductor chip and thermally cured, or the support may be peeled off before laminating the encapsulating resin sheet on the semiconductor chip. good.
  • the application conditions are the same as those for forming the resin composition layer described in relation to the method for producing a multilayer resin sheet of the present invention. It is the same, and the preferred range is also the same.
  • Step (4)- The method of peeling off the substrate and the temporary fixing film can be appropriately changed according to the material of the temporary fixing film.
  • the heating conditions are usually 100 to 250° C. for 1 to 90 seconds or 5 to 15 minutes.
  • the irradiation dose of ultraviolet rays is usually 10 mJ/cm 2 to 1000 mJ/cm 2 .
  • step (5) The material for forming the rewiring layer (insulating layer) is not particularly limited as long as it has insulating properties when the rewiring layer (insulating layer) is formed. can be formed.
  • the multilayer resin sheet of the present invention is laminated such that the surface opposite to the first resin composition layer is bonded to the surface of the semiconductor chip from which the substrate and the temporary fixing film have been peeled off. Thereafter, the multilayer resin sheet is cured to form a rewiring forming layer.
  • a via hole may be formed in the rewiring layer in order to connect the semiconductor chip and a conductor layer, which will be described later, between layers.
  • the via hole may be formed by a known method depending on the material of the rewiring formation layer.
  • Step (6)- The formation of the conductor layer on the rewiring formation layer may be carried out in the same manner as the step (V) described in relation to the printed wiring board manufacturing method.
  • the steps (5) and (6) may be repeated to alternately build up the conductor layers (rewiring layers) and the rewiring formation layers (insulating layers).
  • a semiconductor chip package In manufacturing a semiconductor chip package, (7) forming a solder resist layer on a conductor layer (rewiring layer), (8) forming bumps, (9) separating a plurality of semiconductor chip packages into individual semiconductor chips. A further step of dicing into packages and singulating may be performed. These steps may be performed according to various methods known to those skilled in the art for use in the manufacture of semiconductor chip packages.
  • the multilayer resin sheet of the present invention By forming a rewiring formation layer using the multilayer resin sheet of the present invention, it is possible to distinguish whether a semiconductor package is a fan-in type package or a fan-out type package. Regardless, a semiconductor chip package can be realized. Moreover, the multilayer resin sheet of the present invention can be applied regardless of whether it is a fan-out panel level package (FO-PLP) or a fan-out wafer level package (FO-WLP).
  • FO-PLP fan-out panel level package
  • FO-WLP fan-out wafer level package
  • the semiconductor device of the present invention includes a layer made of the cured multilayer resin sheet of the present invention.
  • the semiconductor device of the present invention can be manufactured using the printed wiring board or semiconductor chip package of the present invention.
  • semiconductor devices examples include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, televisions, etc.) and vehicles (such as motorcycles, automobiles, trains, ships, aircraft, etc.).
  • Thermosetting resin (1) Biphenyl-type epoxy resin ("NC-3000” manufactured by Nippon Kayaku Co., Ltd.) (2) Biphenyl-type epoxy resin ("NC-3000-H” manufactured by Nippon Kayaku Co., Ltd.) (3) p-aminophenol type epoxy resin ("630” manufactured by Mitsubishi Chemical Corporation) (4) Dicyclopentadiene type epoxy resin (manufactured by DIC "HP-7200")
  • curing agent Liquid containing aminotriazine skeleton cresol novolac resin ("LA-3018-50P” manufactured by DIC, containing 50% by mass of solid content and 50% by mass of propylene glycol monoethyl ether) (2) Liquid containing triazine skeleton phenol novolac resin ("LA-7054” manufactured by DIC, containing 60% by mass of solid content and 40% by mass of methyl ethyl ketone) (3) Active ester resin-containing liquid (“HPC-8000-65T” manufactured by DIC, containing 65% by mass of solids and 35% by mass of toluene)
  • LA-3018-50P manufactured by DIC, containing 50% by mass of solid content and 50% by mass of propylene glycol monoethyl ether
  • LA-7054 Liquid containing triazine skeleton phenol novolac resin
  • Active ester resin-containing liquid (“HPC-8000-65T” manufactured by DIC, containing 65% by mass of solids and 35% by
  • Phenoxy resin-containing liquid (“YX6954BH30” manufactured by Mitsubishi Chemical Corporation, containing 30% by mass of solid content, 35% by mass of methyl ethyl ketone, and 35% by mass of cyclohexanone)
  • Polyimide resin 1 polyimide resin synthesized in Synthesis Example 1 below, solid content 20% by mass
  • Maleimide resin 1 (SLK6895-T90, an aliphatic skeleton-containing maleimide resin having a structure represented by the following formula (which may contain an unsaturated bond in part), solid content 90% by mass and toluene 10% by mass)
  • Silica 1 (“SOC4" manufactured by Admatechs Co., Ltd. 100 parts by mass with 0.4 parts by mass of a silane coupling agent having an N-phenyl-3-aminopropyl group ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) Surface-treated spherical silica, average particle size 1.0 ⁇ m)
  • Silica 2 (“SOC2” manufactured by Admatechs Co., Ltd.
  • solvent (1) Solvent (MEK, methyl ethyl ketone, manufactured by Wako Pure Chemical Industries, Ltd.)
  • polyimide resin 1 was presumed to contain a structural unit represented by the following formula (c1a). Also, from the above reaction pathway, it was presumed that the polyimide resin 1 contained a first skeleton derived from BPADA and a second skeleton derived from BPPAN.
  • the glass transition temperature Tg (TMA method) of polyimide resin 1 was 210°C.
  • Tg was measured from 25° C. to 250° C. at a heating rate of 5° C./min using a Rigaku TMA apparatus.
  • first resin composition layer To the obtained resin composition varnish A, 100 parts by mass of spherical silica 3 (“YC100C” manufactured by Admatechs Co., Ltd.) and a silane coupling agent having an N-phenyl-3-aminopropyl group (“KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd. ”) 130 parts by mass of spherical silica surface-treated with 3.0 parts by mass) were mixed and stirred at room temperature until a uniform solution was obtained, to obtain a resin composition varnish B.
  • YC100C manufactured by Admatechs Co., Ltd.
  • KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd. a silane coupling agent having an N-phenyl-3-aminopropyl group
  • the obtained resin composition varnish B was applied onto the release-treated surface of a PET film (thickness: 38 ⁇ m), and then dried in a gear oven at 170°C for 180 seconds to evaporate the solvent. In this manner, a sheet-shaped molding A (first resin composition layer) having a thickness of 2 ⁇ m was obtained on the PET film.
  • Formation of inner layer (layer to be inner layer after lamination (outermost layer before lamination)): Formation method 1 -Lamination by coating Biphenyl type epoxy resin ("NC-3000” manufactured by Nippon Kayaku Co., Ltd.) 20 parts by mass, p-aminophenol type epoxy resin ("630” manufactured by Mitsubishi Chemical Co., Ltd.) 3 parts, dicyclopentadiene type epoxy resin ("HP-7200” manufactured by DIC Corporation) 10 parts by weight, liquid containing aminotriazine skeleton cresol novolac resin ("LA-3018-50P” manufactured by DIC Corporation) 15 parts by weight (solid content: 7.5 parts by weight), active ester Resin-containing liquid (“HPC-8000-65T” manufactured by DIC) 80 parts by mass (52 parts in solid content), imidazole compound (“2P4MZ” manufactured by Shikoku Chemical Industry Co., Ltd.) 2 parts by mass, phenoxy resin-containing liquid (Mitsubishi Chemical "YX6954BH30”) 5 parts by mass (1.5 parts by mass in solid
  • spherical silica 2 (“SOC2” manufactured by Admatechs Co., Ltd.) and a silane coupling agent having an N-phenyl-3-aminopropyl group (manufactured by Shin-Etsu Chemical Co., Ltd. “KBM-573 ”) 290 parts by mass of spherical silica surface-treated with 0.6 parts by mass) were mixed and stirred at room temperature until a uniform solution was obtained, to obtain a resin composition varnish D.
  • SOC2 spherical silica 2
  • KBM-573 silane coupling agent having an N-phenyl-3-aminopropyl group
  • the multilayer resin sheet B has a sheet-shaped molded body A and a sheet-shaped molded body C. As shown in FIG.
  • the obtained multilayer resin sheet B is superimposed on the substrate surface from the sheet-shaped compact C side, and a batch-type vacuum pressure laminator (manufactured by Nichigo-Morton Co., Ltd. 2-stage build-up laminator CVP700) is used to form a sheet. It laminated
  • laminated sample D The laminated multilayer resin sheet with a support was heated at 100°C for 30 minutes and then at 170°C for 30 minutes to thermally cure the multilayer resin sheet to form an insulating layer.
  • laminated sample D The obtained laminated sample is called "laminated sample D".
  • the obtained laminated sample D was subjected to the following swelling treatment, roughening treatment, and electroless plating treatment.
  • Roughening treatment (permanganate treatment): Put the swelling-treated laminated sample in an 80 ° C. sodium permanganate roughening aqueous solution ("Concentrate Compact CP” manufactured by Atotech Japan, “Sodium Hydroxide” manufactured by Wako Pure Chemical Industries, Ltd.), and the roughening temperature Rocked at 80° C. for 20 minutes. Then, after washing for 10 minutes with a 40° C. washing solution (“Reduction Securigant P” manufactured by Atotech Japan, “Sulfuric Acid” manufactured by Wako Pure Chemical Industries, Ltd.), the layered sample E was obtained by further washing with pure water.
  • Concentrate Compact CP manufactured by Atotech Japan, “Sodium Hydroxide” manufactured by Wako Pure Chemical Industries, Ltd.
  • Reduction Securigant P manufactured by Atotech Japan, “Sulfuric Acid” manufactured by Wako Pure Chemical Industries, Ltd.
  • Electroless plating process The surface of Laminated Sample E was treated with an alkaline cleaner (“Cleaner Securigant 902” manufactured by Atotech Japan Co., Ltd.) at 60° C. for 5 minutes to be degreased and washed. After washing, the cured product was treated with a pre-dip liquid ("Pre-dip Neogant B” manufactured by Atotech Japan Co., Ltd.) at 25°C for 2 minutes. Thereafter, the cured product was treated with an activator liquid (“Activator Neogant 834” manufactured by Atotech Japan Co., Ltd.) at 40° C. for 5 minutes to attach a palladium catalyst. Next, the cured product was treated with a reducing liquid (“Reducer Neogant WA” manufactured by Atotech Japan Co., Ltd.) at 30° C. for 5 minutes.
  • an alkaline cleaner (“Cleaner Securigant 902” manufactured by Atotech Japan Co., Ltd.) at 60° C. for 5 minutes to be degreased and washed
  • the cured product is placed in a chemical copper solution ("Basic Printgant MSK-DK”, “Copper Printgant MSK”, “Stabilizer Printgant MSK”, and “Reducer Cu”, all manufactured by Atotech Japan) and subjected to electroless plating. was carried out until the plating thickness reached about 0.1 ⁇ m. After electroless plating, annealing was applied at a temperature of 120° C. for 30 minutes to remove residual hydrogen gas. All the steps up to the electroless plating step were performed using a beaker scale with a treatment solution of 2 L and shaking the cured product.
  • the electroless-plated cured product was electroplated until the plating thickness reached 25 ⁇ m.
  • electrolytic copper plating copper sulfate solution (“Copper sulfate pentahydrate” manufactured by Wako Pure Chemical Industries, “Sulfuric acid” manufactured by Wako Pure Chemical Industries, Ltd. “Basic Leveler Cupalaside HL” manufactured by Atotech Japan, “ Electroplating was carried out using a correction agent "Capalacid GS”) and applying a current of 0.6 A/cm 2 until the plating thickness reached about 25 ⁇ m.
  • the cured product was heated at 190° C. for 1 hour to further cure the cured product.
  • a laminated sample F having a copper plating layer laminated on the upper surface was obtained.
  • Arithmetic mean roughness (Ra) is less than 100 nm ⁇ : Arithmetic mean roughness (Ra) is 100 nm or more and less than 180 nm ⁇ : Arithmetic mean roughness (Ra) is 180 nm or more
  • the minimum value of the measurement value within the measurement area 35 mm is 0.5 kgf / cm or more ⁇ : The minimum value of the measurement value within the measurement area 35 mm is 0.4 kgf / cm, less than 0.5 kgf / cm ⁇ : Within the measurement area 35 mm The minimum value of the measured value is less than 0.4 kgf / cm
  • the resulting resin composition varnish B was applied onto the release-treated surface of a PET film (thickness: 38 ⁇ m), and dried in a gear oven at 100° C. for 2 minutes to evaporate the solvent.
  • a 38 ⁇ m-thick sheet-like molding A′ was obtained on the PET film.
  • a sheet-shaped molding C′ having a thickness of 38 ⁇ m was obtained on a PET film in the same manner except that the resin composition varnish D was used.
  • the PET film was peeled off from the sheet-shaped molded product A′ obtained, and a Rheometer device (“AR-2000” manufactured by TA Instruments Co., Ltd.) was used to measure a frequency of 6.28 rad/sec, a starting temperature of 60° C., and a heating rate. Dynamic viscoelasticity was measured at 5° C./min and a strain of 0.75% to measure the storage modulus G′(A). Similarly, the storage elastic modulus G' (B) of the sheet-like formed article C' obtained was measured. Then, (Log10(G'(B)) at 100°C) - (Log10(G'(A)) at 100°C) (referred to as G' difference in the table) was obtained.
  • a Rheometer device (“AR-2000” manufactured by TA Instruments Co., Ltd.) was used to measure a frequency of 6.28 rad/sec, a starting temperature of 60° C., and a heating rate. Dynamic viscoelasticity was measured at 5° C./min and
  • Example 2 A sample was prepared and evaluated in the same manner as in Example 1, except that the method for forming the inner layer was changed to Formation Method 2 below and the obtained multilayer resin sheet B' was used.
  • Formation of inner layer Formation method 2-Lamination by lamination Using an applicator, the resin composition varnish D obtained on the release-treated surface of a PET film (thickness 38 ⁇ m) was applied, and then placed in a gear oven at 100 ° C. Dry for 2 minutes to evaporate the solvent. In this manner, a sheet-like molded article C having a thickness of 38 ⁇ m was obtained on the PET film.
  • the sheet-shaped molded body A and the sheet-shaped molded body C are laminated with a lamination pressure of 0.4 MPa and a lamination temperature of 0.4 MPa using a vacuum pressure laminator machine ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) so that the coated surfaces overlap each other. Only lamination was performed at 100° C. for 60 seconds to obtain a multilayer resin sheet B′.
  • MVLP-500 vacuum pressure laminator machine
  • Examples 3-6 and Comparative Examples 1-3 A sample was prepared and evaluated in the same manner as in Example 1, except that the composition of Example 1 was changed as shown in Tables 1 and 2.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une nouvelle feuille de résine qui présente une bonne planéité de surface même si elle est superposée sur un élément d'objet d'empilement qui présente une surface irrégulière, tout en permettant l'obtention d'un produit durci qui présente une bonne adhérence à une couche conductrice. Cette feuille de résine est une feuille de résine multicouche qui est pourvue de deux couches de composition de résine ou plus, tout en étant caractérisée en ce que si G'(A) est le module d'élasticité (Pa) d'une première couche de composition de résine qui sert de couche la plus à l'extérieur, et G'(B) est le module d'élasticité (Pa) de couches autres que la première couche de composition de résine, lors de la réalisation d'une mesure de viscoélasticité dynamique de la feuille de résine multicouche à une fréquence de 6,28 rad/sec, ((Log10(G'(B)) à 100°C) – (Log10(G'(A)) à 100°C)) est supérieur ou égal à -2 mais inférieur à 0.
PCT/JP2022/040994 2021-11-11 2022-11-02 Feuille de résine multicouche WO2023085184A1 (fr)

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US20240110098A1 (en) * 2022-09-13 2024-04-04 Government Of The United States, As Represented By The Secretary Of The Air Force Highly aromatic and liquid-crystalline co-polyimides endcapped with aromatic groups and crosslinked products therefrom

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JP2010235744A (ja) * 2009-03-31 2010-10-21 Arakawa Chem Ind Co Ltd 接着シート、及び当該接着シートを使用して得られる多層プリント基板
JP2015188073A (ja) * 2014-03-13 2015-10-29 積水化学工業株式会社 多層絶縁フィルム、多層基板の製造方法及び多層基板
JP2020042080A (ja) * 2018-09-07 2020-03-19 東洋紡フイルムソリューション株式会社 多層積層フィルム、それを用いた輝度向上部材および偏光板
WO2020235164A1 (fr) * 2019-05-22 2020-11-26 三菱ケミカル株式会社 Film multicouche
JP2021163767A (ja) * 2020-03-30 2021-10-11 味の素株式会社 プリント配線板の製造方法

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WO2003047324A1 (fr) * 2001-11-30 2003-06-05 Ajinomoto Co., Inc. Procede de stratification de carte a circuit imprime et procede de formation de couche isolante, carte a circuit imprime multicouche et procede de production associe, et film adhesif pour carte a circuit imprime multicouche
JP2010235744A (ja) * 2009-03-31 2010-10-21 Arakawa Chem Ind Co Ltd 接着シート、及び当該接着シートを使用して得られる多層プリント基板
JP2015188073A (ja) * 2014-03-13 2015-10-29 積水化学工業株式会社 多層絶縁フィルム、多層基板の製造方法及び多層基板
JP2020042080A (ja) * 2018-09-07 2020-03-19 東洋紡フイルムソリューション株式会社 多層積層フィルム、それを用いた輝度向上部材および偏光板
WO2020235164A1 (fr) * 2019-05-22 2020-11-26 三菱ケミカル株式会社 Film multicouche
JP2021163767A (ja) * 2020-03-30 2021-10-11 味の素株式会社 プリント配線板の製造方法

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US20240110098A1 (en) * 2022-09-13 2024-04-04 Government Of The United States, As Represented By The Secretary Of The Air Force Highly aromatic and liquid-crystalline co-polyimides endcapped with aromatic groups and crosslinked products therefrom
US11976231B2 (en) * 2022-09-13 2024-05-07 United States Of America As Represented By The Secretary Of The Air Force Highly aromatic and liquid-crystalline co- polyimides endcapped with aromatic groups and crosslinked products therefrom

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