CN107129589A - Resin sheet with supporter - Google Patents

Resin sheet with supporter Download PDF

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Publication number
CN107129589A
CN107129589A CN201710108030.8A CN201710108030A CN107129589A CN 107129589 A CN107129589 A CN 107129589A CN 201710108030 A CN201710108030 A CN 201710108030A CN 107129589 A CN107129589 A CN 107129589A
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CN
China
Prior art keywords
resin
supporter
epoxy resin
mass
resin sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710108030.8A
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Chinese (zh)
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CN107129589B (en
Inventor
中村茂雄
鸟居恒太
藤原千寻
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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Publication of CN107129589A publication Critical patent/CN107129589A/en
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Publication of CN107129589B publication Critical patent/CN107129589B/en
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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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive
    • 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
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B32B2310/0843—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using laser
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Epoxy Resins (AREA)

Abstract

The problem of the present invention is the resin sheet with supporter, the manufacture method of printed wiring board, printed wiring board and the semiconductor device for providing the generation for inhibiting the recessed damage portion generated on the bearing of trend at the interface of cured each resin composition layer.The solution of the present invention is a kind of resin sheet with supporter, and it has supporter and the resin sheet being arranged on supporter, wherein, resin sheet has：It is arranged at the second resin composition layer formed by the second resin combination of first resin composition layer formed by the first resin combination on the support side side opposite with support side with being arranged on；First resin combination includes (a) inorganic filling material, and the content of (a) composition is below 30 mass %；Second resin combination includes (a) inorganic filling material, and the content of (a) composition is more than 60 mass %；The difference of the thermal conductivity factor of the thermal conductivity factor of first thermosetting compound and the second thermosetting compound is below 0.4W/mK.

Description

Resin sheet with supporter
Technical field
The present invention relates to the resin sheet with supporter.Further relate to manufacture method, the printed wiring board and half of printed wiring board Conductor device.
Background technology
As printed wiring board (hereinafter also referred to " wiring plate ".) manufacture method, be widely used for alternately accumulation entered The conductor layer of circuit of having gone formation and stacking (build up) mode of insulating barrier, it is known that insulating barrier is by including being connect with conductor layer Tactile side and implement plating processing side 2 layers of resin composition layer be solidified to form (for example, referring to patent document 1)。
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2014-17301 publications.
The content of the invention
Invent problem to be solved
In recent years, the information traffic increases, and therefore, in the manufacture of printed wiring board, expects fine wiring.
In order to reach fine wiring, surface of insulating layer is set to turn into low roughness, in addition, in 2 layers of resin composition layer In, the resin composition layer of the side (side contacted with conductor layer) for implementing plating processing is expected to reduce inorganic fill The content of material.On the other hand, from the viewpoint of reduction thermal coefficient of expansion, for the opposing party's (side contacted with substrate) Resin composition layer, expects to increase the content of inorganic filling material.
The present inventor etc. has attempted to form logical on the insulating barrier for being solidified to form such 2 layers of resin composition layer Hole.As a result find, recessed damage is produced on the bearing of trend at the interface of cured each resin composition layer on the side wall of through hole Portion's (picking out れ portions) (reference picture 1).If producing such recessed damage portion, cause to produce space, Ke Nengcheng when carrying out plating processing For the obstacle of fine wiring.
The problem of the present invention, which is to provide, to be inhibited on the bearing of trend at the interface of cured each resin composition layer The resin sheet with supporter, the manufacture method of printed wiring board, printed wiring board and the semiconductor of the generation in the recessed damage portion of generation Device.
Means for solving the problems
The present inventor etc. have made intensive studies for above-mentioned problem, as a result find, by reducing first and second resin combination The difference of the thermal conductivity factor of the thermosetting compound of nitride layer, can reduce on the bearing of trend at the interface of cured each resin composition layer The length in the recessed damage portion produced.The present inventor etc. carried out deeper into research, as a result find, by making carry out plating processing The content of the inorganic filling material of first resin composition layer of side is less than the inorganic filling material of the second resin composition layer Content, the difference of above-mentioned thermal conductivity factor can be reduced, so as to complete the present invention.
That is, the present invention includes following content.
[1] resin sheet with supporter, it has supporter and the resin sheet being arranged on supporter, it is characterised in that
Resin sheet has：
Be arranged at support side the first resin composition layer formed by the first resin combination and
The second resin composition layer formed by the second resin combination of the side opposite with support side is arranged on,
First resin combination includes (a) inorganic filling material, regard the nonvolatile component in the first resin combination as 100 matter When measuring %, the content of (a) composition is below 30 mass %,
Second resin combination includes (a) inorganic filling material, regard the nonvolatile component in the second resin combination as 100 matter When measuring %, the content of (a) composition is more than 60 mass %,
The difference of the thermal conductivity factor of the thermal conductivity factor of first thermosetting compound and the second thermosetting compound is below 0.4W/mK,
The first thermosetting compound is to make the first resin combination in 100 DEG C of heat cures 30 minutes and then in 190 DEG C of heat cures 90 Obtained from minute,
The second thermosetting compound is to make the second resin combination in 100 DEG C of heat cures 30 minutes and then in 190 DEG C of heat cures 90 Obtained from minute.
[2] resin sheet with supporter according to [1], wherein, the thickness of resin sheet is less than 40 μm.
[3] resin sheet with supporter according to [1] or [2], wherein, the thickness of resin sheet is less than 25 μm.
[4] resin sheet with supporter according to any one of [1] ~ [3], wherein, by the first resin combination The average grain diameter of (a) composition be designated as R1 (μm), the average grain diameter of (a) composition in the second resin combination is designated as R2 (μm) When, the ratio between R1 and R2, i.e. R2/R1 are 1~15.
[5] resin sheet with supporter according to any one of [1] ~ [4], wherein, the first resin combination is included (b) epoxy resin, (b) composition has mesomorphic skeleton (mesogenic skeleton).
[6] resin sheet with supporter according to [5], wherein, (b) composition is selected from di- cresols type asphalt mixtures modified by epoxy resin More than a kind in fat, bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin and naphthalene type epoxy resin.
[7] resin sheet with supporter according to any one of [1] ~ [6], it is used to form the exhausted of printed wiring board Edge layer.
[8] manufacture method of printed wiring board, methods described includes following processes：
Process (I), by the resin sheet with supporter any one of [1]~[7] with the second resin composition layer and internal layer The mode of substrate engagement is layered on internal substrate,
Process (II), insulating barrier is formed by the resin sheet heat cure with supporter, and
Process (III), forms through hole on the insulating layer, removes supporter.
[9] manufacture method of the printed wiring board according to [8], wherein, in process (III), using laser in insulation Through hole is formed on layer.
[10] manufacture method of the printed wiring board according to [8] or [9], wherein, the opening diameter of through hole is 40 μm Below.
[11] printed wiring board, it is exhausted comprising what is formed as the resin sheet with supporter any one of [1]~[7] Edge layer.
[12] semiconductor device, it possesses [11 [described printed wiring boards.
The effect of invention
Pass through the present invention, it is possible to provide inhibit generated on the bearing of trend at the interface of cured each resin composition layer recessed The resin sheet with supporter, the manufacture method of printed wiring board, printed wiring board and the semiconductor device of the generation in damage portion.
Brief description of the drawings
Fig. 1 is the cross-section photograph of the insulating barrier with recessed damage portion.
Fig. 2 is the schematic diagram for a mode for representing the resin sheet with supporter of the present invention.
Fig. 3 is for the cross-section photograph for the length for illustrating recessed damage portion.
Embodiment
Hereinafter, to the resin sheet with supporter of the present invention, the manufacture method of printed wiring board, printed wiring board and half Conductor device is described in detail.
Before the resin sheet with supporter of the present invention is described in detail, to the first resin combination and the second tree Oil/fat composition is illustrated, and first resin combination and the second resin combination be, the resin of the invention with supporter Used in piece, in the first resin composition layer and the second resin composition layer included in forming resin sheet.
(the first resin combination)
The first resin combination for forming the first resin composition layer includes (a) inorganic filling material, by the first resin combination In nonvolatile component as 100 mass % when, as long as the content of (a) composition be below 30 mass %, be just not particularly limited, only Want its solidfied material that there is sufficient coating fissility and insulating properties.As the first resin combination, for example, can enumerate except Include the composition outside inorganic filling material also comprising curable resin and its curing agent.As curable resin, it can be used The workable known curable resin when forming the insulating barrier of printed wiring board, wherein, preferred epoxy.Cause This, in one embodiment, the first resin combination includes (b) epoxy resin and (c) curing agent.As needed, the first tree Oil/fat composition also includes thermoplastic resin, curing accelerator, fire retardant and organic filler material.
Hereinafter, pair it can be described in detail as each composition of the materials'use of the first resin combination.
- (a) inorganic filling materials-
The material of inorganic filling material is not particularly limited, for example, silica, aluminum oxide, glass, cordierite, silicon can be enumerated Oxide, barium sulfate, barium carbonate, talcum, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminium hydroxide, magnesium hydroxide, Calcium carbonate, magnesium carbonate, magnesia, boron nitride, aluminium nitride, nitrogenized manganese, aluminium borate, strontium carbonate, strontium titanates, calcium titanate, magnesium titanate, Bismuth titanates, titanium oxide, zirconium oxide, barium titanate, metatitanic acid barium zirconate, barium zirconate, calcium zirconate, basic zirconium phosphate and phosphoric acid tungsten wire array, carbonization Silicon etc..In these, preferably carborundum, silica, particularly preferably silica.In addition, as silica, being preferably Preparing spherical SiO 2.Inorganic filling material can be used alone a kind, and two or more also can be combined and uses.
The average grain diameter of inorganic filling material is not particularly limited, from obtain the small insulating barrier of surface roughness viewpoint, From the viewpoint of fine wiring formative is improved, preferably less than 2 μm, more preferably more preferably less than 1.5 μm, 1 μm Below.The lower limit of the average grain diameter is not particularly limited, preferably more than 0.01 μm, more preferably more than 0.1 μm, further excellent Elect more than 0.3 μm as.As the commercially available product of the inorganic filling material with such average grain diameter, for example, electrification can be enumerated Learn Industrial Co., Ltd's system " UFP-30 ", Zhu Jin materials Co., Ltd. of Nippon Steel (Nippon Steel Sumikin Materials co., Ltd) system " SPH516-05 ", Shinano Electric Refining Co., Ltd.'s system " SER-A06 " etc..
The average grain diameter of inorganic filling material is surveyed using the laser diffraction based on Michaelis (Mie) scattering theory-scattering method It is fixed.Specifically, using laser diffraction and scattering formula particle size distribution device, inorganic filling material is made according to volume reference Size distribution, using its median particle diameter as average grain diameter, be thus measured.For determination sample, preferably use Inorganic filling material is scattered in the product in methyl ethyl ketone using ultrasonic wave.It is used as laser diffraction and scattering formula granularity point Cloth determines device, and Shimadzu Scisakusho Ltd's system " SALD-2200 " etc. can be used.
For inorganic filling material, from the viewpoint of moisture-proof and dispersiveness is improved, preferably with silane coupler, At least one kind of surface conditioning agent in alkoxysilane compound containing trialkylsilyl group in molecular structure and organic silazane hydride compounds is surface-treated.They can be with It is oligomer.As the example of surface conditioning agent, amino silicone methane series coupling agent, epoxy silane system coupling agent, sulfydryl silicon can be enumerated Methane series coupling agent, silane series coupling agent, organic silazane hydride compounds, titanate esters system coupling agent etc..It is used as the city of surface conditioning agent Sell product, for example, can enumerate Shin-Etsu Chemial Co., Ltd's system " KBM403 " (3- glycidoxypropyltrime,hoxysilanes), Shin-Etsu Chemial Co., Ltd's system " KBM803 " (3-mercaptopropyi trimethoxy silane), Shin-Etsu Chemial Co., Ltd's system " KBE903 " (APTES), Shin-Etsu Chemial Co., Ltd's system " KBM573 " (N- phenyl -3- amino Propyl trimethoxy silicane), Shin-Etsu Chemial Co., Ltd's system " SZ-31 " (HMDS), SHIN-ETSU HANTOTAI's chemical industry Co. Ltd. system " KBM103 " (phenyltrimethoxysila,e), Shin-Etsu Chemial Co., Ltd's system " KBM-4803 " (oblong link Oxygen type silane coupler) etc..Surface conditioning agent can be used alone a kind, also can be combined and uses two or more.
The degree of surface treatment based on surface conditioning agent can utilize the carbon amounts of the per unit surface area of inorganic filling material Evaluated.For the carbon amounts of the per unit surface area of inorganic filling material, from the dispersiveness for improving inorganic filling material From the viewpoint of, preferably 0.02mg/m2More than, more preferably 0.1mg/m2More than, more preferably 0.2mg/m2More than. On the other hand, from the viewpoint of the melt viscosity under the melt viscosity and sheet form for suppressing resin varnish rises, it is preferably 1mg/m2Hereinafter, more preferably 0.8mg/m2Hereinafter, more preferably 0.5mg/m2Below.
The carbon amounts of the per unit surface area of inorganic filling material can be right using solvent (for example, methyl ethyl ketone (MEK)) Inorganic filling material after surface treatment is measured after carrying out carrying out washing treatment.Specifically, the enough of solvent will can be used as MEK is added in the inorganic filling material being surface-treated with surface conditioning agent, and supersound washing in 5 minutes is carried out in 25 DEG C. Supernatant is removed, solid constituent is dried, then, the carbon of the per unit surface area of inorganic filling material is determined using carbon analysis meter Amount.As carbon analysis meter, Horiba Ltd's system " EMIA-320V " etc. can be used.
For the content of the inorganic filling material in the first resin combination, examined from the viewpoint for improving coating fissility Consider, during using the nonvolatile component in the first resin combination as 100 mass %, be below 30 mass %, preferably 25 mass % with Under, more preferably below 20 mass %.The lower limit of the content of (c) composition in the first resin combination is not particularly limited, can be with For 0 mass %, typically more than 5 mass %, 10 mass % are with first-class.
- (b) epoxy resin-
As epoxy resin, for example, di- first phenol-type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy tree can be enumerated Fat, bisphenol-s epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene-type epoxy resin, tris phenol type epoxy, naphthols Phenol aldehyde type epoxy resin (naphthol novolac epoxy resin), novolac type epoxy resin (phenol Novolac epoxy resin), the tert-butyl group-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene Type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, Cresol formaldehyde (cresol Novolac) type epoxy resin, biphenyl type epoxy resin, wire aliphatic epoxy resin, the asphalt mixtures modified by epoxy resin with butadiene structure Fat, cycloaliphatic epoxy resin, hetero ring type epoxy resin, containing whorled epoxy resin, cyclohexanedimethanol type epoxy resin, Asia Naphthyl ether type epoxy, trihydroxy methyl type epoxy resin, tetraphenyl ethane type epoxy resin etc..Epoxy resin can be used alone 1 kind, two or more also can be combined and uses.From the aspect of thermal conductivity factor is improved, (b) composition is preferably with mesomorphic skeleton Epoxy resin, more preferably selected from di- first phenol-type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl More than a kind in type epoxy resin and naphthalene type epoxy resin.So-called mesomorphic skeleton, refers to comprising bar-shaped or tabular, presentation liquid The general name of the group of upright and outspoken group (aromatic ring) as crystalline substance.
Epoxy resin preferably is contained in 1 molecule the epoxy resin with more than 2 epoxy radicals.By epoxy resin not When volatile ingredient is as 100 mass %, preferably at least more than 50 mass % are the epoxy with more than 2 epoxy radicals in 1 molecule Resin.Wherein, preferably be contained in 1 molecule have more than 2 epoxy radicals and at a temperature of 20 DEG C for liquid epoxy resin (with It is referred to as " liquid-state epoxy resin " down.) and in 1 molecule have more than 3 epoxy radicals and at a temperature of 20 DEG C be solid-state epoxy Resin is (hereinafter referred to as " solid epoxy resin ".).It is used as epoxy resin by and with liquid-state epoxy resin and solid epoxy resin, It can obtain with excellent flexible resin combination.In addition, the fracture strength of the solidfied material of resin combination is also improved.
It is used as liquid-state epoxy resin, preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol AF type asphalt mixtures modified by epoxy resin Fat, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, novolac type epoxy Resin, the cycloaliphatic epoxy resin with ester skeleton, cyclohexanedimethanol type epoxy resin, glycidyl amine type asphalt mixtures modified by epoxy resin Fat and the epoxy resin with butadiene structure, more preferably glycidyl amine type epoxy resin, bisphenol A type epoxy resin, Bisphenol f type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin.As the concrete example of liquid-state epoxy resin, it can lift Go out " HP4032 ", " HP4032D ", " HP4032SS " (naphthalene type epoxy resin), Mitsubishi chemical Co., Ltd of Dainippon Ink Chemicals " 828US ", " jER828EL ", " 825 " (bisphenol A type epoxy resin), " jER807 ", " 1750 " (bisphenol F type epoxy tree of system Fat), " jER152 " (novolac type epoxy resin), " 630 ", " 630LSD " (glycidyl amine type epoxy resin), new day Iron live aurification Co. Ltd. system " ZX1059 " (melange of bisphenol A type epoxy resin and bisphenol f type epoxy resin), " EX-721 " (the glycidyl ester type epoxy resin) of Nagase ChemteX Co. Ltd. systems, Co., Ltd.'s Daicel " Celloxide 2021P " (cycloaliphatic epoxy resin with ester skeleton), " PB-3600 " (have the epoxy of butadiene structure Resin), " ZX1658 ", " ZX1658GS " (the liquid 1,4- glycidols butylcyclohexane) of Nippon Steel Chemical Co., Ltd, three " 630LSD " (the glycidyl amine type epoxy resin) of water chestnut KCC etc..They can be used alone a kind, also can group Close two or more and use.
It is used as solid epoxy resin, the preferably functional epoxy resins of naphthalene type 4, Cresol formaldehyde type epoxy resin, two rings penta 2 Ene-type epoxy resin, tris phenol type epoxy, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy, Anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenyl ethane type epoxy resin, the more preferably functional epoxy resins of naphthalene type 4, Naphthol type epoxy resin and biphenyl type epoxy resin.As the concrete example of solid epoxy resin, Dainippon Ink Chemicals's system can be enumerated " HP4032H " (naphthalene type epoxy resin), " HP-4700 ", " HP-4710 " (functional epoxy resins of naphthalene type 4), " N-690 " (cresols Formaldehyde type epoxy resin), " N-695 " (Cresol formaldehyde type epoxy resin), " HP-7200 " (dicyclopentadiene-type epoxy resin), “HP-7200HH”、“HP-7200H”、“EXA-7311”、“EXA-7311-G3”、“EXA-7311-G4”、“EXA-7311-G4S”、 " HP6000 " (naphthylene ether type epoxy), " EPPN-502H " (tris phenol type epoxy) of Nippon Kayaku K. K, " NC7000L " (naphthol novolac type epoxy resin), " NC3000H ", " NC3000 ", " NC3000L ", " NC3100 " (biphenyl type ring Oxygen tree fat), " ESN475V " (naphthalene type epoxy resin) of Nippon Steel ＆ Sumitomo Metal Corporation, " ESN485 " (naphthol novolac type Epoxy resin), " YX4000H ", " YL6121 " (biphenyl type epoxy resin), " YX4000HK " of Mitsubishi chemical Co., Ltd (di- first phenol-type epoxy resin), " YX8800 " (anthracene type epoxy resin), chemical (Osaka ガ ス ケ ミ カ Le) the strain formula of Osaka combustion gas " PG-100 ", " CG-500 " of commercial firm, " YL7760 " (the bisphenol AF type epoxy resin) of Mitsubishi chemical Co., Ltd, " YL7800 " (fluorenes type epoxy resin), " jER1010 " (the solid-state bisphenol A type epoxy resin) of Mitsubishi chemical Co., Ltd, " jER1031S " (tetraphenyl ethane type epoxy resin) etc..They can be used alone a kind, and two or more also can be combined and uses.
When liquid-state epoxy resin and solid epoxy resin are as epoxy resin, their amount ratio (liquid epoxy tree Fat：Solid epoxy resin) it is preferably 1 by quality ratio：0.1~1：15 scope.By making liquid-state epoxy resin and solid-state ring The amount ratio of oxygen tree fat is above range, can obtain following effects：I) with the form of resin sheet in use, can bring appropriate viscous Conjunction property；Ii) with the form of resin sheet, in use, can obtain sufficient flexibility, treatability is improved；And, iii) can be had There is the solidfied material of sufficient fracture strength；Etc..From it is above-mentioned i)~iii) effect from the viewpoint of, liquid-state epoxy resin with it is solid Amount ratio (the liquid-state epoxy resin of state epoxy resin：Solid epoxy resin) 1 is more preferably by quality ratio：0.3~1：10 model Enclose, more preferably 1：0.6~1：8 scope.
For the content of the epoxy resin in the first resin combination, from obtaining showing good mechanical strength, absolutely From the viewpoint of the insulating barrier of edge reliability, preferably more than 1 mass %, more preferably more than 2 mass %, more preferably 3 More than quality %.For the upper limit of the content of epoxy resin, as long as playing the effect of the present invention, it is not particularly limited, Preferably below 80 mass %, more preferably below 70 mass %, more preferably below 60 mass %.
It should be noted that in the present invention, for the content of each composition in resin combination, as long as no separately Clearly state, refer to regard the nonvolatile component in resin combination as value during 100 mass %.
The epoxide equivalent of epoxy resin is preferably 50~5000, more preferably 50~3000, more preferably 80~ 2000, it is still more preferably 110~1000.By as above range, so that the crosslink density of solidfied material becomes abundant, can Form the small insulating barrier of surface roughness.It should be noted that epoxide equivalent can be determined according to JIS K7236, it is to include 1 equivalent Epoxy radicals resin quality.
The weight average molecular weight of epoxy resin is preferably 100~5000, more preferably 250~3000, more preferably 400 ~1500.Herein, the weight average molecular weight of epoxy resin is to be changed using what gel permeation chromatography (GPC) method was measured according to polystyrene The weight average molecular weight of calculation.
- (c) curing agent-
As curing agent, as long as with the function of epoxy resin cure is made, being not particularly limited, for example, phenol can be enumerated (phenol) be curing agent, naphthols system curing agent, active ester system curing agent, benzoxazine system curing agent, cyanate system curing agent, And carbodiimide system curing agent etc..Curing agent can be used alone a kind, or also and can use two or more.(c) composition is preferably choosing From in phenol system curing agent, naphthols system curing agent, active ester system curing agent, carbodiimide system curing agent and cyanate system curing agent More than a kind.
As phenol system curing agent and naphthols system curing agent, from the viewpoint of heat resistance and water resistance, it is however preferred to have The phenol system curing agent of phenolic resin (novolac) structure or the naphthols system curing agent with phenolic resin structure.In addition, from From the viewpoint of the adaptation of conductor layer, preferably nitrogenous phenol system curing agent, the more preferably phenol containing triazine skeleton It is curing agent.Wherein, from the viewpoint of height meets heat resistance, water resistance and adaptation with conductor layer, preferably contain The linear phenol-aldehyde resin curing agent of triazine skeleton.
As phenol system curing agent and the concrete example of naphthols system curing agent, for example, bright and chemical conversion Co. Ltd. system can be enumerated " MEH-7700 ", " MEH-7810 ", " MEH-7851 ", " MEH-7851H ", " NHN " of Nippon Kayaku K. K, " CBN ", " GPH ", " SN170 ", " SN180 ", " SN190 ", " SN475 ", " SN485 " of Nippon Steel ＆ Sumitomo Metal Corporation, " SN495 ", " SN375 ", " SN395 ", " TD-2090 ", " LA-7052 ", " LA-7054 ", " LA- of Dainippon Ink Chemicals 1356 ", " LA-3018-50P ", " EXB-9500 " etc..
From the viewpoint of the insulating barrier with the excellent adhesion of conductor layer is obtained, further preferably active ester system curing agent.Make For active ester system curing agent, it is not particularly limited, generally, preferably using phenol esters, benzenethiol esters, N- hydroxylamine esters Class, esters of heterocycle hydroxyl compound etc. have the compound of the high ester group of more than 2 reactivities in 1 molecule.The activity Ester system curing agent preferably passes through carboxylic acid compound and/or thiocarboxylic acid compound and hydroxy compounds and/or mercaptan compound Condensation reaction and obtain.Especially from the viewpoint of heat resistance is improved, being preferably can be by carboxylic acid compound and hydroxy compounds Obtained active ester system curing agent, can more preferably be obtained by carboxylic acid compound and oxybenzene compound and/or naphthol compound Active ester system curing agent.As carboxylic acid compound, for example, benzoic acid, acetic acid, butanedioic acid, maleic acid, itaconic acid, neighbour can be enumerated Phthalic acid, M-phthalic acid, terephthalic acid (TPA), pyromellitic acid etc..As oxybenzene compound or naphthol compound, for example, can Enumerate quinhydrones, resorcinol, bisphenol-A, Bisphenol F, bisphenol S, phenolphthalin, the bisphenol-A that methylates, the Bisphenol F that methylates, methylate bis-phenol S, phenol, orthoresol, metacresol, paracresol, catechol, alpha-Naphthol, betanaphthol, 1,5- dihydroxy naphthlenes, 1,6- dihydroxy naphthlenes, 2,6- dihydroxy naphthlenes, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, two Cyclopeutadiene type bisphenol compounds, linear phenol-aldehyde resin etc..Herein, " dicyclopentadiene-type bisphenol compounds " refer to, 1 Bisphenol compounds obtained from 2 molecule phenol are condensed on molecule bicyclopentadiene.
Specifically, preferably comprising dicyclopentadiene-type biphenol structure active ester compound, naphthalene structure is included Active ester compound, the active ester compound of the acetylate comprising linear phenol-aldehyde resin, the benzene first comprising linear phenol-aldehyde resin The active ester compound of acylate, wherein, more preferably the active ester compound comprising naphthalene structure, include dicyclopentadiene-type hexichol The active ester compound of phenol structure." dicyclopentadiene-type biphenol structure " is represented by the cyclopentylene of phenylene-two (ジ シ Network ロ ペ Application チ レ Application)-phenylene formation divalent construction unit.
As the commercially available product of active ester system curing agent, it can enumerate as the activity for including dicyclopentadiene-type biphenol structure " EXB9451 ", " EXB9460 ", " EXB9460S ", " HPC-8000-65T ", " HPC-8000H-65TM " of ester compounds, " EXB-8000L-65TM " (Dainippon Ink Chemicals's system), " EXB9416-70BK " as the active ester compound comprising naphthalene structure (Dainippon Ink Chemicals's system), as the acetylate comprising linear phenol-aldehyde resin active ester compound " DC808 " (Mitsubishi Learn Co. Ltd. system), as the benzoylate comprising linear phenol-aldehyde resin active ester compound " YLH1026 " (Mitsubishi KCC's system), as the acetylate for linear phenol-aldehyde resin active ester system curing agent " DC808 " (Mitsubishi Learn Co. Ltd. system), as the benzoylate for linear phenol-aldehyde resin active ester system curing agent " YLH1026 " (Mitsubishi KCC's system), " YLH1030 " (Mitsubishi chemical Co., Ltd's system), " YLH1048 " (Mitsubishi chemical Co., Ltd's system) Deng.
As the concrete example of benzoxazine system curing agent, can enumerate Showa Highpolymer Co., Ltd " HFB2006M ", " P-d ", " F-a " of Shikoku Chem.
As cyanate system curing agent, for example, can enumerate bisphenol A dicyanate, polyphenol cyanate, it is oligomeric (3- methylene- 1,5- phenylenecyanates), 4,4 '-di-2-ethylhexylphosphine oxide (2,6- 3,5-dimethylphenyls cyanate), 4,4 '-ethylidene (ethylidene) Double (the 4- cyanic acid ester group) phenyl-propanes of dicyanate, hexafluoro bisphenol-a dicyanate, 2,2-, double (the 4- cyanic acid ester groups of 1,1- Phenylmethane), double (4- cyanic acid ester group -3,5- 3,5-dimethylphenyls) methane, double (4- cyanatephenyls -1- (the methyl Asia second of 1,3- Base)) the 2 function cyanate ester resins such as benzene, double (4- cyanatephenyls) thioethers and double (4- cyanatephenyls) ethers, by line style Multifunctional cyanate ester resin, these cyanate ester resins carry out a part of triazine derived from phenolic resin and CF etc. Obtained from prepolymer etc..As the concrete example of cyanate system curing agent, Lonza Japan Co. Ltd. systems can be enumerated " PT30 " and " PT60 " (being novalac-type multifunctional cyanate ester resin), " BA230 ", " BA230S75 " (bisphenol-A two Part or all of cyanate carries out triazine and forms the prepolymer of trimer) etc..
As the concrete example of carbodiimide system curing agent, " the V- of Nisshinbo Chemical Co. Ltd. systems can be enumerated 03 ", " V-07 " etc..
For the amount ratio of epoxy resin and curing agent, with [total number of the epoxy radicals of epoxy resin]：[curing agent The total number of reactive group] ratiometer, preferably 1：0.01~1：2 scope, more preferably 1：0.015~1：1.5, enter one Step is preferably 1：0.02~1：1.Herein, the reactive group of curing agent is activity hydroxy, active ester groups etc., according to the kind of curing agent Class it is different and different.In addition, the total number of the epoxy radicals of epoxy resin refers to calculate each ring for whole epoxy resin Value obtained from the summation being worth obtained from the solid constituent quality divided by epoxide equivalent of oxygen tree fat, the reactive group of curing agent Total number, which refers to calculate for whole curing agent, obtains the solid constituent quality divided by reactive group equivalent of each curing agent Value summation obtained from be worth.By making the amount ratio of epoxy resin and curing agent be above range so that resin combination The heat resistance of solidfied material is further improved.
In one embodiment, the first resin combination includes foregoing (b) epoxy resin and (c) curing agent.For For resin combination, it is preferred that respectively, as (b) epoxy resin, liquid-state epoxy resin and solid epoxy resin are included Mixture (liquid-state epoxy resin：The mass ratio of solid epoxy resin is preferably 1：0.1~1：15, more preferably 1：0.3~1： 12, more preferably 1：0.6~1：10), as (c) curing agent, comprising selected from by phenol system curing agent, the solidification of naphthols system More than a kind in the group that agent, active ester system curing agent, carbodiimide system curing agent and cyanate system curing agent are constituted.
The content of curing agent in first resin combination is not particularly limited, preferably below 45 mass %, more preferably Below 43 mass %, more preferably below 40 mass %.In addition, lower limit is not particularly limited, preferably more than 10 mass %, More preferably more than 15 mass %.
- (d) thermoplastic resins-
First resin combination can also contain (d) thermoplastic resin in addition to containing (a)~(c) compositions.
As thermoplastic resin, for example, phenoxy resin, polyvinyl acetal resin, vistanex, poly- fourth can be enumerated It is diene resin, polyimide resin, polyamide-imide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, poly- Phenylene ether resins, polycarbonate resin, polyether-ether-ketone resin, polyester resin, preferably phenoxy resin.Thermoplastic resin can be independent Using a kind, or also can be combined use two or more.
The weight average molecular weight converted according to polystyrene of thermoplastic resin is preferably 8,000~70,000 scope, more Preferably 10,000~60,000 scope, more preferably 20,000~60,000 scope.Thermoplastic resin according to The weight average molecular weight of polystyrene conversion can be determined using gel permeation chromatography (GPC) method.Specifically, for thermoplastic resin The weight average molecular weight converted according to polystyrene for, be used as survey using Shimadzu Scisakusho Ltd LC-9A/RID-6A Determine device, using Showa Denko K. K Shodex K-800P/K-804L/K-804L as post, using chloroform etc. as Mobile phase, is measured under 40 DEG C of column temperature, is calculated using the standard curve of polystyrene standard.
As phenoxy resin, for example, can enumerate with being selected from by bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, double Phenol acetophenone skeleton, phenol-formaldehyde resin matrix, biphenyl backbone, fluorene skeleton, bicyclopentadiene skeleton, ENB skeleton, naphthalene skeleton, The benzene oxygen of more than a kind of skeleton in the group that anthracene skeleton, adamantane framework, terpenes skeleton and trimethyl-cyclohexane skeleton are constituted Base resin.The end of phenoxy resin can be any functional group of phenolic hydroxyl, epoxy radicals etc..Phenoxy resin can be independent Using a kind, two or more also can be combined and uses.As the concrete example of phenoxy resin, Mitsubishi chemical Co., Ltd's system can be enumerated " 1256 " and " 4250 " (being the phenoxy resin containing bisphenol A skeleton), " YX8100 " (benzene oxygen containing bisphenol S skeleton Base resin) and " YX6954 " (phenoxy resin containing bis-phenol acetophenone skeleton), in addition, can also enumerate Nippon Steel's firmly aurification " FX280 " and " FX293 ", " YX6954BH30 ", " YX7553 " of Mitsubishi chemical Co., Ltd of Co. Ltd. system, " YX7553BH30 ", " YL7769BH30 ", " YL6794 ", " YL7213 ", " YL7290 ", " YL7891BH30 " and " YL7482 " Deng.
As polyvinyl acetal resin, for example, vinyl-formal resin, polyvinyl butyral resin tree can be enumerated Fat, preferably polyvinyl butyral resin.As the concrete example of polyvinyl acetal resin, for example, can enumerate electrochemically " Denka Butyral 4000-2 ", " Denka Butyral 5000-A ", " the Denka Butyral of Industrial Co., Ltd 6000-C ", " Denka Butyral 6000-EP ", the S-LEC BH series of Sekisui Chemical Co., Ltd, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series.
As the concrete example of polyimide resin, " the RIKACOAT SN20 " of New Japan Chem Co., Ltd can be enumerated And " RIKACOAT PN20 ".As the concrete example of polyimide resin, in addition, can enumerate makes 2 functional hydroxyl groups end polybutadienes Alkene, diisocyanate cpd and (the Japanese Unexamined Patent Publication 2006-37083 public affairs of wire polyimides obtained from quaternary anhydride reaction Report the polyimides recorded), (Japanese Unexamined Patent Publication 2002-12667 publications and Japan are special for polyimides containing silicone matrix Open the polyimides described in 2000-319386 publications etc.) etc. modified polyimide.
As the concrete example of polyamide-imide resin, " the VYLOMAX of Toyo Boseki K. K can be enumerated HR11NN " and " VYLOMAX HR16NN ".As the concrete example of polyamide-imide resin, in addition, Hitachi's chemical conversion work can be enumerated Modified polyamide acyls such as " KS9100 ", " KS9300 " (polyamidoimides containing silicone matrix) of industry Co. Ltd. system Imines.
As the concrete example of polyethersulfone resin, it can enumerate " PES5003P " of Sumitomo Chemical Co etc..
As the concrete example of polysulfone resin, the polysulfones of Solvay Advanced Polymers Co. Ltd. systems can be enumerated " P1700 ", " P3500 " etc..
As the concrete example of polyphenylene oxide resin, oligomeric polyphenylene oxide-benzene second of Mitsubishi Gas Chemical Co., Ltd can be enumerated Olefine resin " OPE-2St1200 " etc..
Wherein, as thermoplastic resin, preferably phenoxy resin, polyvinyl acetal resin.Therefore, preferred one In individual embodiment, thermoplastic resin includes a kind in the group being made up of phenoxy resin and polyvinyl acetal resin More than.
When first resin combination contains thermoplastic resin, the content of thermoplastic resin is preferably the matter of 0.5 mass %~15 Measure %, the mass % of more preferably 0.6 mass %~12 mass %, more preferably 0.7 mass %~10.
- (e) curing accelerators-
First resin combination can also contain (e) curing accelerator in addition to containing (a)~(c) compositions.
As curing accelerator, for example, phosphorus system curing accelerator, amine system curing accelerator, imidazoles system solidification rush can be enumerated Enter agent, guanidine system curing accelerator, metal system curing accelerator, organic peroxide system curing accelerator etc., preferably phosphorus system consolidates Change accelerator, amine system curing accelerator, imidazoles system curing accelerator, metal system curing accelerator, more preferably amine system solidification promotees Enter agent, imidazoles system curing accelerator, metal system curing accelerator.Curing accelerator can be used alone a kind, also can be combined 2 kinds with Above use.
As phosphorus system curing accelerator, for example, triphenylphosphine, Phosphonium borate compound, tetraphenylphosphoniphenolate tetraphenyl can be enumerated Borate, Zheng Ding Ji Phosphonium tetraphenyl borate salts, 4-butyl-phosphonium caprate, (4- aminomethyl phenyls) triphenyl phosphonium rhodanate, four benzene Ji Phosphonium rhodanate, Ding base triphenyl phosphonium rhodanates etc., preferably triphenylphosphine, 4-butyl-phosphonium caprate.
As amine system curing accelerator, for example, the trialkylamines such as triethylamine, tri-butylamine, 4- dimethylaminos can be enumerated Yl pyridines, benzyldimethylamine, 2,4,2,4,6- tri- (dimethylaminomethyl) phenol, the carbon of 1,8- diazabicyclos (5,4,0)-ten one Alkene etc., preferably 4-dimethylaminopyridine, 1,8- diazabicyclos (5,4,0)-endecatylene.
As imidazoles system curing accelerator, for example, 2-methylimidazole, 2- undecyl imidazoles, 2- heptadecyls can be enumerated Imidazoles, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl Imidazoles, 2- phenyl -4-methylimidazole, 1 benzyl 2 methyl imidazole, 1- benzyl -2- phenylimidazoles, 1- cyano ethyl -2- methyl Imidazoles, 1- cyano ethyl -2- undecyl imidazoles, 1- cyano ethyls -2-ethyl-4-methylimidazole, 1- cyano ethyl -2- phenyl Imidazoles, 1- cyano ethyl -2- undecyl imidazole trimellitic acids salt, 1- cyano ethyl -2- phenylimidazole trimellitic acids salt, 2,4- diaminourea -6- [2 '-methylimidazolyl-(1 ')]-ethyl s-triazine, 2,4- diaminourea -6- [2 '-undecyl imidazole base - (1 ')]-ethyl s-triazine, 2,4- diaminourea -6- [2 '-ethyl -4 '-methylimidazolyl-(1 ')]-ethyl s-triazine, 2,4- bis- Amino -6- [2 '-methylimidazolyl-(1 ')]-ethyl s-triazine isocyanuric acid adduct, 2- phenylimidazole isocyanuric acid additions Thing, 2- phenyl -4,5- bishydroxymethyls imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazoles, 2,3- dihydro -1H- pyrrolo-es [1,2-a] benzimidazole, 1- dodecyl -2- methyl-3-benzyl imidazoles chloride, 2-methylimidazole quinoline, 2- phenylimidazoles The adduct of the imidazolium compounds such as quinoline and imidazolium compounds and epoxy resin, preferably 2-ethyl-4-methylimidazole, 1- benzyls- 2- phenylimidazoles.
As imidazoles system curing accelerator, commercially available product can be used, for example, Mitsubishi chemical Co., Ltd can be enumerated " P200-H50 " etc..
As guanidine system curing accelerator, for example, dicyandiamide, 1- methylguanidines, 1- ethyl guanidines, 1- cyclohexyl guanidine, 1- can be enumerated Guanidines, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethyl guanidine, TMG, pentamethyl guanidine, the nitrogen of 1,5,7- tri- Miscellaneous bicyclic [4.4.0] decyl- 5- alkene, 7- methyl isophthalic acids, the azabicyclos of 5,7- tri- [4.4.0] decyl- 5- alkene, 1- methyl biguanides, 1- ethyls Biguanides, 1- normal-butyls biguanides, 1- n-octadecane bases biguanides, 1,1- dimethylbiguanides, 1,1- diethyl biguanides, 1- cyclohexyl are double Guanidine, 1- pi-allyls biguanides, 1- phenyl biguanides, 1- (o-tolyl) biguanides etc., preferably dicyandiamide, 1,5,7- tri- azabicyclos [4.4.0] decyl- 5- alkene.
As metal system curing accelerator, for example, the organic metal of the metals such as cobalt, copper, zinc, iron, nickel, manganese, tin can be enumerated Complex compound or organic metal salt.As the concrete example of metal-organic complex, acetylacetone cobalt (II), acetylacetone cobalt can be enumerated (III) the organic zinc complexing such as organic copper complex, zinc acetylacetonate (II) such as organic cobalt complex, acetylacetone copper (II) such as Organic nickel complexes such as the Organic-iron complexes such as thing, ferric acetyl acetonade (III), nickel acetylacetonate (II), manganese acetylacetonate (II) Etc. organic manganese complex etc..As organic metal salt, for example, zinc octoate can be enumerated, it is tin octoate, zinc naphthenate, cobalt naphthenate, hard Resin acid tin, zinc stearate etc..
As organic peroxide system curing accelerator, for example, dicumyl peroxide, cyclohexanone peroxidating can be enumerated Thing, t-butyl peroxybenzoate, methyl-ethyl-ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, two uncles Butylperoxide, di-isopropylbenzene hydroperoxide, cumyl hydroperoxide, TBHP etc..It is used as organic peroxy Thing system curing accelerator, can be used commercially available product, for example, " PERCUMYL D " etc. of day oily company system can be enumerated.
The content of curing accelerator in first resin combination is not particularly limited, by epoxy resin and curing agent When nonvolatile component is as 100 mass %, the mass % of preferably 0.01 mass %~3.
- (f) fire retardants-
First resin combination can include (f) fire retardant.As fire retardant, for example, organic phosphorus flame retardant, organic system can be enumerated Nitrogenous phosphorus compound, nitrogen compound, silicone flame retardant, metal hydroxides etc..Fire retardant can be used alone a kind, or Person also and can use two or more.
As fire retardant, commercially available product can be used, for example, " HCA-HQ " of Sanko Co., Ltd., big eight chemistry can be enumerated " PX-200 " of Industrial Co., Ltd etc..
When first resin combination contains fire retardant, the content of fire retardant is not particularly limited, and preferably 0.5 mass %~ The mass % of 20 mass %, more preferably 0.5 mass %~15 mass %, more preferably 0.5 mass %~10.
- (g) organic filler materials-
For resin combination, from the viewpoint of elongation is improved, (g) organic filler material can be included.As organic Packing material, may be used at workable arbitrary organic filler material during the insulating barrier to form printed wiring board, for example, can lift Go out rubber particles, polyamide particles, organic silicon particle etc..
As rubber particles, commercially available product can be used, for example, DOW Chemical Amada Co., Ltd. can be enumerated " AC3816N " of " EXL2655 ", ガ Application Star chemical conversion Co. Ltd. system etc..
When first resin combination contains organic filler material, the content of organic filler material is preferably 0.1 mass %~20 The matter of the mass % or 0.5 mass % of quality %, more preferably 0.2 mass %~10 mass %, more preferably 0.3 mass %~5~3 Measure %.
- additive optional (h)-
As needed, the first resin combination can also include other additives, as other described additives, for example, can enumerate The organo-metallic compounds such as organocopper compound, organic zinc compound and organic cobalt compounds and thickener, defoamer, Resin additives such as agent, adaptation imparting agent and colouring agent etc..
(the second resin combination)
The second resin combination for forming the second resin composition layer includes (a) inorganic filling material, for the content of (a) composition For, during using the nonvolatile component in the second resin combination as 100 mass %, if more than 60 mass %, i.e., composition with First resin combination is different, is just not particularly limited, as the second resin combination, preferably comprises inorganic filling material, ring Oxygen tree fat and curing agent.
As the inorganic filling material in the second resin combination, it can enumerate and the explanation in (the first resin combination) column The same inorganic filling material of inorganic filling material.
The average grain diameter of inorganic filling material in second resin combination is not particularly limited, from through hole (via) side From the viewpoint of wall shape uniformity, preferably less than 2.5 μm, more preferably less than 2.0 μm, more preferably 1.5 μm with Under.The lower limit of the average grain diameter is not particularly limited, preferably more than 0.8 μm, more preferably more than 0.9 μm, further preferably For more than 1.0 μm.As the commercially available product of the inorganic filling material with such average grain diameter, lived for example, Nippon Steel can be enumerated Golden material Co. Ltd. system " SP60-05 ", " SP507-05 ", Co., Ltd.'s Admatechs systems " YC100C ", " YA050C ", " YA050C-MJE ", " YA010C ", Deuki Kagaku Kogyo Co., Ltd's system " UFP-30 ", Tokuyama Corp (ト Network ヤ マ) system " シ Le Off ィ Le NSS-3N ", " シ Le Off ィ Le NSS-4N ", " シ Le Off ィ Le NSS-5N ", Co., Ltd.'s Admatechs systems " SC2500SQ ", " SO-C4 ", " SO-C2 ", " SO-C1 " etc..
The average grain diameter of inorganic filling material in first resin combination is designated as R1 (μm), by the second resin combination In the average grain diameter of inorganic filling material when being designated as R2 (μm), preferably meet R1≤R2 relation.In addition, the ratio between R1 and R2 (R2/R1) it is preferably more than 1, more preferably more than 1.1, more preferably more than 1.5 or for more than 2.The R2/R1 upper limit It is not particularly limited, preferably less than 15, more preferably less than 10, more preferably less than 8.It should be noted that for example, When the first resin combination contains a variety of inorganic filling materials, by the average value of each average grain diameter of a variety of inorganic filling materials It is designated as R1 (for the second resin combination similarly.).
As the second resin combination, from the viewpoint of warpage is suppressed, by the second resin combination it is non-volatile into The content for the inorganic filling material being allocated as during for 100 mass % is more than 60 mass % preferably more than 65 mass %, more preferably More than 67 mass %.The upper limit of the content of inorganic filling material in second resin combination is preferably below 95 mass %, more excellent Elect as below 90 mass %, more preferably below 80 mass %.
The content of inorganic filling material in first resin combination is designated as A1 (quality %), by the second resin combination In the content of inorganic filling material when being designated as A2 (quality %), preferably meet A1 ＜ A2 relation.In addition, A1 and A2 difference (A2-A1) it is preferably more than 30 mass % more preferably more than 40 mass %, more preferably more than 50 mass %.Difference (A2- A1 the upper limit) is not particularly limited, and typically below 90 mass %, 80 mass % are such as the following.
In one embodiment, the second resin combination is in addition to comprising inorganic filling material, also comprising asphalt mixtures modified by epoxy resin Fat and curing agent.As needed, the second resin combination can also include thermoplastic resin, curing accelerator, fire retardant and organic The additives such as packing material.
As epoxy resin, curing agent and the additive included in the second resin combination, can enumerate with the trees of ＜ first (b) epoxy resin, (c) curing agent and the same material of additive illustrated in oil/fat composition ＞ columns.
For the content of the epoxy resin in the second resin combination, from obtaining showing good mechanical strength, absolutely From the viewpoint of the insulating barrier of edge reliability, preferably more than 0.1 mass %, more preferably more than 5 mass %, more preferably More than 10 mass %.The upper limit of the content of epoxy resin is not particularly limited, as long as playing the effect of the present invention, is preferably Below 30 mass %, more preferably below 25 mass %, more preferably below 22 mass %.Therefore, in the second resin combination The content of (b) epoxy resin be preferably 0.1~30 mass %, more preferably 5~25 mass %, more preferably 8~22 matter Measure %.
The content of epoxy resin in first resin combination is designated as B1 (quality %), by the second resin combination When the content of epoxy resin is designated as B2 (quality %), B1 ＞ B2 relation is preferably met.In addition, B1 and B2 difference (B1-B2) is preferably For more than 5 mass %, more preferably more preferably more than 8 mass %, more than 10 mass %.The upper limit of poor (B1-B2) is without spy Do not limit, generally, can be such as the following for below 60 mass %, 50 mass %.
When liquid-state epoxy resin and solid epoxy resin are as epoxy resin, their amount ratio (liquid epoxy tree Fat：Solid epoxy resin) it is preferably 1 by quality ratio：0.1~1：15 scope.By making liquid-state epoxy resin and solid-state ring The amount ratio of oxygen tree fat is above range, thus, can obtain following effects：I) with the form of resin sheet in use, can bring suitable The cohesive of degree；Ii) with the form of resin sheet, in use, can obtain sufficient flexibility, treatability is improved；And, iii) can Obtain the solidfied material with sufficient fracture strength；Etc..From it is above-mentioned i)~iii) effect from the viewpoint of, liquid epoxy tree Amount ratio (the liquid-state epoxy resin of fat and solid epoxy resin：Solid epoxy resin) 1 is more preferably by quality ratio：0.3~1： 10 scope, more preferably 1：0.6~1：8 scope.
It should be noted that the epoxide equivalent and the Weight-average molecular of epoxy resin of the epoxy resin in the second resin combination The preferred scope of amount is same with the epoxy resin included in the first resin combination.
The content of curing agent in second resin combination is not particularly limited, from obtaining the exhausted of low dielectric loss angle tangent From the viewpoint of edge layer, preferably more than 0.1 mass %, more preferably more than 1 mass %, more preferably more than 5 mass %. The upper limit of the content of curing agent is not particularly limited, as long as playing the effect of the present invention, preferably below 20 mass %, more Preferably below 15 mass %, more preferably below 12 mass %.Therefore, the content of the curing agent in the second resin combination Preferably 0.1~20 mass %, more preferably 1~15 mass %, more preferably 5~12 mass %.
For the amount ratio of the epoxy resin in the second resin combination and curing agent, with [the epoxy radicals of epoxy resin Total number]：The ratiometer of [total number of the reactive group of curing agent], preferably 1：0.2~1：2 scope, more preferably 1：0.3~1：1.5, more preferably 1：0.4~1：1.By making the amount ratio of epoxy resin and curing agent be above range, from And the heat resistance of the solidfied material of the second resin combination is further improved.
The content of thermoplastic resin in second resin combination is not particularly limited, the mass % of preferably 0 mass %~10, The mass % of more preferably 0.2 mass %~8 mass %, more preferably 0.5 mass %~5.
The content of curing accelerator in second resin combination is not particularly limited, preferably with the matter of 0.001 mass %~3 Amount % scope is used.
The content of fire retardant in second resin combination is not particularly limited, the mass % of preferably 0.2 mass %~20, more The mass % of preferably 0.5 mass %~15 mass %, more preferably 0.8 mass %~10.
The content of organic filler material in second resin combination is preferably the mass % of 0.1 mass %~20, more preferably The mass % of 0.2 mass %~10.
Second resin combination is same with the first resin combination, as needed, can include arbitrary additive, for example, The organo-metallic compounds such as organocopper compound, organic zinc compound and organic cobalt compounds and organic filler, thickener, Resin additives such as defoamer, levelling agent, adaptation imparting agent and colouring agent etc..
[resin sheet with supporter]
The resin sheet with supporter of the present invention is with supporter with supporter and the resin sheet being arranged on supporter Resin sheet, resin sheet has：It is arranged at first resin composition layer formed by the first resin combination on support side and sets Put the second resin composition layer formed by the second resin combination in the side opposite with support side；First resin combination Thing includes (a) inorganic filling material, during using the nonvolatile component in the first resin combination as 100 mass %, (a) composition Content is below 30 mass %, and the second resin combination includes (a) inorganic filling material, by not waving in the second resin combination When sending out composition as 100 mass %, the content of (a) composition is more than 60 mass %, the thermal conductivity factor and second of the first thermosetting compound The difference of the thermal conductivity factor of thermosetting compound is below 0.4W/mK, and the first thermosetting compound is to make the first resin combination in 100 DEG C Heat cure 30 minutes and then obtained from 190 DEG C of heat cures 90 minutes, the second thermosetting compound is to make the second resin combination Thing is in 100 DEG C of heat cures 30 minutes and then obtained from 190 DEG C of heat cures 90 minutes.
Fig. 2 is illustrated in by the one of the resin sheet with supporter of the present invention.In Fig. 2, the resin sheet 10 with supporter has Supporter 11 and the resin sheet 12 being arranged on supporter 11.In Fig. 2, resin sheet 12 includes：It is arranged at the first of support side Resin composition layer 13 and the second resin composition layer 14 for being arranged on the side opposite with support side.
Hereinafter, the supporter and resin sheet of the resin sheet with supporter of the invention are described in detail.
＜ supporters ＞
It is preferably by plastics material for instance, it may be preferable to enumerate the film being molded of plastic material, metal foil, processing release paper as supporter Expect film, the metal foil formed.
During using the film being molded of plastic material as supporter, as plastic material, for example, poly- terephthaldehyde can be enumerated Sour glycol ester is (hereinafter sometimes referred to simply as " PET ".), PEN (hereinafter sometimes referred to simply as " PEN ".) etc. it is poly- Ester, makrolon are (hereinafter sometimes referred to simply as " PC ".), the acrylic compounds such as polymethyl methacrylate (PMMA), cyclic polyolefin, Triacetyl cellulose (TAC), polyether sulfides (PES), polyether-ketone, polyimides etc..Wherein, preferably poly terephthalic acid second Diol ester, PEN, particularly preferably cheap polyethylene terephthalate.
During using metal foil as supporter, as metal foil, for example, copper foil, aluminium foil etc., preferably copper foil can be enumerated. Be used as copper foil, the paper tinsel that is formed by single metallic copper can be used, it is possible to use by copper and other metals (for example, tin, chromium, silver, Magnesium, nickel, zirconium, silicon, titanium etc.) alloy formation paper tinsel.
, can pair face engaged with the first resin composition layer implementation delustring processing, sided corona treatment for supporter.
In addition, as supporter, maying be used at carrying with release layer on the face engaged with the first resin composition layer The supporter of release layer.As the releasing agent used in the release layer of the supporter with release layer, it is selected from for example, can enumerate More than a kind of releasing agent in the group being made up of alkyd resin, vistanex, polyurethane resin and organic siliconresin.Carry Commercially available product can be used in the supporter of release layer, for example, can enumerate as with de- by principal component of alkyd resin system releasing agent " SK-1 ", " AL-5 ", " AL-7 " of the Lindeke Co., Ltd of the PET film of mold layer etc..
As the thickness of supporter, it is not particularly limited, preferably 5 μm~75 μm of scope, more preferably 10 μm~60 μ M scope.It should be noted that when using supporter with release layer, supporter preferably with release layer is overall Thickness is above range.
＜ resin sheets ＞
Resin sheet has：It is arranged at first resin composition layer on the support side side opposite with support side with being arranged on The second resin composition layer formed by the second resin combination, second resin combination with formed the first resin combination First resin combination of nitride layer is different composition.
In the resin sheet with supporter of the present invention, the thickness of resin sheet is preferably more than 3 μm, more preferably more than 5 μm. For the upper limit of the thickness of resin sheet, from the viewpoint of the setting of the thickness of the resin bed on conductor, preferably 40 μm with Under, more preferably less than 35 μm, more preferably less than 30 μm or for less than 25 μm.
The thickness of the first resin composition layer formed by the first resin combination is preferably less than 10 μm, more preferably 7 μ Below m, more preferably less than 8 μm.The lower limit of the thickness of first resin composition layer is not particularly limited, from obtaining thick Viewpoint, the manufacture of the resin sheet with supporter of the insulating barrier of excellent peel strength is presented after roughening processing relative to conductor layer From the viewpoint of easiness, generally, can for more than 0.05 μm, 0.1 μm with first-class.By there is the first resin composition layer, Coating fissility can be improved.
The thickness of the second resin composition layer formed by the second resin combination is preferably more than 2.5 μm, more preferably 5 More than μm, more preferably more than 7 μm, more than 8 μm, more than 9 μm or more than 10 μm.The thickness of second resin composition layer The upper limit is preferably less than 30 μm, more preferably less than 25 μm, more preferably less than 20 μm.By there is the second resin combination Nitride layer, can suppress warpage.
The resin sheet 10 with supporter of the present invention can be in the face not engaged with supporter 11 of resin sheet 12 (that is, with branch The face of the opposite side of support body) on also include diaphragm.Diaphragm contributes to the surface for preventing dust etc. to be attached to resin sheet 12 Deng, prevent resin sheet 12 produce damage.As the material of diaphragm, it can be used identical with the material illustrated on supporter 11 Material.The thickness of diaphragm is not particularly limited, for example, for 1 μm~40 μm.For the resin sheet 10 with supporter, When manufacturing printed wiring board, it can be used by the way that diaphragm is peeled off.
Make the first resin combination in 100 DEG C of heat cures 30 minutes and then obtained from 190 DEG C of heat cures 90 minutes The thermal conductivity factor of one thermosetting compound is preferably below 1W/mK, more preferably below 0.7W/mK, more preferably 0.5W/mK with Under.Lower limit is not particularly limited, can be more than 0.01W/mK.Thermal conductivity factor can be according to (the heat conduction system of solidfied material described later Several measure) the step of determine.
Make the second resin combination in 100 DEG C of heat cures 30 minutes and then obtained from 190 DEG C of heat cures 90 minutes The thermal conductivity factor of two thermosetting compounds is preferably below 1.5W/mK, more preferably below 1.0W/mK, more preferably 0.7W/mK Below.Lower limit is not particularly limited, can be more than 0.01W/mK.Thermal conductivity factor can be according to (the heat conduction of solidfied material described later The measure of coefficient) the step of determine.
In the present invention, the difference of the thermal conductivity factor of the first thermosetting compound and the second thermosetting compound is below 0.4W/mK.By such as The difference for above making the thermal conductivity factor of the first thermosetting compound and the second thermosetting compound describedly is below 0.4W/mK, can be reduced solid The length in the recessed damage portion that the bearing of trend at the interface for each thermosetting compound changed is produced.On its mechanism, it is considered to be to be based on following machine Reason：By the difference for the thermal conductivity factor for reducing the first thermosetting compound and the second thermosetting compound, so that because of the first heat caused by laser Solidfied material and the pyrolytic of the second thermosetting compound become uniform.
In the present invention, the difference of the thermal conductivity factor of the first thermosetting compound and the second thermosetting compound is below 0.4W/mK, is preferably Below 0.35W/mK, more preferably below 0.3W/mK.It is not particularly limited for lower limit, can is more than 0.01W/mK.
The length in the recessed damage portion of interface bearing of trend is defined as below.When observing the vertical cross-section of through hole, inserted in outside extraction logical The straight line of the side wall in hole, will be designated as from the straight line to the first resin composition layer and the distance at the interface of the second resin composition layer The length d in recessed damage portion.Specifically, for the length in recessed damage portion, one shown in Fig. 3 like that, draws straight line, recessed damage The length in portion refers to from the interface of the first resin composition layer and the second resin composition layer to straight line apart from d.
For the length in recessed damage portion, from the viewpoint of suppression produces space when carrying out plating processing, it is preferably Less than 2.0 μm, more preferably less than 1.8 μm, more preferably less than 1.5 μm or less than 1.4 μm.For lower limit without spy Do not limit, be more than 0.01 μm.The length in recessed damage portion can according to it is described later " confirmation of the shape of through hole (length in recessed damage portion and Laser Processing property evaluation) " the step of be measured.
For the resin sheet with supporter of the present invention, due to that can reduce in cured each resin composition layer The length in the recessed damage portion produced on the bearing of trend at interface, therefore, shows following characteristic：Even if opening diameter (top diameter) For less than 40 μm, Laser Processing property is also excellent.Thus, the fine wiring of printed wiring board is possibly realized.
[manufacture method of the resin sheet with supporter]
Hereinafter, the example of the manufacture method of the resin sheet with supporter of the present invention is illustrated.
First, the first resin composition layer for being formed by the first resin combination is formed on supporter and by the second tree Second resin composition layer of oil/fat composition formation.
As forming the method for the first resin composition layer and the second resin composition layer, for example, can enumerate with by first The mode that resin composition layer and the second resin composition layer are bonded with each other carries out laminating method.As with by the first resin combination The method that nitride layer is laminated with the mode that the second resin composition layer is bonded with each other, for example, following methods can be enumerated：In support The first resin combination is coated with body and makes coated film dry to form the first resin composition layer, then in the first resin group The second resin combination is coated with compound layer, coated film is dried and the second resin composition layer is set.
In this method, the first resin composition layer can make by the following method：Prepare and dissolve the first resin combination Resin varnish in organic solvent, branch is coated on using metal mold coating machine (die coater) etc. by the resin varnish On support body, dry resin varnish.
As organic solvent, for example, the ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, acetic acid fourth can be enumerated The acetate esters such as ester, cellosolve acetate, propylene glycol monomethyl ether and carbitol acetate, cellosolve and butyl card must The aromatic hydrocarbon, dimethylformamides such as the carbitol such as alcohol class, toluene and dimethylbenzene, dimethyl acetamide and N- crassitudes Acid amides series solvents such as ketone etc..Organic solvent can be used alone a kind, or also and can use two or more.
The drying of resin varnish can be implemented using drying means known to heating, blowing hot-air etc..Although with resin varnish In organic solvent boiling point it is different and different, but for example using comprising 30 mass %~60 mass % organic solvent resin During varnish, by the way that in 50 DEG C~150 DEG C dryings 1 minute~10 minutes, the first resin composition layer can be formed on supporter.
In the above method, the second resin composition layer can make by the following method：Prepare the second resin combination is molten The resin varnish will be coated on the shape on supporter by solution in the resin varnish of organic solvent using metal mold coating machine etc. Into the first resin composition layer on, dry resin varnish.
As organic solvent used in the preparation for the resin varnish for being dissolved with the second resin combination, it can be used and dissolving There is the same organic solvent of organic solvent used in the preparation of the resin varnish of the first resin combination, be dissolved with the second resin The resin varnish of composition, enters using the same method of the drying means of the resin varnish with being dissolved with the first resin combination Row drying.
It should be noted that in addition to above-mentioned rubbing method, resin sheet also using on 1 coating line sequentially The series connection rubbing method of 2 kinds of resin varnish of coating is formed.In addition, resin sheet is also formed using following methods：In the second resin group The first resin combination is coated with compound layer, the method that coated film is dried and the first resin composition layer is set；And, will The method that the mode that the first resin composition layer and the second resin composition layer respectively prepared is bonded with each other is laminated；Deng Deng.
In addition, in the present invention, for example, can also sequentially form the second resin composition layer and the first resin group on diaphragm Support body layer, is then laminated on the first resin composition layer and makes the resin sheet with supporter by compound layer.
[manufacture method of printed wiring board and printed wiring board]
The printed wiring board of the present invention includes what is formed by the solidfied material of the resin sheet in the resin sheet with supporter of the present invention Insulating barrier.In addition, the manufacture method of the printed wiring board of the present invention includes：
Process (I), by the resin sheet with supporter of the present invention in the way of the second resin composition layer is engaged with internal substrate It is layered on internal substrate,
Process (II), insulating barrier is formed by the resin sheet heat cure with supporter, and,
Process (III), forms through hole on the insulating layer, removes supporter.
" internal substrate " used in process (I) is primarily referred to as glass epoxy substrate, metal substrate, polyester substrate, polyamides The substrates such as imines substrate, BT resin substrates, thermohardening type polyphenylene oxide substrate are formed with through figure in the one or both sides of the substrate The circuit substrate of the conductor layer (circuit) of case processing.In addition, " internal substrate " described in the present invention is additionally included in manufacture printing During wiring plate, it should further form the internal layer circuit substrate of insulating barrier and/or the middle manufacture thing of conductor layer.Printed wiring board is During part internal circuit board, (conductor layer also can be referred to as wiring layer) using the internal substrate for being built-in with part.
The stacking of internal substrate and the resin sheet with supporter for example can by from support side by the resin with supporter Piece heating is crimped on internal substrate and carried out.As by with supporter resin sheet heating be crimped on internal substrate component (with Lower also referred to as " heating crimping component ".), for example, heated metallic plate (SUS end plates etc.) or metallic roll (SUS rollers) can be enumerated Deng.It should be noted that preferably, and the indirect crimping component that will heat pressurizes to the resin sheet with supporter, but every Heat resistant rubber elastomeric material to be pressurizeed, with cause the resin sheet with supporter fully follow internal substrate surface it is recessed It is convex.
The stacking of internal substrate and the resin sheet with supporter can be implemented using vacuum layer platen press.In vacuum layer platen press, plus Hot pressing jointing temp is preferably 60 DEG C~160 DEG C, more preferably 80 DEG C~140 DEG C of scope, and heating crimping pressure is preferably 0.098MPa~1.77MPa, more preferably 0.29MPa~1.47MPa scope, the heating crimping time is preferably 20 seconds~400 Second, the scope of more preferably 30 seconds~300 seconds.Stacking is preferably implemented in the case where pressure is below 26.7hPa reduced pressure.
Stacking can be carried out using commercially available vacuum lamination apparatus.As commercially available vacuum lamination apparatus, for example, strain can be enumerated Formula commercial firm name mechanism makees made vacuum pressure type laminater, the vacuum pack system device of Nikko-Materials Co. Ltd. systems (vacuum applicator) etc..
After stacking, at ambient pressure (under atmospheric pressure), for example, heating crimping component is pressurizeed from support side, by This, the smoothing techniques for the resin sheet that can be laminated.The pressurized conditions of smoothing techniques may be set to above-mentioned stacking plus The same condition of thermo-compression bonding condition.Smoothing techniques can be carried out using commercially available laminater.It should be noted that stacking is with putting down Above-mentioned commercially available vacuum lamination apparatus can be used continuously to carry out for cunningization processing.
In process (II), the resin sheet heat cure of the resin sheet with supporter is formed into insulating barrier.
The heat cure condition of resin sheet (first and second resin composition layer) is not particularly limited, and may be used to form print Usual adoptable condition during the insulating barrier of brush wiring plate.
For example, the heat cure condition of resin sheet is according to the different and different of the species of first and second resin combination etc., Scope (preferably 150 DEG C~220 DEG C of scope, more preferably 170 DEG C~200 that solidification temperature is 120 DEG C~240 DEG C can be made DEG C scope), hardening time for 5 minutes~120 minutes scope (be preferably 10 minutes~100 minutes, more preferably 15 minutes ~90 minutes).
Before resin sheet heat cure is made, resin sheet can be preheated under than solidification temperature lower temperature.Example Such as, before resin sheet heat cure is made, 50 DEG C less than 120 DEG C (be preferably less than more than 60 DEG C 110 DEG C, more preferably For less than more than 70 DEG C 100 DEG C) at a temperature of, to resin sheet carry out more than 5 minutes (preferably 5 minutes~150 minutes, it is more excellent Elect as 15 minutes~120 minutes) preheating.
In process (III), through hole is formed on the insulating layer, removes supporter.The formation of through hole is not particularly limited, and can lift Go out laser irradiation, etching, machine drilling etc., irradiate and carry out preferably by laser.From the viewpoint for further suppressing recessed damage portion generation Consider, preferably peel off supporter after formation through hole on the insulating layer, specifically, preferably utilizing laser shape on the insulating layer Supporter is peeled off after into through hole.
Laser irradiation can be by the use of using carbon dioxide laser, YAG laser, PRK etc. to be used as the arbitrary of light source Suitable laser machine is carried out.As workable laser machine, for example, the sub- machinery (Via of dimension can be enumerated Mechanics) Co. Ltd. system CO2Laser machine " LC-2k212/2C ", the 605GTWIII of Mitsubishi Electric Corporation (- P), Panasonic weld the laser machine of シ ス テ system (Panasonic Welding Systems) Co. Ltd. system.
The condition of laser irradiation is not particularly limited, and laser irradiation can be by according to routine side corresponding with the means of selection The arbitrary suitable process of method is implemented.
The shape of through hole, the shape of the profile of opening when being observed along bearing of trend are not particularly limited, and usually justify Shape (circular).Hereinafter, when mentioning " footpath (diameter) " of through hole, refer to along bearing of trend observe when opening profile Footpath (diameter).In this specification, opening diameter (top diameter) refers to the insulating barrier (solidification of the first resin composition layer of through hole Thing) side profile diameter, base diameter r2 refers to the diameter of the profile of the wiring layer side of through hole.
It is preferred that forming through hole in the way of the opening diameter r1 of through hole turns into following values：Preferably less than 40 μm, more preferably For less than 35 μm, more preferably less than 30 μm or less than 25 μm.
Can by opening diameter r1 be more than base diameter r2 in the way of form through hole, also can according to through hole opening diameter r1 Through hole is formed with the base diameter r2 identical modes of through hole.If it does, then the imbedibility of through hole becomes good, it can suppress Space is produced.
When manufacturing printed wiring board, it can further implement the process that (IV) is roughened to insulating barrier；(V) shape Into the process of conductor layer.Above-mentioned operation (IV)~(V) can be according to workable people in the art in the manufacture of printed wiring board The known various methods of member are implemented.
Process (IV) is the process being roughened to insulating barrier.The step of roughening processing, condition be not special Limitation, can use formed printed wiring board insulating barrier when it is usually used known in step, condition.For example, can be real successively The swelling treatment based on swelling solution, the roughening processing based on oxidant, the neutralisation treatment based on neutralizer are applied, insulating barrier is entered The processing of row roughening.As swelling solution, it is not particularly limited, aqueous slkali, surfactant solution etc., preferably alkali soluble can be enumerated Liquid, is used as the aqueous slkali, more preferably sodium hydroxide solution, potassium hydroxide solution.As commercially available swelling solution, for example, can lift Go out " Swelling Dip Securiganth P ", " the Swelling Dip of ATOTECH JAPAN Co. Ltd. systems Securiganth SBU " etc..Swelling treatment based on swelling solution is not particularly limited, for example, can be by the way that insulating barrier is impregnated in In 30 DEG C~90 DEG C of swelling solution 1 minute~20 minutes and carry out.Appropriate water is suppressed to from by being swelled for the resin of insulating barrier From the viewpoint of flat, preferably firming body is impregnated in 40 DEG C~80 DEG C of swelling solution 5 minutes~15 minutes.It is used as oxidant (roughening liquid), is not particularly limited, and potassium permanganate, sodium permanganate are dissolved in the aqueous solution of sodium hydroxide for example, can enumerate Alkaline permanganic acid solution.Roughening processing based on oxidants such as alkaline permanganic acid solutions can be by the way that insulating barrier be impregnated Carried out in being heated in 60 DEG C~80 DEG C of oxidizing agent solution 10 minutes~30 minutes.In addition, in alkaline permanganic acid solution The concentration of permanganate be preferably the mass % of 5 mass %~10.As commercially available oxidant, for example, ATOTECH can be enumerated " Concentrate Compact CP ", " Concentrate Compact P ", " Dosing of JAPAN Co. Ltd. systems The alkalescence permanganic acid solution such as Solution Securiganth P ".In addition, as neutralizer, being preferably the acid aqueous solution, making For commercially available product, for example, " the Reduction Solution Securiganth of ATOTECH JAPAN Co. Ltd. systems can be enumerated P”.Processing based on neutralizer can be by being impregnated in 30 DEG C~80 by the process face for having carried out the roughening processing based on oxidant DEG C neutralizer in 5 minutes~30 minutes and carry out.Consider in terms of operability, will preferably carry out based on the thick of oxidant The method that the object of roughening processing is impregnated in 5 minutes~20 minutes in 40 DEG C~70 DEG C of neutralizer.
Process (V) is the process to form conductor layer.
The conductor material used in conductor layer is not particularly limited.In a preferred embodiment, conductor layer is included and is selected from More than a kind of metal in the group being made up of gold, platinum, palladium, silver, copper, aluminium, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium.Conductor Layer can be single metal layer, or alloy-layer, as alloy-layer, for example, can enumerate by two or more in above-mentioned group Metal alloy (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) formation layer.Wherein, from conductor layer formation The viewpoint considerations, the preferably list of chromium, nickel, titanium, aluminium, zinc, gold, palladium, silver or copper such as versatility, cost, the easiness of pattern formation Metal level or nickel-chromium alloy, copper-nickel alloy, the alloy-layer of copper-titanium alloy, more preferably chromium, nickel, titanium, aluminium, zinc, gold, palladium, The single metal layer or the single metal layer of the alloy-layer of nickel-chromium alloy, more preferably copper of silver or copper.
Conductor layer can be single layer structure, or the single metal layer formed by different types of metal or alloy or conjunction Layer gold is laminated more than 2 layers of sandwich construction.When conductor layer is sandwich construction, the layer contacted with insulating barrier is preferably chromium, zinc Or the single metal layer or the alloy-layer of nickel-chromium alloy of titanium.
The thickness of conductor layer depends on the design of desired printed wiring board, preferably usually 3 μm~35 μm, 5 μm ~30 μm.
In one embodiment, conductor layer can be formed by plating.For example, using semi-additive process, full additive method etc. Known technology carries out plating on the surface of insulating barrier, forms the conductor layer with desired wiring pattern.Hereinafter, Example using semi-additive process formation conductor layer is shown.
First, め っ I is solved using chemical plating (No Electricity) plating inculating crystal layer (め っ I シ is formed on the surface of insulating barrier ー De Layer).Next, on the plating inculating crystal layer of formation, corresponding to desired wiring pattern, formation makes plating inculating crystal layer The mask pattern that a part is exposed.On the plating inculating crystal layer exposed, using electrolytic coating formation metal level, then, removing is covered Mould pattern.Then, unwanted plating inculating crystal layer is removed using etching etc., leading with desired wiring pattern can be formed Body layer.
[semiconductor device]
The semiconductor device of the present invention includes the printed wiring board of the present invention.The semiconductor device of the present invention can be used the present invention's Printed wiring board is manufactured.
As semiconductor device, can enumerate by for electric product (for example, computer, mobile phone, digital camera and electricity Depending on machine etc.) and the vehicles (for example, motorcycle, automobile, electric car, ship and aircraft etc.) etc. various semiconductor devices.
The semiconductor device of the present invention can be by the conduction position installing component (semiconductor chip) in printed wiring board Manufacture." conduction position " refers to " position of the transmission electric signal in printed wiring board ", and its position is surface or is embedded in Position.In addition, as long as electrical circuit components of the semiconductor chip using semiconductor as material, are just not particularly limited.
For the installation method of semiconductor chip when the semiconductor device of the manufacture present invention, as long as making semiconductor core Piece effectively function, is not particularly limited, specifically, can enumerate wire bonding installation method, flip-chip peace Dress method, the installation method based on bumpless build up layer (Bump less Build-Up Layer, BBUL), based on each to different The installation method of property conducting film (ACF), installation method based on non-conductive film (NCF) etc..Herein, " based on built-in non-recessed The installation method of convex layer (BBUL) " refers to, " semiconductor chip is directly embedded to the recess of printed wiring board, makes semiconductor chip The installation method being connected with the wiring on printed wiring board ".
Embodiment
Hereinafter, the present invention is specifically described using embodiment, but the present invention is not restricted by the embodiments.Need explanation , in following record, for " part " and " % ", as long as no separately clearly stating, respectively represent " mass parts " and " quality % ".
[making of the resin sheet with supporter]
Using the resin varnish (resin combination) prepared using following step, the band supporter of embodiment and comparative example is made Resin sheet.
(preparation of resin varnish 1)
Stir while making di- first phenol-type epoxy resin that (Mitsubishi chemical Co., Ltd's system " YX4000HK ", epoxide equivalent is about For 185) 10 parts, (Nippon Kayaku K. K's system " NC3000L ", epoxide equivalent is 288) 25 parts and benzene to biphenyl type epoxy resin (Mitsubishi chemical Co., Ltd's system " YX7553BH30 ", solid constituent is 30 mass % cyclohexanone to epoxide resin：Methyl ethyl ketone (MEK) 1：1 solution) 20 parts of in the mixed solvents for dissolving by heating in 5 parts of 5 parts of solvent naphtha and cyclohexanone.It is cooled to room temperature Afterwards, the linear phenol-aldehyde resin system curing agent containing triazine skeleton is mixed wherein, and (hydroxyl equivalent is 125, Dainippon Ink Chemicals's system " LA-7054 ", solid constituent is 60% MEK solution) 10 parts, biphenyl phenolic resin system curing agent (hydroxyl equivalent is 218, it is bright and Co. Ltd. system " MEH-7851H " is melted into, solid constituent is 60% MEK solution) 15 parts, polyvinyl butyral resin (glass Change 105 DEG C of transition temperature, the ethanol of the solid constituent 15% of Sekisui Chemical Co., Ltd's system " KS-1 " and the 1 of toluene：1 Mixed solution) 10 parts, amine system curing accelerator (4-dimethylaminopyridine (DMAP), the mass % of solid constituent 5 MEK solution) 1 (Mitsubishi chemical Co., Ltd's system " P200-H50 ", solid constituent is 50 mass % propane diols list for part, imidazoles system curing accelerator Methyl ethereal solution) 2 parts, carried out at surface with amino silicone methane series coupling agent (Shin-Etsu Chemial Co., Ltd's system " KBM573 ") (golden material Co. Ltd. system " SPH516-05 " is lived to the spherical silicon dioxide of reason by Nippon Steel, and average grain diameter is 0.2 μm, per unit table The carbon amounts of area is 0.43mg/m2) 22 parts, it is with high speed rotary blender that its is dispersed, then, use cartridge filter (ROKITECHNO systems " SHP020 ") is filtered, and prepares resin varnish 1.
(preparation of resin varnish 2)
Stir while making bisphenol f type epoxy resin that (Mitsubishi chemical Co., Ltd's system " 1750 ", epoxide equivalent is about 159) 5 Part, (Mitsubishi chemical Co., Ltd's system " YX4000HK ", epoxide equivalent is about 185) 10 parts, biphenyl to di- first phenol-type epoxy resin (Nippon Kayaku K. K's system " NC3000L ", epoxide equivalent is 288) 20 parts, (DIC plants of naphthalene type epoxy resin to type epoxy resin Formula commercial firm system " HP-4710 ", epoxide equivalent is about 170) 3 parts and phenoxy resin (Mitsubishi chemical Co., Ltd's system " YX7553BH30 ", solid constituent is 30 mass % cyclohexanone：The 1 of methyl ethyl ketone (MEK)：1 solution) 5 parts dissolve by heating in The in the mixed solvent of 5 parts of 20 parts of solvent naphtha and cyclohexanone.It is cooled to after room temperature, the line containing triazine skeleton is mixed wherein (hydroxyl equivalent is 125 to type phenolic resin system curing agent, Dainippon Ink Chemicals's system " LA-7054 ", and solid constituent is molten for 60% MEK Liquid) 5 parts, (hydroxyl equivalent is 151 to the CF system curing agent containing triazine skeleton, Dainippon Ink Chemicals system " LA- 3018-50P ", solid constituent is 50% 2- methoxy propyls alcoholic solution) 10 parts, (aurification strain is lived to naphthols system curing agent by Nippon Steel Formula commercial firm system " SN485 ", hydroxyl equivalent is 215, and solid constituent is 60% MEK solution) 10 parts, amine system curing accelerator (4- bis- Dimethylaminopyridine (DMAP), solid constituent is 5 mass % MEK solution) 1 part, fire retardant (Sanko Co., Ltd. system " HCA- HQ ", 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides, average grain diameter are 1.5 μm) 3 parts, The spherical titanium dioxide being surface-treated with amino silicone methane series coupling agent (Shin-Etsu Chemial Co., Ltd's system " KBM573 ") (golden material Co. Ltd. system " SP60-05 " is lived to silicon by Nippon Steel, and average grain diameter is 1.3 μm, and the carbon amounts of per unit surface area is 0.30mg/m2) 190 parts, it is with high speed rotary blender that its is dispersed, then, with cartridge filter (ROKITECHNO systems " SHP050 ") filtered, prepare resin varnish 2.
(preparation of resin varnish 3)
Stir while making 5 parts of naphthalene type epoxy resin (epoxide equivalent 144, Dainippon Ink Chemicals's system " HP4032SS "), biphenyl type (Nippon Kayaku K. K's system " NC3100 ", epoxide equivalent is 258) 5 parts, naphthylene ether type epoxy (DIC to epoxy resin Co. Ltd. system " EXA-7311 ", epoxide equivalent is 277) 20 parts and phenoxy resin (Mitsubishi chemical Co., Ltd's system " YX7553BH30 ", solid constituent is 30 mass % cyclohexanone：The 1 of methyl ethyl ketone (MEK)：1 solution) 6 parts dissolve by heating in The in the mixed solvent of 5 parts of 5 parts of solvent naphtha and cyclohexanone.It is cooled to after room temperature, (the DIC plants of formula meetings of mixed active ester compounds Society's system " HPC-8000-65T ", weight average molecular weight is about 2700, the mass % of nonvolatile component 65 of active group equivalent about 223 first Benzole soln) 5 parts, carbodiimide resin (Nisshinbo Chemical Co. Ltd. systems " V-03 ", the mass % of nonvolatile component 50 Toluene solution) 5 parts, the prepolymer of bisphenol A dicyanate (work as by Lonza Japan Co. Ltd. systems " BA230S75 ", cyanate Amount about 232, the mass % of nonvolatile component 75 MEK solution) 30 parts, curing accelerator (4-dimethylaminopyridine (DMAP), Gu Body composition is 5 mass % MEK solution) 1 part, imidazoles system curing accelerator (Mitsubishi chemical Co., Ltd's system " P200-H50 ", Gu Body composition is 50 mass % propylene glycol monomethyl ether solution) 0.1 part, (Tokyo is melted into Co. Ltd. system, acetyl to curing accelerator Acetone cobalt (III) [Co (III) Ac, solid constituent is 1 mass % MEK solution]) 3 parts, rubber particles (DOW Chemical Japanese strain Formula commercial firm system, PARALOID EXL2655) 2 parts, with phenyl amino silane series coupling agent (Shin-Etsu Chemial Co., Ltd's system, " KBM573 ") be surface-treated spherical silicon dioxide (golden material Co. Ltd. system " SPH516-05 " is lived by Nippon Steel, put down Equal particle diameter is 0.2 μm, and the carbon amounts of per unit surface area is 0.43mg/m2) 12 parts, with high speed rotary blender by its uniform point Dissipate, then, filtered with cartridge filter (ROKITECHNO systems " SHP020 "), prepare resin varnish 3.
(preparation of resin varnish 4)
Stir while making bisphenol A type epoxy resin that (Mitsubishi chemical Co., Ltd's system " 825 ", epoxide equivalent is about 176) 10 Part, (Dainippon Ink Chemicals's system " EXA-7311 ", epoxide equivalent is 277) 20 parts and phenoxy resin to naphthylene ether type epoxy (Mitsubishi chemical Co., Ltd's system " YX7553BH30 ", solid constituent is 30 mass % cyclohexanone：The 1 of methyl ethyl ketone (MEK)： 1 solution) 12 parts of in the mixed solvents for dissolving by heating in 5 parts of 12 parts of solvent naphtha and cyclohexanone.It is cooled to after room temperature, mixing is lived (Dainippon Ink Chemicals's system " HPC-8000-65T ", weight average molecular weight is about 2700 to property ester compounds, and active group equivalent about 223 is not The mass % of volatile ingredient 65 toluene solution) 30 parts, (4-dimethylaminopyridine, solid constituent is 5 mass %'s to curing accelerator MEK solution) 2 parts, imidazoles system curing accelerator (Shikoku Chem's system " 1B2PZ " 1- benzyl -2- phenylimidazoles, Solid constituent is 5% MEK solution) 0.5 part, fire retardant (Sanko Co., Ltd.'s system " HCA-HQ ", 10- (2,5- dihydroxy benzenes Base) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides, average grain diameter is 2 μm) 3 parts, with amino silicone methane series coupling agent (letter More chemical industry Co. Ltd. system " KBM573 ") (golden material strain formula is lived by Nippon Steel for the spherical silicon dioxide that is surface-treated Commercial firm's system " SP507-05 ", average grain diameter is 1.0 μm, and the carbon amounts of per unit surface area is 0.35mg/m2) 120 parts, revolved with high speed Turn mixer its is dispersed, then, filtered with cartridge filter (ROKITECHNO systems " SHP050 "), prepare resin Varnish 4.
(preparation of resin varnish 5)
Stir while making bisphenol f type epoxy resin that (Mitsubishi chemical Co., Ltd's system " 1750 ", epoxide equivalent is about 159) 5 Part, (Nippon Kayaku K. K's system " NC3000L ", epoxide equivalent is 288) 20 parts, biphenyl type epoxy tree to biphenyl type epoxy resin (Nippon Kayaku K. K's system " NC3100 ", epoxide equivalent is 258) 3 parts and phenoxy resin (Mitsubishi chemical Co., Ltd to fat Make " YX7553BH30 ", solid constituent is 30 mass % cyclohexanone：The 1 of methyl ethyl ketone (MEK)：1 solution) 12 parts of heating are molten Solution is in the in the mixed solvent of 5 parts of 5 parts of solvent naphtha and cyclohexanone.It is cooled to after room temperature, mixing wherein contains triazine skeleton CF system curing agent (hydroxyl equivalent is 151, Dainippon Ink Chemicals's system " LA-3018-50P ", and solid constituent is 50% 2- methoxy propyls alcoholic solution) 5 parts, (Dainippon Ink Chemicals's system " HPC-8000-65T ", weight average molecular weight is about for active ester compound For 2700, the mass % of nonvolatile component 65 of active group equivalent about 223 toluene solution) 15 parts, amine system curing accelerator (4- bis- Dimethylaminopyridine (DMAP), solid constituent is 5 mass % MEK solution) 2 parts, (four countries are melted into work to imidazoles system curing accelerator Industry Co. Ltd. system " 1B2PZ " 1- benzyl -2- phenylimidazoles, solid constituent is 5% MEK solution) 2 parts, the coupling of epoxy silane system 0.1 part of agent (Shin-Etsu Chemial Co., Ltd's system " KBM403 "), micro mist carborundum (Shinano Electric Refining Co., Ltd.'s system " SER-A06 ", average grain diameter is 0.6 μm) 5 parts, it is with high speed rotary blender that its is dispersed, then, use cartridge filter (ROKITECHNO systems " SHP030 ") is filtered, and prepares resin varnish 5.
(preparation of resin varnish 6)
Stir while making bisphenol A type epoxy resin that (Mitsubishi chemical Co., Ltd's system " 825 ", epoxide equivalent is about 176) 10 Part, (Mitsubishi chemical Co., Ltd's system " YX7700 ", epoxide equivalent is 270) 25 parts and phenoxy group tree to xylol type epoxy resin (Mitsubishi chemical Co., Ltd's system " YX7553BH30 ", solid constituent is 30 mass % cyclohexanone to fat：Methyl ethyl ketone (MEK) 1：1 solution) 20 parts of in the mixed solvents for dissolving by heating in 5 parts of 5 parts of solvent naphtha and cyclohexanone.It is cooled to after room temperature, mixes (hydroxyl equivalent is 125 to linear phenol-aldehyde resin system curing agent containing triazine skeleton, Dainippon Ink Chemicals's system " LA-7054 ", solid Composition is 60% MEK solution) 10 parts, naphthols system curing agent (Nippon Steel ＆ Sumitomo Metal Corporation's system " SN485 ", hydroxyl equivalent For 215, solid constituent is 60% MEK solution) 15 parts, polyvinyl butyral resin (105 DEG C of glass transition temperature, ponding Chemical industry Co. Ltd. system " KS-1 ") solid constituent 15% ethanol and toluene 1：1 mixed solution) 10 parts, amine system it is solid Change 1 part of accelerator (4-dimethylaminopyridine (DMAP), solid constituent is 5 mass % MEK solution), the solidification of imidazoles system to promote 2 parts of agent (Mitsubishi chemical Co., Ltd's system " P200-H50 ", solid constituent is 50 mass % propylene glycol monomethyl ether solution), use The spherical silicon dioxide that amino silicone methane series coupling agent (Shin-Etsu Chemial Co., Ltd's system " KBM573 ") is surface-treated (Co., Ltd.'s Admatechs systems " SO-C1 ", average grain diameter is 0.4 μm, and the carbon amounts of per unit surface area is 0.35mg/m2)22 Part, it is with high speed rotary blender that its is dispersed, then, carried out with cartridge filter (ROKITECHNO systems " SHP030 ") Filter, prepares resin varnish 6.
(preparation of resin varnish 7)
Stir while making bisphenol A type epoxy resin that (Mitsubishi chemical Co., Ltd's system " 825 ", epoxide equivalent is about 176) 5 Part, (Mitsubishi chemical Co., Ltd's system " YX4000HK ", epoxide equivalent is about 185) 10 parts, biphenyl to di- first phenol-type epoxy resin (Nippon Kayaku K. K's system " NC3000L ", epoxide equivalent is 288) 20 parts, (DIC plants of naphthalene type epoxy resin to type epoxy resin Formula commercial firm system " HP-4710 ", epoxide equivalent is about 170) 3 parts and phenoxy resin (Mitsubishi chemical Co., Ltd's system " YX7553BH30 ", solid constituent is 30 mass % cyclohexanone：The 1 of methyl ethyl ketone (MEK)：1 solution) 5 parts dissolve by heating in The in the mixed solvent of 5 parts of 10 parts of solvent naphtha and cyclohexanone.It is cooled to after room temperature, the line containing triazine skeleton is mixed wherein (hydroxyl equivalent is 125 to type phenolic resin system curing agent, Dainippon Ink Chemicals's system " LA-7054 ", and solid constituent is molten for 60% MEK Liquid) 5 parts, (hydroxyl equivalent is 151 to the CF system curing agent containing triazine skeleton, Dainippon Ink Chemicals system " LA3018- 50P ", solid constituent is 50% 2- methoxy propyls alcoholic solution) 10 parts, curing agent (Nippon Steel ＆ Sumitomo Metal Corporation of naphthols system Make " SN485 ", hydroxyl equivalent is 215, solid constituent is 60% MEK solution) 10 parts, amine system curing accelerator (4- dimethylaminos Yl pyridines (DMAP), solid constituent is 5 mass % MEK solution) 1 part, fire retardant (Sanko Co., Ltd.'s system " HCA-HQ ", 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides, average grain diameter is 1.5 μm) 3 parts, use amino Crushing silica (the strain formula that silane series coupling agent (Shin-Etsu Chemial Co., Ltd's system " KBM573 ") is surface-treated " IMSIL A-8 ", average grain diameter is 2 μm to the gloomy system of commercial firm dragon, and the carbon amounts of per unit surface area is 0.21mg/m2) 120 parts, with height Fast rotary blender is dispersed by its, then, is filtered with cartridge filter (ROKITECHNO systems " SHP050 "), prepares Resin varnish 7.
The material used in the making of each resin varnish and its use level (mass parts of nonvolatile component) are shown in table 1。
[table 1]
。
＜ embodiments 1：The making ＞ of resin sheet with supporter
As supporter, preparation has carried out demoulding processing with alkyd resin system releasing agent (Lindeke Co., Ltd's system " AL-5 ") PET film (Dongli Ltd.'s system " dew Miller R80 ", 38 μm of thickness, 130 DEG C of softening point, " demoulding PET ").
In the way of the thickness of dried first resin composition layer turns into 5 μm, using metal mold coating machine, by resin Varnish 1 is spread evenly across on demoulding PET, and drying in 5 minutes is carried out at a temperature of from 80 DEG C to 160 DEG C, thus, in demoulding PET On obtain the first resin composition layer.Next, on the first resin composition layer coating resin varnish 2 so that dry after with The aggregate thickness of first resin composition layer turns into 20 μm, carries out drying in 3 minutes in 70 DEG C~110 DEG C (average 90 DEG C), forms 2 The resin composition layer (resin sheet) of layer.Next, in face (i.e. the second resin combination not engaged with supporter of resin sheet The face not engaged with the first resin composition layer of layer) on, the polypropylene screen of diaphragm (ス plants of prince エ Off テ ッ Network will be used as Formula commercial firm system " ア Le Off ァ Application MA-411 ", 15 μm of thickness) asperities, carried out in the way of being engaged with the second resin composition layer Stacking.Thus, obtain (being derived from by supporter, the first resin composition layer (being derived from resin varnish 1), the second resin composition layer Resin varnish 2) and the resin sheet 1 with supporter that sequentially forms of diaphragm.
＜ embodiments 2：The making ＞ of resin sheet 2 with supporter
In embodiment 1,1) replace resin varnish 1 using resin varnish 3, with the thickness of dried first resin composition layer into Mode for 3 μm is coated, and 2) resin varnish 2 is replaced using resin varnish 4, in addition, grasp similarly to Example 1 Make, obtain the resin sheet 2 with supporter.
＜ embodiments 3：The making ＞ of resin sheet 3 with supporter
In embodiment 1,1) replace resin varnish 1 using resin varnish 5, with the thickness of dried first resin composition layer into Mode for 4 μm is coated, and 2) resin varnish 2 is replaced using resin varnish 4, in addition, grasp similarly to Example 1 Make, obtain the resin sheet 3 with supporter.
＜ comparative examples 1：The making ＞ of resin sheet 4 with supporter
In embodiment 1, resin varnish 1 is replaced using resin varnish 6, is turned into the thickness of dried first resin composition layer 4 μm of mode is coated, in addition, is operated similarly to Example 1, obtains the resin sheet 4 with supporter.
＜ comparative examples 2：The making ＞ of resin sheet 5 with supporter
In embodiment 1, resin varnish 2 is replaced using resin varnish 7, in addition, operates similarly to Example 1, obtains band The resin sheet 5 of supporter.
(making of the solidfied material of each resin combination)
In the way of the thickness of dried resin composition layer turns into 50 μm, using metal mold coating machine, by each resin varnish 1 ~7 are spread evenly across with embodiment, comparative example identical demoulding PET film, 5 points are carried out at a temperature of from 70 DEG C to 120 DEG C Clock is dried, thus, obtains being formed with the resin film of resin composition layer on demoulding PET film.
To be stripped the untreated face of PET film (Lindeke Co., Ltd's system " 501010 ", thickness is 38 μm, 240mm square) With glass cloth base material epoxy resin two sides copper-clad laminated board (Matsushita Electric Industrial Co., Ltd's system " R5715ES ", thickness 0.7mm, 255mm square) contact mode, by it is described the demoulding PET film be arranged on the copper-clad laminated board of glass cloth base material epoxy resin two sides, Four sides of the mold release film are fixed with polyimides jointing tape (wide 10mm).
Thickness for resin composition layer is 50 μm of each resin film (167 × 107mm square), uses batch-type vacuum Pressurize laminater (stage of Nikko-Materials Co. Ltd. systems 2 stacks laminater CVP700), with resin combination Layer carries out lamination treatment with being stripped the mode that the stripping surface of PET film is contacted in center.Lamination treatment is carried out by the following method： Depressurize within 30 seconds, air pressure is turned into below 13hPa, then temperature be 100 DEG C, pressure be progress under conditions of 0.74MPa Crimp within 30 seconds.
Next, supporter is peeled off, under the same conditions from the top of resin composition layer and then lamination same resin The resin composition layer of film, is made the resin composition layer of 50 μ m 2=100 μ m-thicks, then, is peeling off the state of supporter Under, make resin composition layer heat cure under the condition of cure of 100 DEG C of solidifications solidification 90 minutes in 30 minutes and then 190 DEG C.
After heat cure, polyimides jointing tape is peeled off, from glass cloth base material epoxy resin two sides, copper-clad laminated board takes Lower resin composition layer.And then demoulding PET film is peeled off from resin composition layer, obtain the sheet solidfied material of about 100 μ m-thicks.By piece Shape solidfied material is referred to as evaluation solidfied material.
(measure of the thermal conductivity factor of solidfied material)
(1) thermal diffusivity α measure
Using ai-Phase company systems, " ai-Phase Mobile 1u " utilize temperature wave analytic approach, evaluation of measuring solidfied material Thickness direction thermal diffusivity α (m2/s).3 measure are carried out for same sample, average value is calculated.
(2) specific heat capacity Cp measure
Using differential scanning calorimetry (DSC) (SII Nano Technology Co. Ltd. systems " DSC7020 "), with 10 DEG C/min from- 40 DEG C are warming up to 80 DEG C, are measured, thus, calculate the specific heat capacity Cp (J/kg K) at 20 DEG C of solidfied material sample.
(3) measure of density p
Solidified using METTLER TOLEDO Co. Ltd. system assay balances XP105 (using gravity test set group) evaluation of measuring Density (the kg/m of thing3)。
(4) thermal conductivity factor λ is calculated
By the thermal diffusivity α (m obtained in above-mentioned (1) ~ (3)2/ s), specific heat capacity Cp (J/kg K) and density p (kg/m3) substitute into Following formula (I)s, calculate thermal conductivity factor λ (W/m K).Show the result in following table；
λ=α × Cp × ρ (I).
The length in the recessed damage portions of ＜ and the evaluation ＞ of Laser Processing property
(making of sample)
(1) base treatment of circuit board
For the glass cloth base material epoxy resin layer for the circular conductive pattern (wiring pattern) that 150 μm of diameter is formed with two sides Lamination (12 μm of the thickness of copper foil, the thickness 0.3mm of substrate, size 510mm × 340mm, uses Panasonic Co. Ltd. system " R- 1515A " forms the circuit board of conductive pattern (residual copper rate about 70%)) two sides, handled (i)：Use MEC plants of formula meetings Society's system " CZ8101 ", carries out about 0.8 μm for thickness and etches and remove, carry out the roughening processing on the surface of conductive pattern.
(2) lamination process of resin sheet
By made in embodiment and comparative example have 2 layers of resin combination it is each with supporter resin sheet (size 504mm × Diaphragm 334mm) is peeled off, and uses batch-type vacuum pressed laminater (Nikko-Materials Co. Ltd. systems, 2 stages Stack laminater CVP700), in the way of the second resin composition layer is contacted with the circuit board treated through foregoing (1), It is laminated in the two sides of circuit board.The lamination process is implemented by the following method：Depressurize within 30 seconds, air pressure is turned into 13hPa Hereinafter, then temperature be 120 DEG C, pressure be crimp within 30 seconds under conditions of 0.74MPa.Next, being 110 in temperature DEG C, pressure be 0.5MPa under conditions of carry out 60 seconds hot pressing process.
(3) solidification of resin composition layer
Circuit board for being laminated with the resin sheet with supporter, 30 minutes at 100 DEG C, then 30 minutes at 175 DEG C Under condition of cure, make resin composition layer heat cure, form insulating barrier (about 15 μ m-thick on conductor).
(4) formation of through hole
Laser is irradiated from the top on support side, in the surface of a diameter of 150 μm of the circular conductive pattern positioned at inner side Insulating barrier on formed minor diameter through hole, obtain evaluate substrate.
The formation process of through hole is carried out under conditions of as follows.
Use Mitsubishi Electric Corporation CO2Laser machine " 605GTWIII (- P) ", shines from the top on support side Laser is penetrated, the through hole that top diameter (diameter) is 30 μm is formed on the insulating layer.The irradiation condition of laser is：Mask diameters are 1mm, pulse width is 16 μ s, and energy is 0.20mJ/ rifles (shot), and rifle number is 2, with burst mode (burst mode) (10kHz) is carried out.
(evaluation)
(5) confirmation (evaluation of the length and Laser Processing property in recessed damage portion) of the shape of through hole
For the evaluation substrate obtained in above-mentioned (4), supporter is peeled off, appropriate size is cut into, by the examination comprising through hole Sample is embedded in cold conditions embedment resin, using buck device (Struers company system RotoPol-22), is made in through hole Centre portion section, is seen using scanning electron microscope (Co., Ltd. Hitachi Ha イ テ Network ノ ロ ジ ー ズ S4800) Examine.By obtained determining image produced in the interface of the first resin composition layer and the second resin composition layer along interface The length (μm) in the recessed damage portion that bearing of trend is produced.Specifically, the straight line of the outer side wall for inserting in through hole is drawn, is determined straight from this Line is to the interface of the first resin composition layer and the second resin composition layer apart from d.4 through holes are measured, asked respectively Go out average value, evaluated according to following benchmark；
○：The length in recessed damage portion is less than 3 μm
×：The length in recessed damage portion is more than 3 μm.
[table 2]
。
Symbol description
10 resin sheets with supporter
11 supporters
12 resin sheets
13 first resin composition layers
14 second resin composition layers.

Claims (12)

1. the resin sheet with supporter, it has supporter and the resin sheet being arranged on supporter, it is characterised in that
Resin sheet has：
Be arranged at support side the first resin composition layer formed by the first resin combination and
The second resin composition layer formed by the second resin combination of the side opposite with support side is arranged on,
First resin combination includes (a) inorganic filling material, regard the nonvolatile component in the first resin combination as 100 matter When measuring %, the content of (a) composition is below 30 mass %,
Second resin combination includes (a) inorganic filling material, regard the nonvolatile component in the second resin combination as 100 matter When measuring %, the content of (a) composition is more than 60 mass %,
The difference of the thermal conductivity factor of the thermal conductivity factor of first thermosetting compound and the second thermosetting compound is below 0.4W/mK,
The first thermosetting compound is to make the first resin combination in 100 DEG C of heat cures 30 minutes and then in 190 DEG C of heat cures 90 Obtained from minute,
The second thermosetting compound is to make the second resin combination in 100 DEG C of heat cures 30 minutes and then in 190 DEG C of heat cures 90 Obtained from minute.
2. the resin sheet with supporter described in claim 1, wherein, the thickness of resin sheet is less than 40 μm.
3. the resin sheet with supporter described in claim 1, wherein, the thickness of resin sheet is less than 25 μm.
4. the resin sheet with supporter described in claim 1, wherein, by being averaged for (a) composition in the first resin combination Particle diameter is designated as R1 (μm), when the average grain diameter of (a) composition in the second resin combination is designated as into R2 (μm), the ratio between R1 and R2, That is R2/R1 is 1~15.
5. the resin sheet with supporter described in claim 1, wherein, the first resin combination includes (b) epoxy resin, (b) Composition has mesomorphic skeleton.
6. the resin sheet with supporter described in claim 5, wherein, (b) composition is selected from di- first phenol-type epoxy resin, double More than a kind in phenol A types epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin and naphthalene type epoxy resin.
7. the resin sheet with supporter described in claim 1, it is used for the insulating barrier to form printed wiring board.
8. the manufacture method of printed wiring board, this method includes following processes：
Process (I), by the resin sheet according to any one of claims 1 to 7 with supporter with the second resin composition layer with The mode of internal substrate engagement is layered on internal substrate；
Process (II), insulating barrier is formed by the resin sheet heat cure with supporter；And
Process (III), forms through hole on the insulating layer, removes supporter.
9. the manufacture method of the printed wiring board described in claim 8, wherein, in process (III), using laser on the insulating layer Form through hole.
10. the manufacture method of the printed wiring board described in claim 8, wherein, the opening diameter of through hole is less than 40 μm.
11. printed wiring board, its include by the resin sheet according to any one of claims 1 to 7 with supporter formed it is exhausted Edge layer.
12. semiconductor device, it possesses the printed wiring board described in claim 11.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110016203A (en) * 2018-01-09 2019-07-16 味之素株式会社 Resin combination
WO2020047920A1 (en) * 2018-09-07 2020-03-12 广东生益科技股份有限公司 Thermosetting resin composition and prepreg, laminate and high frequency circuit substrate containing same
CN112313280A (en) * 2018-06-12 2021-02-02 积水化学工业株式会社 Resin material and multilayer printed wiring board
CN112856336A (en) * 2021-01-14 2021-05-28 广东凯晟照明科技有限公司 High-efficient heat dissipation formula high-power LED lamp holder
CN114144468A (en) * 2019-07-12 2022-03-04 日东电工株式会社 Sealing resin sheet

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* Cited by examiner, † Cited by third party
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KR102669548B1 (en) * 2021-03-31 2024-05-29 스미또모 베이크라이트 가부시키가이샤 Resin composition for encapsulation and electronic devices using the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005239767A (en) * 2004-02-24 2005-09-08 Matsushita Electric Works Ltd Resin composition, and prepreg and laminate using the same
CN103650649A (en) * 2011-07-07 2014-03-19 日立化成株式会社 Adhesive film, multilayer printed wiring board using adhesive film, and method for manufacturing multilayer printed wiring board
CN104053721A (en) * 2012-01-23 2014-09-17 味之素株式会社 Resin composition
CN104842609A (en) * 2014-02-19 2015-08-19 味之素株式会社 Resin sheet with support

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5869871B2 (en) * 2011-12-22 2016-02-24 太陽インキ製造株式会社 Dry film and printed wiring board using the same
JP6044139B2 (en) 2012-07-06 2016-12-14 味の素株式会社 Insulating resin sheet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005239767A (en) * 2004-02-24 2005-09-08 Matsushita Electric Works Ltd Resin composition, and prepreg and laminate using the same
CN103650649A (en) * 2011-07-07 2014-03-19 日立化成株式会社 Adhesive film, multilayer printed wiring board using adhesive film, and method for manufacturing multilayer printed wiring board
CN104053721A (en) * 2012-01-23 2014-09-17 味之素株式会社 Resin composition
CN104842609A (en) * 2014-02-19 2015-08-19 味之素株式会社 Resin sheet with support

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110016203A (en) * 2018-01-09 2019-07-16 味之素株式会社 Resin combination
CN110016203B (en) * 2018-01-09 2023-10-31 味之素株式会社 Resin composition
CN112313280A (en) * 2018-06-12 2021-02-02 积水化学工业株式会社 Resin material and multilayer printed wiring board
WO2020047920A1 (en) * 2018-09-07 2020-03-12 广东生益科技股份有限公司 Thermosetting resin composition and prepreg, laminate and high frequency circuit substrate containing same
CN114144468A (en) * 2019-07-12 2022-03-04 日东电工株式会社 Sealing resin sheet
CN112856336A (en) * 2021-01-14 2021-05-28 广东凯晟照明科技有限公司 High-efficient heat dissipation formula high-power LED lamp holder
CN112856336B (en) * 2021-01-14 2021-10-29 广东凯晟照明科技有限公司 High-efficient heat dissipation formula high-power LED lamp holder

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