CN104349614A - Method for manufacturing multilayer printed wiring board - Google Patents

Method for manufacturing multilayer printed wiring board Download PDF

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Publication number
CN104349614A
CN104349614A CN201410374825.XA CN201410374825A CN104349614A CN 104349614 A CN104349614 A CN 104349614A CN 201410374825 A CN201410374825 A CN 201410374825A CN 104349614 A CN104349614 A CN 104349614A
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CN
China
Prior art keywords
prepreg
insulating barrier
quality
strain
epoxy resin
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Granted
Application number
CN201410374825.XA
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Chinese (zh)
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CN104349614B (en
Inventor
宫本亮
中村茂雄
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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Publication of CN104349614A publication Critical patent/CN104349614A/en
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

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

Abstract

The invention provides a method for manufacturing a multilayer printed wiring board, wherein, even when an insulating layer is formed by a prepreg having a high total content of a fiber basal material and an inorganic filling material, the insulating layer that has excellent surface smoothness, small difference of thicknesses of the substrate central portion and the substrate end portions, and excellent layer thickness balance can be achieved. The method for manufacturing the multilayer printed wiring board comprises: (I) a step of laminating the prepreg with a carrier having the prepreg formed on a carrier film on an inner layer circuit substrate in a manner that the prepreg is jointed with the inner layer circuit substrate; (II) a step of hot-pressing and smoothing the laminated prepreg with the carrier; and (III) a step of thermocuring the prepreg to form the insulating layer. The method for manufacturing the multilayer printed wiring board is characterized in that when the total mass of the prepreg is set to be 100 mass%, the total mass of the fiber basal material and the inorganic filling material in the prepreg is more than 70 mass%, melt viscosity of the prepreg at the hot pressing temperature is 300-10000 P, the maximum cross-section height (Rt) of the carrier film surface of the prepreg with the carrier is less than 5 [mu]m, and when the laminating temperature in the step (I) is set to be T1 (DEG C) and the hot pressuring temperature in the step (II) is set to be T2 (DEG C), T1 and T2 satisfy the relationship that T2<=T1+10.

Description

The manufacture method of multilayer printed circuit board
Technical field
The present invention relates to the manufacture method of multilayer printed circuit board.In detail, the present invention relates to the manufacture method of the multilayer printed circuit board of the prepreg employing band carrier.
Background technology
As the manufacturing technology of multilayer printed circuit board, the known manufacture method that make use of stacking (PVC Le De ア ッ プ) mode of alternately stacked insulating barrier and conductor layer.In the manufacture method that make use of stack manner, usually, insulating barrier is formed by making resin combination hot curing.Such as can use following method: use define on a carrier film resin composition layer adhesive film, utilize vacuum laminator formed insulating barrier.In addition in recent years, improve the mechanical strength of insulating barrier in order to the requirement of the slimming with multilayer printed circuit board, propose and use the prepreg of band carrier, utilize vacuum laminator to form the method (patent documentation 1) of insulating barrier.
Prior art document
Patent documentation
Patent documentation 1: No. 2009/35014th, International Publication.
Summary of the invention
the technical problem that invention will solve
On the other hand, with the slimming of multilayer printed circuit board, in order to prevent the crackle etc. caused by the thermal expansion difference with conductor layer, the reduction of the thermal coefficient of expansion of insulating barrier becomes more and more important.As the method for making the thermal coefficient of expansion of insulating barrier reduce, the content can enumerating fiber base material in the prepreg such as making to use in the formation of insulating barrier and/or inorganic filling material increases.But, during the prepreg using the content of fiber base material and/or inorganic filling material high, have the tendency being difficult to the insulating barrier forming surface smoothing.Such as in the technology of above-mentioned patent documentation 1 record, implement to use vacuum laminator to be pressed in after on internal layer circuit substrate by the prepreg of band carrier, metallic plate is utilized to carry out the step of hot pressing and smoothing on the surface of the prepreg of the band carrier through lamination, but during the prepreg using the content of fiber base material and/or inorganic filling material high, prepreg is difficult to follow the concave-convex surface presence or absence of circuit conductor (result from) of internal layer circuit substrate, the surface of the insulating barrier of gained has the fluctuating corresponding with the concave-convex surface of the internal layer circuit substrate as ground, there is the tendency of the insulating barrier being difficult to obtain surface smoothing.
Such as, when carrying out hot pressing under the hot pressing temperature in smoothing step being set to high value etc., making the mobility of resin uprise such condition, the trackability of prepreg to the concave-convex surface of internal layer circuit substrate can be improved, the fluctuating on the surface of insulating barrier can be made to diminish.But in this case, the present inventor etc. find that there is following tendency: due to oozing out of resin, cause the disturbance of equilibrium of the thickness of insulating barrier, in a substrate centre portion and base ends, the thickness of the insulating barrier of gained produces large difference.
Problem of the present invention is the manufacture method providing multilayer printed circuit board, wherein, even if when using the high prepreg of the total content of fiber base material and inorganic filling material to form insulating barrier, the insulating barrier that flatness is excellent, the equilibrium that is little, thickness of the difference of the thickness of centre portion and base ends is also good in a substrate on surface also can be realized.
the means of technical solution problem
The present inventor etc. are in view of above-mentioned problem, carry out making great efforts research, found that when using the prepreg of band carrier to form insulating barrier, the maximum cross-section height (Rt) on the carrier film surface of the prepreg of the band carrier after lamination step is made to maintain below certain value, and make the difference of the laminating temperature of lamination step and the hot pressing temperature of smoothing step maintain particular range, the prepreg of described band carrier to be the total content being formed with fiber base material and inorganic filling material be on a carrier film a certain amount of more than, there is the prepreg of specific melt viscosity, above-mentioned problem can be solved thus, thus complete the present invention.
That is, the present invention contains following content:
[1] manufacture method of multilayer printed circuit board, it comprises
(I) prepreg being formed with the band carrier of prepreg is on a carrier film laminated to the step on internal layer circuit substrate in the mode making prepreg and engage with internal layer circuit substrate,
(II) by the prepreg hot pressing of the band carrier through lamination the step of smoothing and
(III) prepreg hot curing is formed the step of insulating barrier,
The feature of the manufacture method of described multilayer printed circuit board is,
When the total quality of prepreg is set to 100 quality %, the fiber base material in prepreg and the gross mass of inorganic filling material are more than 70 quality %,
The melt viscosity of the prepreg under the hot pressing temperature of step (II) is 300 ~ 10000 pools,
The maximum cross-section height (Rt) on the carrier film surface of the prepreg of the band carrier after step (I) is less than 5 μm, and
The laminating temperature of step (I) is set to T1 (DEG C), the hot pressing temperature of step (II) is when being set to T2 (DEG C), T1 and T2 meets the relation of T2≤T1+10;
[2] method Gen Ju [1], wherein, T1 and T2 meets the relation of T2≤T1+5;
[3] according to [1] or the method described in [2], wherein, step (II) is implemented more than 2 times;
[4] according to the method according to any one of [1] ~ [3], wherein, the maximum cross-section height (Rt) of the surface of insulating layer after step (III) is less than 3 μm;
[5] according to the method according to any one of [1] ~ [4], wherein, prepreg is further containing epoxy resin and curing agent;
[6] according to the method according to any one of [1] ~ [5], wherein, prepreg is formed in fiber base material by making the resin combination containing epoxy resin, curing agent and inorganic filling material infiltrate;
[7] according to the method according to any one of [1] ~ [6], wherein, carrier film is stripped after step (III);
[8] according to the method according to any one of [1] ~ [7], wherein, in step (III), prepreg is configured with plumbness in heating furnace, carries out hot curing and form insulating barrier;
[9] multilayer printed circuit board, it contains the insulating barrier of the condition meeting following (a) to (c):
When the total quality of this insulating barrier is set to 100 quality % by () a, the gross mass of fiber base material and inorganic filling material is more than 70 quality %;
B the maximum cross-section height (Rt) on the surface of () this insulating barrier is less than 3 μm; With
C the difference of the thickness of the base ends of () this insulating barrier and the thickness in substrate center portion is less than 2.5 μm.
invention effect
According to method of the present invention, even if when using the high prepreg of the total content of fiber base material and inorganic filling material to form insulating barrier, the difference that the flatness that also can manufacture surface is excellent, centre portion and base ends have thickness is in a substrate little, the multilayer printed circuit board of the balanced good insulating barrier of thickness.
Embodiment
Before the manufacture method for multilayer printed circuit board of the present invention is described in detail, " prepreg of band carrier " used in the method for the invention is described.
< is with the prepreg > of carrier
In the method for the invention, the prepreg being formed with the band carrier of prepreg is on a carrier film used.
As carrier film, the film, metal forming (Copper Foil, aluminium foil etc.), the processing release paper that are formed by plastic material can be enumerated, preferably use the film formed by plastic material.As plastic material, acrylic acid series, cyclic polyolefin, tri acetyl cellulose (TAC), polyether sulfides (PES), polyether-ketone, the polyimides etc. such as the such as polyester such as polyethylene terephthalate (below sometimes referred to as " PET "), Polyethylene Naphthalate (below sometimes referred to as " PEN "), Merlon (below sometimes referred to as " PC "), polymethyl methacrylate (PMMA) can be enumerated.Wherein, preferred polyethylene terephthalate, Polyethylene Naphthalate, particularly preferably low-cost polyethylene terephthalate.In suitable execution mode, carrier film is polyethylene terephthalate film.
Delustring process, corona treatment can be implemented to the face engaged with prepreg of carrier film.
In addition, as carrier film, the carrier film face that engages with prepreg with the band release layer of release layer can be used in.As the release agent used in the release layer of the carrier film of band release layer, the release agent of more than a kind of being such as selected from alkyd resins, vistanex, polyurethane resin and organic siliconresin can be enumerated.
In the present invention, the carrier film of release layer is with to use commercially available product.As commercially available product, " PET501010 ", " SK-1 ", " AL-5 ", " AL-7 " etc. that such as リ Application テ ッ Network (strain) is made can be enumerated.
The thickness of carrier film is not particularly limited, and is preferably the scope of 10 μm ~ 70 μm, is more preferably the scope of 20 μm ~ 60 μm, and then is preferably the scope of 20 μm ~ 50 μm.Should illustrate, when carrier film is the carrier film of band release layer, the thickness of the carrier film entirety of preferably with release layer is in above-mentioned scope.
Prepreg makes resin combination infiltration be formed in fiber base material.
Fiber base material is not particularly limited, and can be used as the fiber base material that the prepreg base materials such as glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabrics are conventional.When the insulating barrier for the formation of multilayer printed circuit board, thickness can be preferably used to be the slim sheet-like fiber base material of less than 50 μm, especially, preferred thickness is the sheet-like fiber base material of 10 μm ~ 40 μm, and more preferably thickness is the sheet-like fiber base material of 10 μm ~ 30 μm.
As the concrete example of glass cloth that can be used as sheet-like fiber base material, can enumerate: " ス タ イ Le 1027MS " (warp count 75/25mm, weft count 75/25mm, cloth weight 20g/m that rising sun シ ュ エ ー ベ Le (strain) makes 2, thickness 19 μm), " ス タ イ Le 1037MS " (warp count 70/25mm, weft count 73/25mm, cloth weight 24g/m of making of rising sun シ ュ エ ー ベ Le (strain) 2, thickness 28 μm), (strain) has pool to make made " 1078 " (warp count 54/25mm, weft count 54/25mm, cloth weight 48g/m 2, thickness 43 μm), (strain) have pool to make made " 1037NS " (warp count 72/25mm, weft count 69/25mm, cloth weight 23g/m 2, thickness 21 μm) (strain) have pool to make made " 1027NS " (warp count 75/25mm, weft count 75/25mm, cloth weight 19.5g/m 2, thickness 16 μm), (strain) have pool to make made " 1015NS " (warp count 95/25mm, weft count 95/25mm, cloth weight 17.5g/m 2, thickness 15 μm), (strain) have pool to make made " 1000NS " (warp count 85/25mm, weft count 85/25mm, cloth weight 11g/m 2, thickness 10 μm) etc.In addition as the concrete example of liquid crystal polymer nonwoven fabrics, can enumerate (strain) Network ラ レ, " ベ Network Le ス " (weight per unit area 6 ~ 15g/m that make use of meltblown of aromatic polyester nonwoven fabrics 2), " ベ Network ト ラ Application " etc.
For the resin combination for prepreg, as long as its solidfied material has sufficient hardness and insulating properties, be just not particularly limited, the known resin combination used can be used in the formation of the insulating barrier of multilayer printed circuit board.
Suppress for consider compared with the angle of low degree from the thermal coefficient of expansion of the insulating barrier by gained, the resin combination for prepreg preferably contains inorganic filling material.
Inorganic filler can enumerate such as silicon dioxide, silicon nitride, aluminium oxide, glass, cordierite, Si oxide, barium sulfate, brium carbonate, talcum, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminium nitride, nitrogenized manganese, aluminium borate, barium titanate, strontium carbonate, strontium titanates, calcium titanate, magnesium titanate, bismuth titanates, titanium oxide, zirconia, metatitanic acid barium zirconate, barium zirconate, calcium zirconate, basic zirconium phosphate, with phosphoric acid tungsten wire array etc.Wherein, the silicon dioxide such as amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica is specially suitable.Silicon dioxide is preferably spherical silicon dioxide in addition.Inorganic filling material can be used alone a kind, also two or more can be combinationally used.As commercially available spheroidal fused silicon dioxide, (strain) ア De マ テ ッ Network ス system " SOC4 ", " SOC2 ", " SOC1 " can be enumerated.
The average grain diameter of inorganic filling material, considers from the angle obtaining insulating reliability and the good insulating barrier of surface smoothness, is preferably less than 2 μm, is more preferably less than 1 μm, and then be preferably less than 0.8 μm, and then be more preferably less than 0.6 μm.On the other hand, the angle improved from the dispersiveness of inorganic filling material is considered, the average grain diameter of inorganic filling material is preferably more than 0.01 μm, is more preferably more than 0.05 μm, and then is preferably more than 0.1 μm.The average grain diameter of inorganic filling material can utilize the laser diffraction-scattering method based on Michaelis (Mie) scattering theory to measure.Particularly, utilize laser diffraction and scattering formula particle size distribution device, make the particle size distribution of inorganic filling material with volume reference, its median diameter is set to average grain diameter, can measure thus.Working sample preferably can use and utilize ultrasonic wave that inorganic filling material is dispersed in water and the sample obtained.As laser diffraction and scattering formula particle size distribution device, Horiba Ltd LA-950 etc. can be used.
The content of the inorganic filling material in resin combination, suppresses for consider compared with the angle of low degree from the thermal coefficient of expansion of the insulating barrier by gained, is preferably more than 40 quality %, is more preferably more than 50 quality %, and then be preferably more than 60 quality %.The upper limit of the content of the inorganic filling material in resin combination is not particularly limited, and considers, be preferably below 90 quality %, be more preferably below 85 quality % from the angle obtaining the good insulating barrier of surface smoothness.
Should illustrate, in the present invention, the content of each composition in resin combination is the value when non-volatile component in resin combination being set to 100 quality %.
In order to improve moisture-proof, inorganic filling material preferably processes with the surface conditioning agent of more than a kind of epoxy silane system coupling agent, amino silicone methane series coupling agent, hydrosulphonyl silane system coupling agent, silane series coupling agent, organic silazane hydride compounds, titanate esters system coupling agent etc.In surface conditioning agent, amino silicone methane series coupling agent, due to the excellence such as characteristic of moisture-proof, dispersiveness, solidfied material, is therefore suitable.Inorganic filling material can process in advance with surface conditioning agent before being mixed in resin combination.Or inorganic filling material can process with surface conditioning agent by adding inorganic filler and surface conditioning agent (that is, utilizing integral blend method) in resin combination.As the commercially available product of surface conditioning agent, SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM403 " (3-glycidoxypropyltrime,hoxysilane) can be enumerated, SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM803 " (3-mercaptopropyi trimethoxy silane), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBE903 " (APTES), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM573 " (N-phenyl-3-TSL 8330), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM103 " (phenyltrimethoxysila,e), SHIN-ETSU HANTOTAI's chemical industry (strain) system " SZ-31 " (hexamethyldisiloxane) etc.
When inorganic filling material is set to 100 quality %, the treating capacity of surface conditioning agent is preferably 0.01 quality % ~ 5 quality %, is more preferably 0.1 quality % ~ 3 quality %.
Resin combination for prepreg is preferred and then contain epoxy resin and curing agent.Therefore, in suitable execution mode, prepreg contains the resin combination of epoxy resin, curing agent and inorganic filling material by infiltration in fiber base material and is formed.
-epoxy resin-
There is no particular limitation for epoxy resin, in 1 molecule, preferably have the epoxy resin of the epoxy radicals of more than 2.Particularly, bisphenol A type epoxy resin can be enumerated, bisphenol f type epoxy resin, the bisphenol-type epoxy resins such as bisphenol-s epoxy resin and bisphenol AF type epoxy resin, novolac type epoxy resin, tert butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, CF type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, wire aliphatic epoxy resin, there is the epoxy resin of butadiene structure, alicyclic epoxy resin, hetero ring type epoxy resin, containing the epoxy resin of volution, cyclohexanedimethanol type epoxy resin, trihydroxy methyl type epoxy resin, halogenated epoxy resin etc.Epoxy resin can be used alone a kind, also two or more can be combinationally used.
Wherein, consider from the angle of resistance to Hot, insulating reliability and mobility, preferably bisphenol-type epoxy resin (preferred bisphenol A type epoxy resin, bisphenol f type epoxy resin), naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy, glycidyl ester type epoxy resin, anthracene type epoxy resin, there is the epoxy resin of butadiene structure.Especially, epoxy resin is preferably containing more than a kind that is selected from bisphenol-type epoxy resin (preferred bisphenol A type epoxy resin, bisphenol f type epoxy resin), naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin and naphthylene ether type epoxy.Particularly, such as bisphenol A type epoxy resin (Mitsubishi Chemical's (strain) system " jER828EL " can be enumerated, " YL980 "), bisphenol f type epoxy resin (Mitsubishi Chemical's (strain) system " jER806H ", " YL983U "), (DIC (strain) makes " HP4032 " to naphthalene type 2 functional epoxy resins, " HP4032D ", " HP4032SS ", " EXA4032SS "), (DIC (strain) makes " HP4700 " to naphthalene type 4 functional epoxy resins, " HP4710 "), naphthol type epoxy resin (Nippon Steel's chemistry (strain) system " ESN-475V "), there is the epoxy resin (ダ イ セ Le chemical industry (strain) makes " PB-3600 ") of butadiene structure, biphenyl type epoxy resin (Japanese chemical drug (strain) system " NC3000H ", " NC3000L ", " NC3100 ", Mitsubishi Chemical's (strain) system " YX4000 ", " YX4000H ", " YX4000HK ", " YL6121 "), anthracene type epoxy resin (Mitsubishi Chemical's (strain) system " YX8800 "), (DIC (strain) makes " EXA-7310 " to naphthylene ether type epoxy, " EXA-7311 ", " EXA-7311L ", " EXA-7311G3 ", " EXA-7311G4 "), (Na ガ セ ケ system テ ッ Network ス (strain) makes " EX711 " to glycidyl ester type epoxy resin, " EX721 ", (strain) プ リ Application テ ッ Network system " R540 ") etc.
Epoxy resin preferably contains the epoxy resin of the epoxy radicals in 1 molecule with more than 2.When the non-volatile component of epoxy resin is set to 100 quality %, preferably more than at least 50 quality % are the epoxy resin of the epoxy radicals in 1 molecule with more than 2.
Consider from raising prepreg the angle of the trackability of the concave-convex surface of internal layer circuit substrate, epoxy resin is preferably containing the epoxy resin (hereinafter also referred to " liquid-state epoxy resin ") temperature 20 DEG C being liquid state.From improve prepreg to the trackability of the concave-convex surface of internal layer circuit substrate while, angle that the solidification physical property of insulating barrier prepreg hot curing formed is improved considers, epoxy resin preferably contains liquid-state epoxy resin and is solid-state epoxy resin (hereinafter also referred to " solid epoxy resin ") temperature 20 DEG C.As liquid-state epoxy resin, preferably there is in 1 molecule the liquid-state epoxy resin of the epoxy radicals of more than 2, be more preferably the fragrant family liquid-state epoxy resin of the epoxy radicals in 1 molecule with more than 2.As solid epoxy resin, preferably there is in 1 molecule the solid epoxy resin of the epoxy radicals of more than 3, be more preferably the fragrant family solid epoxy resin of the epoxy radicals in 1 molecule with more than 3.In the present invention, the epoxy resin of fragrant family refers to the epoxy resin in its molecule with aromatic rings.
As liquid-state epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac type epoxy resin, glycidyl ester type epoxy resin, naphthalene type epoxy resin etc. can be enumerated, be preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin, naphthalene type epoxy resin.Liquid-state epoxy resin can be used alone a kind, also two or more can be combinationally used.As solid epoxy resin, naphthalene type 4 functional epoxy resins, CF type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol (trisphenol) epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy etc. can be enumerated, more preferably naphthalene type 4 functional epoxy resins, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy.Solid epoxy resin can be used alone a kind, also two or more can be combinationally used.
As epoxy resin, by liquid-state epoxy resin and solid epoxy resin and the used time, the angle improved from the solidification physical property of the insulating barrier making gained is considered, their mixing ratio (liquid-state epoxy resin: solid epoxy resin) is preferably the scope of 1: 0.1 ~ 1: 8 by quality ratio, more preferably the scope of 1: 0.3 ~ 1: 7, and then preferably 1: 0.6 ~ 1: 6 scope, and then more preferably 1: 0.9 ~ 1: 5.5 scope.
The epoxide equivalent of epoxy resin is preferably 50 ~ 3000, is more preferably 80 ~ 2000, and then is preferably 110 ~ 1000.Should illustrate, epoxide equivalent can measure according to JIS K7236, is the quality of the resin of the epoxy radicals containing 1 equivalent.
The content of the epoxy resin in resin combination is preferably 3 quality % ~ 40 quality %, is more preferably 5 quality % ~ 35 quality %, and then is preferably 10 quality % ~ 30 quality %.From raising prepreg, the angle of the trackability of the concave-convex surface of internal layer circuit substrate is considered, the content of the liquid-state epoxy resin in resin combination is preferably 1 quality % ~ 35 quality %, be more preferably 3 quality % ~ 30 quality %, and then be preferably 6 quality % ~ 25 quality %.
-curing agent-
As curing agent, as long as have the function of epoxy resin cure, be just not particularly limited, such as phenol system curing agent, active ester system curing agent, cyanate system curing agent, benzoxazine system curing agent and acid anhydrides system curing agent can be enumerated.Curing agent can be used alone a kind, also two or more can be combinationally used.In suitable execution mode, curing agent is selected from more than a kind in phenol system curing agent, active ester system curing agent and cyanate system curing agent.
As phenol system curing agent, have no particular limits, but preferably biphenyl type curing agent, naphthalene type curing agent, novolac type curing agent, naphthylene ether type curing agent, phenol system curing agent containing triazine skeleton.Phenol system curing agent can be used alone a kind, also two or more can be combinationally used.
As the commercially available product of phenol system curing agent, biphenyl type curing agent can enumerate MEH-7700, MEH-7810, MEH-7851 (bright and change into (strain) system), naphthalene type curing agent can enumerate NHN, CBN, GPH (Japanese chemical drug (strain) system), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (Nippon Steel's chemistry (strain) system), EXB9500, HPC9500 (DIC (strain) system), novolac type curing agent can enumerate TD2090 (DIC (strain) system), naphthylene ether type curing agent can enumerate EXB-6000 (DIC (strain) system), phenol system curing agent containing triazine skeleton can enumerate LA3018, LA7052, LA7054, LA1356 (DIC (strain) system) etc.Wherein, preferably naphthalene type curing agent, phenol system curing agent containing triazine skeleton.
Active ester system curing agent has no particular limits, and usually preferably uses the ester class etc. of phenolic ester class (phenol esters), benzenethiol ester (thiophenol esters) class, N-hydroxylamine ester class, heterocycle hydroxyl compound in 1 molecule, have the compound of the high ester group of more than 2 reactivities.This active ester system curing agent preferably by carboxylic acid compound and/or thiocarboxylic acid compound and hydroxy compounds and/or mercaptan compound condensation reaction and obtain.From the viewpoint of raising thermal endurance, the active ester system curing agent particularly preferably obtained by carboxylic acid compound and hydroxy compounds.More preferably the active ester system curing agent obtained by carboxylic acid compound and oxybenzene compound and/or naphthol compound.As carboxylic acid compound, can enumerate such as: benzoic acid, acetic acid, butanedioic acid, maleic acid, itaconic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), Pyromellitic Acid etc.As oxybenzene compound or naphthol compound, can enumerate such as: quinhydrones, resorcinol, bisphenol-A, Bisphenol F, bisphenol S, phenolphthalin, methylate bisphenol-A, methylate Bisphenol F, methylate bisphenol S, phenol, orthoresol, metacresol, paracresol, catechol, alpha-Naphthol, betanaphthol, 1, 5-dihydroxy naphthlene, 1, 6-dihydroxy naphthlene, 2, 6-dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol (benzenetriol), dicyclopentadiene-type biphenol, linear phenol-aldehyde resin (phenol novolac) etc.
As active ester system curing agent; the active ester system curing agent etc. of the active ester system curing agent preferably containing dicyclopentadiene-type biphenol structure, the active ester system curing agent containing naphthalene structure, the active ester system curing agent as the acetylate of linear phenol-aldehyde resin, the benzoylate as linear phenol-aldehyde resin; wherein from the viewpoint of making the melt viscosity of prepreg reduce, make to improve the trackability of the concave-convex surface of internal layer circuit substrate, the active ester system curing agent more preferably containing dicyclopentadiene-type biphenol structure.Should illustrate, in the present invention, " dicyclopentadiene-type biphenol structure " represents the divalent construction unit comprising phenylene-two ring pentalene (ジ シ Network ロ ペ Application タ レ Application)-phenylene.Active ester system curing agent can be used alone a kind, also two or more can be combinationally used.
As the commercially available product of active ester system curing agent, active ester system curing agent containing dicyclopentadiene-type biphenol structure can enumerate EXB9451, EXB9460, EXB9460S-65T, HPC8000-65T (DIC (strain) system), active ester system curing agent as the acetylate of linear phenol-aldehyde resin can enumerate DC808 (Mitsubishi Chemical's (strain) system), active ester system curing agent as the benzoylate of linear phenol-aldehyde resin can enumerate YLH1026 (Mitsubishi Chemical's (strain) system), YLH1030 (Mitsubishi Chemical's (strain) system), YLH1048 (Mitsubishi Chemical's (strain) system) etc.
As cyanate system curing agent, have no particular limits, such as novalac-type (ノ ボ ラ ッ Network type) (novalac-type, alkyl novalac-type etc.) cyanate system curing agent, dicyclopentadiene-type cyanate system curing agent, bisphenol type (bisphenol A-type, bisphenol-f type, bisphenol S type etc.) cyanate system curing agent and their prepolymer etc. that with a portion of triazine can be enumerated.The weight average molecular weight of cyanate system curing agent is not particularly limited, and is preferably 500 ~ 4500, is more preferably 600 ~ 3000.
As the concrete example of cyanate system curing agent, such as bisphenol A dicyanate can be enumerated, polyphenol cyanate (oligomeric (3-methylene-1, 5-phenylenecyanate)), 4, 4'-di-2-ethylhexylphosphine oxide (2, 6-3,5-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluoro bisphenol-a dicyanate, 2, two (4-cyanate) phenyl-propane of 2-, 1, 1-two (4-cyanate phenylmethane), two (4-cyanate-3, 5-3,5-dimethylphenyl) methane, 1, two (4-cyanate phenyl-1-(methyl the ethylidene)) benzene of 3-, two (4-cyanate phenyl) thioether, can cyanate ester resins with two (4-cyanate phenyl) ether etc. 2 officials, by linear phenol-aldehyde resin, CF, the multifunctional cyanate ester resin that phenolic resins containing bicyclopentadiene structure etc. are derivative, a part for these cyanate ester resins is by the prepolymer etc. of triazine.Cyanate system curing agent can be used alone a kind, also two or more can be combinationally used.
As the commercially available product of cyanate system curing agent, novalac-type multifunctional cyanate ester resin can enumerate PT30 (ロ Application ザ ジ ャ パ Application (strain) system), part or all of bisphenol A dicyanate is become trimerical prepolymer and can enumerate BA230 (ロ Application ザ ジ ャ パ Application (strain) system) by triazine, the cyanate ester resin containing bicyclopentadiene structure can enumerate DT-4000, DT-7000 (ロ Application ザ ジ ャ パ Application (strain) system) etc.
As the object lesson of benzoxazine system curing agent, " HFB2006M " that Showa macromolecule (strain) makes can be enumerated, four countries change into " P-d ", " F-a " that industry (strain) is made.Benzoxazine system curing agent can be used alone a kind, also two or more can be combinationally used.
As acid anhydrides system curing agent, such as phthalic anhydride can be enumerated, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenating methyl carbic anhydride, trialkyl tetrabydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furyl (Off ラ ニ Le))-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, bibenzene tetracarboxylic dianhydride, naphthalenetetracarbacidic acidic dianhydride, hydroxyl two O-phthalic acid dianhydride, 3,3'-4,4'-diphenyl sulfone tetraformic acid dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-C] furans-1,3-diketone, ethylene glycol bis (trimellitate acid anhydride) (エ チ レ Application グ リ コ ー Le PVC ス (ア Application ヒ De ロ ト リ メ リ テ ー ト)), styrene and acid anhydrides etc. that the is maleic acid copolymerized and polymer-type such as styrene-maleic acid resin obtained.Acid anhydrides system curing agent can be used alone a kind, also two or more can be combinationally used.
When the epoxy radix of epoxy resin is preferably set to 1 by the compounding ratio of epoxy resin and curing agent, the reaction radix of curing agent is the ratio of the scope of 0.3 ~ 2.0, be more preferably the ratio of the scope of 0.3 ~ 1.5, and then be preferably the ratio of scope of 0.4 ~ 1.1.Should illustrate, the epoxy radix of epoxy resin refers to, for whole epoxy resin, carries out amounting to and the value obtained divided by the value of epoxide equivalent gained by by the solid constituent quality of each epoxy resin; The reaction radix of curing agent refers to, for whole curing agent, carries out amounting to and the value obtained divided by the value of reactive group equivalent gained by by the solid constituent quality of each curing agent.
For the resin combination of prepreg, as required, and then the additives such as thermoplastic resin, curing accelerator, fire retardant and rubber particles can be contained.
-thermoplastic resin-
For the resin combination of prepreg, from make prepreg solidify after roughening process is carried out on surface and can be formed have appropriateness roughening face insulating barrier angle consider, can thermoplastic resin be contained.Thermoplastic resin can enumerate such as phenoxy resin, polyvinyl acetal resin, vistanex, polybutadiene, polyimide resin, polyamide-imide resin, polyethersulfone resin, polyphenylene oxide resin and polysulfone resin etc.Thermoplastic resin can be used alone a kind, also two or more can be combinationally used.
The weight average molecular weight of the polystyrene conversion of thermoplastic resin is preferably the scope of 8000 ~ 70000, is more preferably the scope of 10000 ~ 60000, and then is preferably the scope of 15000 ~ 60000, and then is more preferably the scope of 20000 ~ 60000.The weight average molecular weight of the polystyrene conversion of thermoplastic resin measures by gel permeation chromatography (GPC) method.Particularly, the weight average molecular weight of the polystyrene conversion of thermoplastic resin can use (strain) Shimadzu Seisakusho Ltd. LC-9A/RID-6A as determinator, uses Showa electrician (strain) Shodex K-800P/K-804L/K-804L processed as pillar, use chloroform as mobile phase, measure under the column temperature of 40 DEG C, use the calibration curve of polystyrene standard to calculate.
Phenoxy resin can enumerate the phenoxy resin such as with the skeleton of more than a kind be selected from bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton, bis-phenol acetophenone skeleton, linear phenol-aldehyde resin skeleton, biphenyl backbone, fluorene skeleton, bicyclopentadiene skeleton, norborene skeleton, naphthalene skeleton, anthracene skeleton, adamantane framework, terpenes skeleton and trimethyl-cyclohexane skeleton.The end of phenoxy resin can be the functional group arbitrarily such as phenolic hydroxyl group, epoxy radicals.Phenoxy resin can be used alone a kind or two or more combinationally used.As the concrete example of phenoxy resin, " 1256 " and " 4250 " (being the phenoxy resin containing bisphenol A skeleton) that Mitsubishi Chemical's (strain) makes, " YX8100 " (phenoxy resin containing bisphenol S skeleton) and " YX6954 " (phenoxy resin containing bis-phenol acetophenone skeleton) can be enumerated, other can also be enumerated Dongdu changes into " FX280 " and " FX293 " that (strain) make, Mitsubishi Chemical's (strain) makes " YL7553 ", " YL6794 ", " YL7213 ", " YL7290 " and " YL7482 " etc.
As the concrete example of polyvinyl acetal resin, electrochemical Block チ ラ ー Le 4000-2 that electrochemically industry (strain) makes can be enumerated, エ ス レ ッ Network BH series that 5000-A, 6000-C, 6000-EP, ponding chemical industry (strain) are made, BX is serial, KS is serial, BL is serial, BM is serial.
As the concrete example of polyimide resin, can enumerate " リ カ コ ー ト SN20 " and " リ カ コ ー ト PN20 " that new Japan Chemical (strain) is made.As the concrete example of polyimide resin, 2 functional hydroxyl groups's end polybutadiene can be enumerated in addition, make diisocyanate cpd and tetra-atomic acid anhydride reactant and the modified polyimide such as wire polyimides (material that Japanese Laid-Open 2006-37083 publication is recorded), polyimides (material recorded in Japanese Laid-Open 2002-12667 publication and Japanese Laid-Open 2000-319386 publication etc.) containing silicone matrix that obtains.
As the concrete example of polyamide-imide resin, can enumerate " バ イ ロ マ ッ Network ス HR11NN " and " バ イ ロ マ ッ Network ス HR16NN " that Japan's weaving (strain) makes.As the concrete example of polyamide-imide resin, the modified polyamide imide such as polyamidoimide " KS9100 ", " KS9300 " containing silicone matrix of Hitachi Chemical Industries (Ltd.) can be enumerated in addition.
As the concrete example of polyethersulfone resin, " PES5003P " that Sumitomo Chemical (strain) makes etc. can be enumerated.
As the concrete example of polysulfone resin, polysulfones " P1700 ", " P3500 " etc. that ソ Le ベ イ ア De バ Application ス ト Port リ マ ー ズ (strain) makes can be enumerated.
The content of the thermoplastic resin in resin combination is preferably 0.1 quality % ~ 60 quality %, is more preferably 0.1 quality % ~ 50 quality %, and then is preferably 0.5 quality % ~ 30 quality %, and then is more preferably 0.5 quality % ~ 10 quality %.
-curing accelerator-
From the viewpoint of the hot curing carrying out prepreg swimmingly, the resin combination for prepreg can contain curing accelerator.Curing accelerator can enumerate such as phosphorus system curing accelerator, amine system curing accelerator, imidazoles system curing accelerator, guanidine system curing accelerator etc.Curing accelerator can be used alone a kind, also two or more can be combinationally used.
The content of the curing accelerator in resin combination, when the total amount of the non-volatile component by epoxy resin and curing agent is set to 100 quality %, be preferably 0.01 quality % ~ 3 quality %, be more preferably 0.01 quality % ~ 2 quality %, and then be preferably 0.01 quality % ~ 1 quality %.
-fire retardant-
For the resin combination of prepreg, consider from the angle improving anti-flammability, can fire retardant be contained.As fire retardant, phosphorus compound, nitrogen compound, silicone flame retardant, metal hydroxides etc. that such as organic phosphorus flame retardant, organic system are nitrogenous can be enumerated.Organic phosphorus flame retardant can enumerate the HCA that three light (strain) are made, HCA-HQ, the luxuriant and rich with fragrance type phosphorus compound such as HCA-NQ, the benzoxazine compound that the HFB-2006M that Showa macromolecule (strain) is made etc. are phosphorous, the レ オ Off ォ ス 30 that monosodium glutamate Off ァ イ Application テ Network ノ (strain) makes, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, the TPPO that Bei Xing chemical industry (strain) is made, PPQ, the OP930 that Network ラ リ ア Application ト (strain) makes, the phosphate compounds such as the PX200 that large eight chemistry (strain) are made.The nitrogenous phosphorus compound of organic system can enumerate that four countries change into SPB100, the SPE100 of phosphoric ester amides compound, great mound chemistry (strain) societies such as SP670, SP703 that industry (strain) makes, (strain) lies prostrate the phosphazene compounds etc. such as the made FP-series of See pharmacy.Metal hydroxides can be enumerated the magnesium hydroxides such as UD65, UD650, the UD653 made in space portion マ テ リ ア Le ズ (strain), cling to the aluminium hydroxides etc. such as B-30, B-325, B-315, B-308, B-303, UFH-20 of industry (strain) society.Fire retardant can be used alone a kind, also two or more can be combinationally used.The content of the fire retardant in resin combination is not particularly limited, and is preferably 0.5 quality % ~ 10 quality %, is more preferably 1 quality % ~ 9 quality %.
-rubber particles-
For the resin combination of prepreg, from make prepreg solidify after roughening process is carried out on surface and can be formed have appropriateness roughening face insulating barrier angle consider, can rubber particles be contained.As rubber particles, can use such as do not dissolve in following organic solvent, with the above-mentioned also inconsistent rubber particles such as epoxy resin, curing agent and thermoplastic resin.Such rubber particles is generally prepared by making the molecular weight of rubber constituent increase to undissolved level, formation particle shape in organic solvent or resin.
Rubber particles can enumerate such as core-sheath-type rubber particles, crosslink propylene nitrile butadiene rubber particle, cross-linked styrene butadiene rubber particle, acrylic rubber particle etc.Core-sheath-type rubber particles is the rubber particles with sandwich layer and sheaths, 2 Rotating fields that such as, outer field sheaths is made up of glassy polymers, the sandwich layer of internal layer is made up of rubber-like polymer; Or the rubber particles etc. of the 3-tier architecture that outer field sheaths is made up of glassy polymers, intermediate layer is made up of rubber-like polymer, sandwich layer is made up of glassy polymers.Glassy polymeric nitride layer is such as made up of the polymer etc. of methyl methacrylate, and rubbery polymeric nitride layer is such as made up of butyl acrylate thing (butyl rubber) etc.As the concrete example of core-sheath-type rubber particles, can enumerate: ス タ Off ィ ロ イ De AC3832, AC3816N, IM-401 change 1, IM-401 changes 7-17 (ガ Application Star changes into (strain) system), メ タ Block レ Application KW-4426 (Mitsubishi レ イ ヨ Application (strain) system).As the concrete example of crosslink propylene nitrile butadiene rubber (NBR) particle, XER-91 (average grain diameter 0.5 μm, JSR (strain) make) etc. can be enumerated.As the concrete example of cross-linked styrene butadiene rubber (SBR) particle, XSK-500 (average grain diameter 0.5 μm, JSR (strain) make) etc. can be enumerated.As the concrete example of acrylic rubber particle, can enumerate: メ タ Block レ Application W300A (average grain diameter 0.1 μm), W450A (average grain diameter 0.2 μm) (Mitsubishi レ イ ヨ Application (strain) system).Rubber particles can be used alone a kind, also two or more can be combinationally used.
The average grain diameter of rubber particles is preferably the scope of 0.005 μm ~ 1 μm, is more preferably the scope of 0.2 μm ~ 0.6 μm.The average grain diameter of rubber particles can use dynamic light scattering method to measure.Such as utilize ultrasonic wave etc. to make rubber particles be evenly dispersed in suitable organic solvent, use dense system particle size analyzer (FPAR-1000; Large mound electronics (strain) system), make the particle size distribution of rubber particles with quality criteria, using its median diameter as average grain diameter, can measure thus.The content of the rubber particles in resin combination is preferably 1 quality % ~ 10 quality %, is more preferably 2 quality % ~ 5 quality %.
-other composition-
Resin combination for prepreg can coordinate other composition as required.As other composition, the such thickener such as the organic filler such as heat-curing resin, silica flour, nylon powder, fluorine powder, オ Le ベ Application, ベ Application ト Application of such as vinyl benzyl based compound, acrylic compounds, maleimide compound, blocked isocyanate compounds, silicone, fluorine system, the defoamer of high score subclass or levelling agent can be enumerated, the colouring agents etc. such as the adaptation imparting agents such as imidazoles system coupling agent, thiazole system coupling agent, triazole system coupling agent, silane series coupling agent, phthalocyanine blue, phthalocyanine green, iodine are green, dual-azo yellow, carbon black.
For prepreg resin combination can by above-mentioned each composition is suitably mixed, utilize mixing facilities (three rollers, ball mill, ball mill, sand mill etc.) or mixing plant (super mixer, planetary stirring machine etc.) to carry out mixing or mixing as required in addition to manufacture.
The manufacture method of the prepreg with carrier is not particularly limited, and can enumerate solvent method, hot melt etc., and the method being selected from more than a kind in following methods (i) ~ (iv) is suitable.
(i): resin combination do not dissolved in organic solvent but resin combination is temporarily coated with on a carrier film, being laminated to the method on fiber base material
(ii): utilize chill coating machine (ダ イ コ ー タ ー) etc. to be directly coated on fiber base material by resin combination, prepreg is formed, then the method for lamination prepreg on a carrier film
(iii): prepare and resin combination is dissolved the resin varnish obtain in organic solvent, fiber base material is immersed in resin varnish, makes it infiltrate, dry, formation prepreg, the then method of lamination prepreg on a carrier film
(iv): the direct coating resin varnish on a carrier film such as use chill coating machine, forms resin composition layer, this resin composition layer is carried out the method for lamination from the two sides of fiber base material.
When using resin varnish, organic solvent can enumerate the acid amides series solvents etc. such as carbitol class, toluene and the dimethylbenzene etc. such as the acetate esters such as ketone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether and carbitol acetate, cellosolve and the butyl carbitol such as such as acetone, methyl ethyl ketone and cyclohexanone are aromatic hydrocarbon based, dimethyl formamide, dimethylacetylamide and 1-METHYLPYRROLIDONE.Organic solvent can be used alone a kind, or two or more is combinationally used.
The drying of resin varnish can utilize the known drying means such as heating, blowing hot-air to implement.Drying condition is not particularly limited, and in the manufacture method of following multilayer printed circuit board, prepreg needs to have mobility (flow) and cementability.Therefore, when resin varnish dry, the solidification of resin combination is not importantly carried out as far as possible.On the other hand, in prepreg in large quantities residual organic solvent time, become the reason producing expansion after hardening.Therefore, carry out drying, be generally below 5 quality %, preferably below 2 quality % to make the residual organic solvent amount in prepreg.Although different according to the boiling point of the organic solvent in resin varnish, such as, when using the varnish of the organic solvent containing 30 quality % ~ 60 quality %, within 3 minutes ~ 20 minutes, be suitable 80 DEG C ~ 180 DEG C dryings usually.
The prepreg of the band carrier used in method of the present invention as described above, is formed by arranging prepreg on a carrier film.Therefore, in one embodiment, the prepreg of carrier is with to contain: carrier film and the prepreg engaged with this carrier film.In the prepreg of this band carrier, very thin resin bed can be contained between carrier film and prepreg.Therefore, in other embodiments, the prepreg of carrier is with to contain: carrier film, the very thin resin bed engaged with this carrier film and the prepreg engaged with this very thin resin bed.Wherein, very thin resin bed refer to thickness be 1 ~ 10 μm, not containing the resin bed (insulating barrier) of fiber base material.
In the prepreg of band carrier, can go up in the face face of carrier film opposition side (that is, with) not engaged with carrier film of prepreg and then diaphragm that lamination and carrier film are fitted mutually.By lamination diaphragm, the attachment on the surface of prepreg such as dust or scar can be prevented.When manufacturing multilayer printed circuit board, can use by peeling off diaphragm.
In the prepreg of band carrier, the angle of seeking the slimming of multilayer printed circuit board from making the lower thickness of insulating barrier is considered, the thickness of prepreg is preferably less than 100 μm, be more preferably less than 90 μm, and then be preferably less than 80 μm, and then be more preferably less than 70 μm, be particularly preferably less than 60 μm or less than 50 μm.Consider from the angle guaranteed as the mechanical strength desired by prepreg, the lower limit of the thickness of prepreg is preferably more than 20 μm, is more preferably more than 30 μm.
In the prepreg of band carrier, when the total quality of prepreg is set to 100 quality %, the fiber base material in prepreg and the gross mass of inorganic filling material are more than 70 quality %.As mentioned above, when the present inventor etc. find the total content height of fiber base material in prepreg and inorganic filling material, the thermal coefficient of expansion of the insulating barrier of gained can be suppressed, for comparatively low degree, to be difficult to the insulating barrier obtaining surface smoothing but then.Details is as described below, but according to the manufacture method of multilayer printed circuit board of the present invention, even if when the prepreg using the total content of fiber base material and inorganic filling material up to more than 70 quality %, the insulating barrier of surface smoothing also advantageously can be realized.
For the prepreg of band carrier, fiber base material in prepreg and inorganic filling material containing ratio (mass ratio of fiber base material/inorganic filling material), consider from the angle of the mechanical strength and slimming that realize prepreg, preferably controlling is 0.2 ~ 2.5.And then, from passing through a large amount of inorganic filling material landfill in the gap of fiber base material, and the angle that the thermal coefficient of expansion of insulating barrier can be made effectively to reduce is considered, the above-mentioned ratio that contains is more preferably less than 2.3, and then be preferably less than 2.1, and then be more preferably less than 1.9, be particularly preferably less than 1.7 or less than 1.5.In addition, from preventing the angle that the melt viscosity of resin combination raises, inorganic filling material can enter the gap of fiber base material expeditiously from considering, the above-mentioned ratio that contains is more preferably more than 0.25, and then is preferably more than 0.3, and then is more preferably more than 0.35.
For the prepreg of the band carrier used in the method for the invention, prepreg at following temperature T2 (namely, the hot pressing temperature of the step (II) in the manufacture method of multilayer printed circuit board of the present invention) time, there is the melt viscosity of 300 ~ 10000 pools.The melt viscosity of prepreg during by making temperature T2 is described scope, while advantageously can realizing having level and smooth surface, the equilibrium that is little, thickness of the difference of the thickness of centre portion and base ends is good in a substrate insulating barrier.The melt viscosity of prepreg during temperature T2, considered from entreating the angle of insulating barrier that the difference of the thickness in portion and base ends is little further in a substrate, be preferably more than 600 pools, be more preferably more than 900 pools, and then be preferably more than 1000 pools, and then be more preferably more than 1200 pools, be particularly preferably more than 1400 pools, 1600 pools are above, 1800 pools are above, 2000 pools are above, 2200 pools are above, 2400 pools are above, 2600 pools are above, 2800 pools are above or more than 3000 pools.In addition, from obtain having surface level and smooth further insulating barrier angle and prevent the angle being involved in, suppressing hole to produce of air from considering, the melt viscosity of prepreg during temperature T2 is preferably below 9000 pools, be more preferably below 8000 pools, and then be preferably below 7000 pools, and then be more preferably below 6000 pools, be particularly preferably below 5000 pools.The melt viscosity of prepreg during temperature T2 can by carrying out Measurement of Dynamic Viscoelasticity to obtain.Such as, the melt viscosity of prepreg during temperature T2 can obtain as follows: measure initial temperature 60 DEG C, programming rate 5 DEG C/min, vibration number 1Hz, degree of skewness (ひ ず body) 1deg, measure 2.5 DEG C, temperature interval condition under carry out Measurement of Dynamic Viscoelasticity, by temperature and melt viscosity drawing, read temperature T2 (DEG C) time melt viscosity.As Measurement of Dynamic Viscoelasticity device, " Rheosol-G3000 " of (strain) UBM society can be enumerated such as.
Below explain the present invention.
[manufacture method of multilayer printed circuit board]
The manufacture method of multilayer printed circuit board of the present invention comprises: the prepreg being formed with the band carrier of prepreg is on a carrier film laminated to the step on internal layer circuit substrate by (I) in the mode making prepreg and engage with internal layer circuit substrate, (II) step of smoothing by the prepreg hot pressing of the band carrier through lamination, (III) prepreg hot curing is formed the step of insulating barrier, it is characterized in that, when the total quality of prepreg is set to 100 quality %, fiber base material in prepreg and the gross mass of inorganic filling material are more than 70 quality %, the melt viscosity of the prepreg under the hot pressing temperature of step (II) is 300 ~ 10000 pools, the maximum cross-section height (Rt) on the carrier film surface of the prepreg of the band carrier after step (I) is less than 5 μm, and the laminating temperature of step (I) is set to T1 (DEG C), when the hot pressing temperature of step (II) is set to T2 (DEG C), T1 and T2 meets the relation of T2≤T1+10.
< step (I) >
In step (I), the prepreg being formed with the band carrier of prepreg is on a carrier film laminated on internal layer circuit substrate in the mode making prepreg and engage with internal layer circuit substrate.
About the prepreg of band carrier, as mentioned above.The feature of the prepreg used in the method for the invention is, when the total quality of prepreg is set to 100 quality %, fiber base material in prepreg and the gross mass of inorganic filling material are more than 70 quality %, and the melt viscosity under the hot pressing temperature of step (II) is 300 ~ 10000 pools.
In the manufacture method of multilayer printed circuit board of the present invention, " internal layer circuit substrate " refers to middle manufacture thing, it has the conductor layer (circuit conductor) having carried out pattern processing on the one or both sides of the substrates such as glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermohardening type polyphenylene oxide substrate, when manufacturing multilayer printed circuit board, insulating barrier and conductor layer to be formed further.
The thickness that the one or both sides of substrate have carried out the circuit conductor of pattern processing is not particularly limited, but consider from the angle of the slimming of multilayer printed circuit board, be preferably less than 70 μm, be more preferably less than 60 μm, and then be preferably less than 50 μm, and then be more preferably less than 40 μm, be particularly preferably less than 30 μm, less than 20 μm, less than 15 μm or less than 10 μm.The lower limit of the thickness of circuit conductor is not particularly limited, and is preferably more than 1 μm, is more preferably more than 3 μm, and then is preferably more than 5 μm.
Live width/gap ratio (ラ イ Application/ス ペ ー ス ratio) that the one or both sides of substrate have carried out the circuit conductor of pattern processing is not particularly limited, but the angle obtaining the insulating barrier of surface smoothness excellence from suppressing the fluctuating of surface of insulating layer is considered, be generally less than 900/900 μm, be preferably less than 700/700 μm, be more preferably less than 500/500 μm, and then be preferably less than 300/300 μm, and then be more preferably less than 200/200 μm.The lower limit of the live width/gap ratio of circuit conductor is not particularly limited, but in order to imbedding in making prepreg between spacing good, be preferably more than 1/1 μm.
In addition, the circuit conductor occupation rate ((area of circuit conductor part)/(surface area of internal layer circuit substrate) × 100 [%]) on the surface of internal layer circuit substrate can determine according to required characteristic.Circuit conductor occupation rate when circuit conductor copper is formed also referred to as " residual copper rate ".Circuit conductor occupation rate can in the surface distributed of internal layer circuit substrate.Such as can use the internal layer circuit substrate in the region defining and there is the 1st circuit conductor occupation rate and the region with the 2nd circuit conductor occupation rate.As general tendency, circuit conductor occupation rate is lower, and the thickness on the circuit conductor of the insulating barrier that internal layer circuit substrate is formed is thinner.Especially, the thickness for the formation of the prepreg of insulating barrier is thinner, and described tendency is more remarkable.Wherein, " thickness on the circuit conductor of insulating barrier " refers to the thickness of the insulating barrier directly over circuit conductor.In the present invention, owing to realizing at the little insulating barrier of the difference of base ends and substrate center portion thickness, though use thickness thin prepreg when, also can realize the insulating barrier of the insulating reliability desired by performance in the scope of whole substrate.Should illustrate, in the present invention, the thickness of the insulating barrier of base ends refers to the thickness on the circuit conductor of the insulating barrier of base ends, and the thickness of the insulating barrier in substrate center portion refers to the thickness on the circuit conductor of the insulating barrier in substrate center portion.
The lamination treatment of step (I) such as can by reduced pressure conditions, the mode to engage with internal layer circuit substrate with prepreg, on internal layer circuit substrate, add thermo-compressed carry out by being with the prepreg of carrier.On internal layer circuit substrate, carry out as by the prepreg of band carrier the component (hereinafter also referred to " adding thermo-compressed component ") heating crimping, can enumerate such as through metallic plate (SUS end plate etc.) or the metallic roll (SUS roller) etc. of heating.Should illustrate, preferably will not add thermo-compressed component direct weighting on the prepreg of band carrier, but pressurize via heat resistant rubber elastomeric material, with the concave-convex surface making prepreg fully follow internal layer circuit substrate.Prepreg with carrier can be laminated in the one side of internal layer circuit substrate, also can be laminated on the two sides of internal layer circuit substrate.
Heating-up temperature (hereinafter also referred to " laminating temperature ") during lamination treatment, from raising prepreg, the trackability of the concave-convex surface of internal layer circuit substrate is obtained to the angle consideration of the insulating barrier of surface smoothing, be preferably more than 60 DEG C, be more preferably more than 70 DEG C, and then be preferably more than 80 DEG C, and then be more preferably more than 90 DEG C, be particularly preferably more than 100 DEG C, more than 110 DEG C or more than 120 DEG C.In addition, from preventing oozing out of resin, the angle obtaining the good insulating barrier of the equilibrium of thickness is considered, the upper limit of laminating temperature is preferably less than 160 DEG C, is more preferably less than 150 DEG C, and then is preferably less than 140 DEG C, and then is more preferably less than 130 DEG C.Should illustrate, laminating temperature refers to the surface temperature adding thermo-compressed component, when pressurizeing via heat resistant rubber elastomeric material, refers to the temperature on the surface of this elastomeric material engaged with the prepreg with carrier.
Crimping pressure during lamination treatment, from raising prepreg, the trackability of the concave-convex surface of internal layer circuit substrate is obtained to the angle consideration of the insulating barrier of surface smoothing, be preferably more than 0.098MPa, be more preferably more than 0.29MPa, and then be preferably more than 0.40MPa, and then be more preferably more than 0.49MPa.In addition, from the viewpoint of the insulating barrier preventing the equilibrium of oozing out, obtaining thickness of resin good, crimping upper limit of pressure is preferably below 1.77MPa, is more preferably below 1.47MPa, and then is preferably below 1.10MPa.
Crimping time during lamination treatment, from the viewpoint of the concave-convex surface making prepreg fully follow internal layer circuit substrate, be preferably more than 10 seconds, be more preferably more than 15 seconds, and then be preferably more than 20 seconds, and then be more preferably more than 25 seconds.In addition, consider from productive viewpoint, the upper limit of crimping time is preferably less than 300 seconds, is more preferably less than 250 seconds, and then is preferably less than 200 seconds, and then is more preferably less than 150 seconds, is particularly preferably less than 100 seconds or less than 50 seconds.
Vacuum degree during lamination treatment, from the viewpoint of effectively implementing lamination treatment, is preferably more than 0.01hPa, is more preferably more than 0.05hPa, and then be preferably more than 0.1hPa.In addition, produce from the viewpoint of the viewpoint of the insulating barrier obtaining surface smoothing with the intrusion preventing air to insulating barrier, suppression hole, the upper limit of vacuum degree is preferably below 27hPa, is more preferably below 22hPa, and then be preferably below 17hPa, and then be more preferably below 13hPa.Should illustrate, produce from the viewpoint of suppression hole, the pumpdown time is preferably more than 20 seconds, is more preferably more than 30 seconds, more than 40 seconds, more than 50 seconds or more than 60 seconds.
Utilize step (I), can obtain containing internal layer circuit substrate and the duplexer of the prepreg of band carrier that arranges in the mode that prepreg engages with this internal layer circuit substrate.In the present invention, in order to obtain the insulating barrier of surface smoothness excellence, importantly implementation step (I), is less than 5 μm to make the maximum cross-section height (Rt) on the carrier film surface of the prepreg of the band carrier after step (I).Such as according to the prepreg of use and composition, the kind of carrier film, operate the lamination treatment condition such as above-mentioned laminating temperature, crimping pressure, crimping time, vacuum degree, implementation step (I), is less than 5 μm to make the maximum cross-section height (Rt) on carrier film surface.
Consider from the angle of the insulating barrier obtaining surface smoothness excellence, the maximum cross-section height (Rt) on the carrier film surface of the prepreg of the band carrier after step (I) is preferably less than 4.5 μm, be more preferably less than 4 μm, and then be preferably less than 3.5 μm.The lower limit of this maximum cross-section height (Rt) is not particularly limited, but from preventing oozing out of resin, and the angle obtaining the good insulating barrier of the equilibrium of thickness is considered, is generally more than 0.1 μm.
The maximum cross-section height (Rt) on carrier film surface can use non-contact type surface roughness meter to measure.As the object lesson of non-contact type surface roughness meter, " the WYKO NT9300 " of ビ ー コ イ Application ス Star Le メ Application Star can be enumerated.
Should illustrate, as long as peel off before the insulating barrier that carrier film obtains making prepreg solidify arranges the step of conductor layer (circuit layout), such as can peel off between following step (II) and step (III), also can peel off after following step (III).In suitable execution mode, carrier film is peeled off after following step (III).Carrier film can, with manually peeling off, also can utilize automatic stripper to carry out mechanical stripping.
The lamination treatment of step (I) can utilize commercially available vacuum laminator to carry out.As commercially available vacuum laminator, the vacuum pack system device etc. that (strain) name mechanism makes made vacuum pressure type laminating machine, ニ チ ゴ ー モ ー ト Application (strain) makes can be enumerated such as.
< step (II) >
In step (II), smoothingization by the prepreg hot pressing of the band carrier through lamination.
Smoothing techniques in step (II) is such as implemented from the pressurization of carrier film side by adding thermo-compressed component.As adding thermo-compressed component, can use with the component illustrated in step (I) is same component.
During obtaining surface smoothness excellence, at the insulating barrier that the difference equilibrium that is little, thickness of base ends and substrate center portion thickness is good, the hot pressing temperature of step (II) is importantly made to be the scope of regulation.In detail, when making that the laminating temperature of step (I) is T1 (DEG C), the hot pressing temperature of step (II) is T2 (DEG C), importantly T2 is set, with the relation making T1 and T2 meet T2≤T1+10.Consider from the angle obtaining the more excellent insulating barrier of both surface smoothness and thickness equilibrium, T1 and T2 preferably meets the relation of T2≤T1+5, more preferably meets the relation of T2≤T1.As long as meet described with the relational expression of T1 and the melt viscosity of the prepreg under T2 is above-mentioned specific scope, T2 is just not particularly limited, but its lower limit is 70 DEG C usually, and its upper limit is 160 DEG C.Should illustrate, the hot pressing temperature of step (II) refers to the surface temperature adding thermo-compressed component, when pressurizeing via heat resistant rubber elastomeric material, refers to the temperature on the surface of this elastomeric material engaged with the prepreg with carrier.
Crimping pressure during smoothing techniques and crimping time can be same with the lamination treatment condition in step (I).In addition, smoothing techniques is applicable to (under atmospheric pressure) enforcement at ambient pressure.
The smoothing techniques of step (II) can implement 1 time, also can implement more than 2 times.When being implemented by smoothing techniques more than 2 times, more than 2 times can be implemented under the same conditions, also can implement more than 2 times under different conditions.Such as, when the smoothing techniques of step (II) being implemented 2 times, when the hot pressing temperature in the smoothing techniques of the 1st time being set to the hot pressing temperature in T2 (DEG C), the smoothing techniques of the 2nd time and being set to T3 (DEG C), T2 and T3 preferably meets the relation of T2-30≤T3≤T2+20, more preferably meets the relation of T2-20≤T3≤T2+10.
The smoothing techniques of step (II) can utilize commercially available laminating machine to carry out.Should illustrate, step (I) and step (II) can use above-mentioned commercially available vacuum laminator to carry out continuously.Such as can use the vacuum laminator possessing Room the 1st of lamination treatment and Room the 2nd of smoothing techniques, continuously implementation step (I) and step (II).When the smoothing techniques of step (II) is implemented more than 2 times, the smoothing techniques of more than 2 times repeatedly can be implemented in above-mentioned Room 2nd, maybe can using and then possess the vacuum laminator of the room (such as Room the 3rd, Room the 4th) for implementing the 2nd later smoothing techniques, implementing the smoothing techniques of more than 2 times.
< step (III) >
In step (III), prepreg hot curing is formed insulating barrier.
The condition of hot curing is not particularly limited, the condition usually adopted when can be used in the insulating barrier forming multilayer printed circuit board.
Such as, the hot curing condition of prepreg is different according to composition of resin combination used in prepreg etc., curing temperature can be made to be that the scope of 120 DEG C ~ 240 DEG C (is preferably the scope of 150 DEG C ~ 210 DEG C, be more preferably the scope of 170 DEG C ~ 190 DEG C), make be the scope (preferably 10 minutes ~ 75 minutes, be more preferably 15 minutes ~ 60 minutes) of 5 minutes ~ 90 minutes curing time.
Before carrying out hot curing, prepreg can be preheated at the temperature lower than curing temperature.Such as before hot curing, 120 DEG C of (preferably more than 60 DEG C and less than 110 DEG C can be less than more than 50 DEG C, be more preferably more than 70 DEG C and less than 100 DEG C) temperature under, prepreg is carried out preheating of more than 5 minutes (preferably 5 minutes ~ 150 minutes, be more preferably 15 minutes ~ 120 minutes).Under carrying out pre-warmed situation, described in preheat and be also contained in step (III).
The hot curing preferred under atmospheric pressure (under normal pressure) of the prepreg in step (III) is carried out.
The hot curing of step (III) can use heating furnace to implement.When using heating furnace to implement the hot curing of prepreg, prepreg is configured with plumbness in heating furnace, carry out hot curing and form insulating barrier, can disposable a large amount of numbers be put in heating furnace thus, to carry out operation smoothly from step (II) to the continuation mode of step (III), productivity can be contributed to and improves.As heating furnace, such as cleaning oven (ヤ マ ト science (strain) makes " Network リ ー Application オ ー Block Application DE610 ") etc. can be used.
Utilize step (III), can obtain containing internal layer circuit substrate and the duplexer of insulating barrier that engages with this internal layer circuit substrate.As mentioned above, during the prepreg using the total content of fiber base material and inorganic filling material high, the thermal coefficient of expansion of gained insulating barrier can be suppressed for low degree, on the other hand, the surface of the insulating barrier of gained has the fluctuating corresponding with the concave-convex surface of the internal layer circuit substrate as ground, is difficult to the insulating barrier obtaining surface smoothing.If the fluctuating of surface of insulating layer is large, then, when forming conductor layer with fine Wiring pattern on this surface of insulating layer, there is the situation becoming obstacle.By the hot pressing temperature in smoothing step being set as higher degree etc., the mobility of resin carries out hot pressing under uprising such condition, how much can improve the surface smoothness of insulating barrier, but under these circumstances, due to oozing out of resin, cause the disturbance of equilibrium of the thickness of insulating barrier, centre portion and base ends in a substrate, the thickness of rewarding insulating barrier produces the tendency of large difference.According to the tendency in recent years also obtaining with the slimming of multilayer printed circuit board, the slimming of insulating barrier being in progress, the bad reduction sometimes ascribing the insulating reliability of local to of the equilibrium of described thickness.Relative to this, according to the manufacture method of multilayer printed circuit board of the present invention, even if use the prepreg that the total content of fiber base material and inorganic filling material is high, the flatness that also can form surface excellent and the difference of base ends and substrate center portion thickness little, insulating barrier that the equilibrium of thickness is also good.Therefore the present invention is when using prepreg that the total content of fiber base material and inorganic filling material is high to manufacture multilayer printed circuit board, significantly contributes to the fine distribution of multilayer printed circuit board and the invention both slimming.The feature of the multilayer printed circuit board of method manufacture of the present invention is utilized to be, containing insulating barrier, this insulating barrier be high, the surperficial maximum cross-section height (Rt) of the total content of fiber base material and inorganic filling material low, at base ends and the little insulating barrier of substrate center portion difference in thickness.The details of the maximum cross-section height (Rt) on the surface of insulating barrier, the base ends of insulating barrier and the difference in thickness in substrate center portion is as described below.In one embodiment, the feature of this multilayer printed circuit board is, the insulating barrier of condition containing meeting following (a) to (c): when the total quality of this insulating barrier is set to 100 quality % by (a), the gross mass of fiber base material and inorganic filling material is more than 70 quality %; B the maximum cross-section height (Rt) on the surface of () this insulating barrier is less than 3 μm; (c) difference of the thickness of the base ends of this insulating barrier and the thickness in substrate center portion is less than 2.5 μm.
The maximum cross-section height (Rt) of the surface of insulating layer after step (III) is considered from the angle that can form conductor layer at this surface of insulating layer with fine Wiring pattern, preferably be less than 3 μm, be more preferably less than 2.8 μm, and then be preferably less than 2.6 μm, and then be more preferably less than 2.5 μm.The lower limit of this maximum cross-section height (Rt) is not particularly limited, and is generally 0.1 μm with first-class.
The maximum cross-section height (Rt) of surface of insulating layer, can measure for the exposing surface of the insulating barrier after stripping carrier film, use non-contact type surface roughness meter.
The difference of the thickness of the thickness of insulating barrier after step (III), base ends and the insulating barrier in substrate center portion, the angle of the insulating reliability needed for realizing from the scope at whole substrate is considered, preferably be less than 2.5 μm, be more preferably less than 2.4 μm, and then be preferably less than 2.2 μm, and then be more preferably less than 2.0 μm, be particularly preferably less than 1.8 μm or less than 1.6 μm.The lower limit of the difference of the thickness of the thickness of the insulating barrier of base ends and the insulating barrier in substrate center portion is not particularly limited, and can be 0 μm.In the present invention, due to the insulating barrier that the difference that can be formed in base ends and substrate center portion thickness is like this little, even the situation that therefore insulating barrier is thin, the insulating reliability needed for also can realizing in the scope of whole substrate.
The difference of the thickness of the thickness of the insulating barrier of base ends and the insulating barrier in substrate center portion, for the central portion of duplexer of gained in step (III) and each cross section of end, the thickness of the insulating barrier directly over measurement microscope circuit conductor can be used and calculates.As microscopical object lesson, can enumerate " microscope VK-8510 " that KEYENCE (strain) makes.
Other step > of <
The manufacture method of multilayer printed circuit board of the present invention can and then comprise: (IV) this insulating barrier is carried out the step of roughening process by the step of perforate, (V) on the insulating layer, (VI) utilize plating on the surface of insulating layer through roughening, form the step of conductor layer.These steps (IV) to (VI) can according to use in the manufacture of multilayer printed circuit board, well known to a person skilled in the art that various method is implemented.Should illustrate, when peeling off carrier film after step (III), the stripping of this carrier film can be implemented between step (III) and step (IV) or between step (IV) and step (V).
Step (IV) is the step of perforate on the insulating layer, can form through hole etc. on the insulating layer thus.Through hole is set up in order to the electrical connection of interlayer, considers the characteristic of insulating barrier, can be formed by the known method employing drill bit, laser, plasma etc.Such as, when there is carrier film, from irradiating laser carrier film, and through hole can be formed at insulating barrier.
As laser light source, such as carbon dioxide laser, YAG laser, excimer laser etc. can be enumerated.Wherein, consider from the angle of process velocity, cost, preferably carbon dioxide laser.
Perforate processing can use commercially available laser device to implement.As commercially available carbon dioxide laser device, LC-2E21B/1C that such as Hitachi's PVC ア メ カ ニ Network ス (strain) makes can be enumerated, ML605GTWII that Mitsubishi Electric's (strain) makes, Panasonic weld the substrate perforate laser machine that シ ス テ system (strain) makes.
Step (V) is the step of insulating barrier being carried out roughening process.Operation, the condition of roughening process are not particularly limited, and can adopt normally used known operation, condition when forming the insulating barrier of multilayer printed circuit board.Such as can implement to make use of the swelling process of swelling liquid successively, make use of the roughening process of oxidant, make use of the neutralisation treatment of neutralizer, and insulating barrier is carried out roughening process.As swelling liquid, be not particularly limited, can enumerate aqueous slkali, surfactant solution etc., preferably aqueous slkali, this aqueous slkali is more preferably sodium hydroxide solution, potassium hydroxide solution.As commercially available swelling liquid, ス ウ ェ リ Application グ デ ィ ッ プ セ キ ュ リ ガ Application ス P, ス ウ ェ リ Application グ デ ィ ッ プ セ キ ュ リ ガ Application ス SBU etc. that such as ア ト テ ッ Network ジ ャ パ Application (strain) is made can be enumerated.The swelling process that make use of swelling liquid is not particularly limited, such as can by insulating barrier being flooded 1 minute ~ 20 minutes to carry out in the swelling liquid of 30 ~ 90 DEG C.Suppress, for the angle of suitable level is considered, in the swelling liquid of 40 ~ 80 DEG C, preferably to make insulating barrier flood 5 seconds ~ 15 minutes from the swelling of the resin by insulating barrier.Oxidant is not particularly limited, and can enumerate the alkaline permanganic acid solution such as having dissolved potassium permanganate, sodium permanganate in the aqueous solution of NaOH.The roughening process that make use of the oxidants such as alkaline permanganic acid solution is being heated to flood in the oxidizing agent solution of 60 DEG C ~ 80 DEG C carry out for 10 minutes ~ 30 minutes preferably by making insulating barrier.In addition, the concentration of the permanganate in alkaline permanganic acid solution is preferably 5 quality % ~ 10 quality %.As commercially available oxidant, the alkaline permanganic acid solutions such as the コ Application セ Application ト レ ー ト コ Application パ Network ト P, ド ー ジ Application グ ソ リ ュ ー シ ョ Application セ キ ュ リ ガ Application ス P that such as ア ト テ ッ Network ジ ャ パ Application (strain) makes can be enumerated.In addition, as neutralizer, the preferably acid aqueous solution, as commercially available product, can enumerate the リ ダ Network シ ョ Application ソ リ ュ ー シ ョ Application セ キ ュ リ ガ Application ト P that such as ア ト テ ッ Network ジ ャ パ Application (strain) is made.The process that make use of neutralizer can be carried out by making the treated side utilizing oxidizing agent solution to carry out roughening process flood in the neutralizer of 30 ~ 80 DEG C for 5 minutes ~ 30 minutes.From the viewpoint of operability etc., the object preferably will oxidizing agent solution being utilized to have carried out roughening process, floods the method for 5 minutes ~ 20 minutes in the neutralizer of 40 ~ 70 DEG C.
Step (VI) is the step utilizing plating to form conductor layer on the surface of insulating layer through roughening.
The conductor material used in conductor layer is not particularly limited.In suitable execution mode, conductor layer contains the metal of more than a kind of being selected from 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, can enumerate the layer such as formed by the alloy (such as nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) of the metal of more than two kinds being selected from above-mentioned metal.Wherein, from conductor layer formed versatility, cost, patterning easiness angularly consider, be preferably the alloy-layer of the single metal layer of chromium, nickel, titanium, aluminium, zinc, gold, palladium, silver or copper or nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy, be more preferably the single metal layer of chromium, nickel, titanium, aluminium, zinc, gold, palladium, silver or copper or the alloy-layer of nickel-chromium alloy, and then be preferably the single metal layer of copper.
Conductor layer can be single layer structure, also can be the single metal layer comprising different types of metal or alloy of more than 2 layers or alloy-layer lamination and the sandwich construction obtained.When conductor layer is sandwich construction, the layer connected with insulating barrier is preferably the single metal layer of chromium, zinc or titanium or the alloy-layer of nickel-chromium alloy.
The thickness dependence of conductor layer in the design of required multilayer printed circuit board, but is generally 3 μm ~ 35 μm, is preferably 5 μm ~ 30 μm.
Conductor layer can utilize plating to be formed.The known technology such as semi-additive process, full additive method such as can be utilized to carry out plating on the surface of insulating barrier, form the conductor layer with required Wiring pattern.Below, the example utilizing semi-additive process to form conductor layer is shown.
First, utilize non-electrolytic plating to form plating layer (め っ I シ ー De Layer) on the surface of insulating barrier.Then, on the plating layer formed, corresponding to required Wiring pattern, the mask pattern that a part for plating layer is exposed is formed.On the plating layer exposed, after utilizing plating to form metal level, removing mask pattern.Then, utilize etching to wait the unwanted plating layer of removing, the conductor layer with required Wiring pattern can be formed.In the manufacture method of multilayer printed circuit board of the present invention, the insulating barrier of surface smoothness excellence can be formed, therefore, it is possible to form conductor layer with fine Wiring pattern on which insulating layer.
By using the multilayer printed circuit board utilizing method of the present invention to manufacture, semiconductor device can be manufactured.By the conducting position mounting semiconductor chip at multilayer printed circuit board of the present invention, semiconductor device can be manufactured." conducting position " refers to " position of the signal of telecommunication in conduction multilayer printed circuit board ", and this position can be any one of the position of surface or landfill.In addition, as long as semiconductor chip take semiconductor as the electrical circuit components of material, be not particularly limited.
As long as the installation method of semiconductor chip when manufacturing semiconductor device of the present invention makes semiconductor chip effectively play function, be not particularly limited, particularly, wire-bonded installation method, flip-chip installation method, the installation method utilizing bumpless build up layer (バ Le プ な PVC Le De ア ッ プ Layer, BBUL), the installation method etc. that utilizes the installation method of anisotropic conductive film (ACF), utilize non-conductive film (NCF) can be enumerated.
Embodiment
Below, based on embodiment and comparative example, further illustrate the present invention, but the present invention is not limited to following embodiment.Should illustrate, " part " in below recording refers to " mass parts ".
First, the assay method in the evaluation of physical property of this specification, evaluation method are described.
(preparation of mensuration, evaluation substrate)
(1) making of internal layer circuit substrate
At the upper pattern (live width/gap ratio=600/660 μm comb pattern (residual copper rate 48%)) forming IPC MULTI-PURPOSE TEST BOARD NO. IPC C-25 of the copper foil covered lamination in glass cloth base material epoxy resin two sides (thickness 35 μm of Copper Foil, the thickness 0.8mm of substrate, SUNX (strain) system " R5715ES ").Then, the two sides micro-etching agent (メ ッ Network (strain) system " CZ8100 ") of substrate is carried out roughening process, makes internal layer circuit substrate.
Should illustrate, about embodiment 4, use the copper foil covered lamination in the glass cloth base material epoxy resin two sides thickness of Copper Foil being changed into 7 μm.
(2) lamination of the prepreg of carrier is with
Use the laminating machine (name machine (strain) system " MVLP500/600-IIB ") with 2 Room pressurizations, by the mode that the prepreg of the band carrier made in following production example engages with internal layer circuit substrate to make prepreg, be laminated on the two sides of internal layer circuit substrate.Lamination treatment by decompression 30 seconds after making air pressure be below 13hPa, makes it crimp 30 seconds under the laminating temperature T1 (DEG C) shown in table 2 and the condition of pressure 0.74MPa and carries out.Should illustrate, be laminated in the Room the 1st with the laminating machine of 2 Room pressurizations and implement.
(3) smoothing of the prepreg of carrier is with
The prepreg of the band carrier through lamination is carried out hot pressing and smoothing in Room the 2nd of the above-mentioned laminating machine with 2 Room pressurizations.Make it crimp 90 seconds under the condition of smoothing techniques by the hot pressing temperature T2 (DEG C) under atmospheric pressure (normal pressure), shown in table 2 and pressure 0.55MPa to carry out.
Should illustrate, for embodiment 7, in Room the 2nd of the above-mentioned laminating machine with 2 Room pressurizations, implement 2 smoothing techniques.Make it crimp 90 seconds under the smoothing techniques of the 1st time condition by the hot pressing temperature T2 (DEG C) under atmospheric pressure (normal pressure), shown in table 2 and pressure 0.55MPa to carry out.Make it crimp 90 seconds under the smoothing techniques of the 2nd time condition by the hot pressing temperature T3 (DEG C) under atmospheric pressure (normal pressure), shown in table 2 and pressure 0.55MPa to carry out.
(4) hot curing of prepreg
After smoothing, by substrate 180 DEG C of heating 30 minutes, prepreg hot curing is formed insulating barrier.
The mensuration > of the melt viscosity of < prepreg
20 overlaps are formed the thick prepreg of 1mm and is punched to diameter 20mm, formation determination sample.For the working sample of preparation, Measurement of Dynamic Viscoelasticity device ((strain) UBM system " Rheogel-G3000 ") is used to measure melt viscosity.Under the condition determination of programming rate 5 DEG C/min, mensuration 2.5 DEG C, temperature interval, vibration frequency 1Hz, measure dynamic viscoelastic rate, try to achieve the melt viscosity (pool) during temperature T2 (DEG C) shown in table 2.Cone-plate is used in the fixture measured.
The mensuration > of the maximum cross-section height (Rt) on the carrier film surface after < lamination step
The prepreg of band carrier is pressed in after on internal layer circuit substrate, cuts out the evaluation substrate of 200mm × 200mm, measure the maximum cross-section height (Rt) on the carrier film surface of the prepreg of band carrier.The maximum cross-section height (Rt) on carrier film surface utilizes following numerical value to try to achieve, described numerical value uses non-contact type surface roughness meter (PVC ー コ イ Application ス ツルメン Star society's system " WYKO NT9300 "), utilize VSI contact mode, 10 times of lens, make measurement range be the numerical value that 0.82mm × 1.1mm obtains.Mensuration is be attached to the state on prepreg in carrier film under, carry out for the exposing surface of carrier film.
The mensuration > of the maximum cross-section height (Rt) of < surface of insulating layer
After prepreg is carried out hot curing, the demoulding PET film as carrier film is peeled off, for the exposing surface of insulating barrier, measure maximum cross-section height (Rt).The maximum cross-section height (Rt) of surface of insulating layer utilizes following numerical value to try to achieve, described numerical value uses non-contact type surface roughness meter (PVC ー コ イ Application ス ツルメン Star society's system " WYKO NT9300 "), utilize VSI contact mode, 10 times of lens, make measurement range be the numerical value that 0.82mm × 1.1mm obtains.Should illustrate, be determined as follows and state such enforcement: for the region of circuit layout of comb pattern (residual copper rate 48%) being provided with live width/gap ratio=600/660 μm, to cross over the part with circuit layout and the mode not having the part of circuit layout such, try to achieve the mean value at 3 places.
In table 2, situation Rt being less than 2.5 μm is set to "○", Rt is more than 2.5 μm and the situation being less than 3 μm is set to " △ ", is that the situation of more than 3 μm is set to "×" by Rt.Should illustrate, for comparative example 1,3 and 5, produce fold due to the generation of the fluctuating of the concave-convex surface based on internal layer circuit substrate, therefore omit the mensuration of maximum cross-section height (Rt).In addition, about comparative example 6, owing to producing hole, therefore omit the mensuration of maximum cross-section height (Rt).
The evaluation > of the outward appearance of < surface of insulating layer
After prepreg hot curing, the demoulding PET film as carrier film is peeled off, for the exposing surface of insulating barrier, observe outward appearance.For the outward appearance of surface of insulating layer, microscope (KEYENCE (strain) makes " microscope VK-8510 ") is used to observe the surperficial 3cm of insulating barrier 2.
In table 2, by not having the situation of fold or hole to be denoted as " 〇 ", the situation with fold or hole is denoted as "×".
The mensuration > of the difference of the thickness of the insulating barrier in < base ends and substrate center portion
After prepreg hot curing, the demoulding PET film as carrier film is peeled off, measure the difference of the thickness of the insulating barrier in base ends and substrate center portion.In detail, for each region (1cm in base ends and substrate center portion 2), after making cross section smoothing by grinding, use microscope (KEYENCE (strain) makes " microscope VK-8510 ") to measure the thickness of the insulating barrier directly over circuit conductor.
In table 2, the situation that the difference of the thickness of the insulating barrier in base ends and substrate center portion is less than 2.5 μm is denoted as " 〇 ", the situation for more than 2.5 μm is denoted as "×".
(production example 1)
(1) preparation of resin varnish
Stir while make liquid bisphenol A type epoxy resin (epoxide equivalent 180, Mitsubishi Chemical's (strain) system " jER828EL ") 15 parts, naphthalene type 4 functional epoxy resins (epoxide equivalent 163, DIC (strain) makes " HP4710 ") 25 parts, naphthylene ether type epoxy (epoxide equivalent 213, DIC (strain) makes " EXA-7311G4 ") 45 parts, with phenoxy resin (ジ ャ パ Application エ Port キ シ レ ジ Application (strain) makes " YL7553BH30 ") 8 parts of heating for dissolving in the mixed solvent of MEK30 part and cyclohexanone 30 parts.Mixing is containing the phenol system curing agent (hydroxyl equivalent 125 of triazine skeleton wherein, DIC (strain) makes " LA7054 ", nitrogen content about 12 quality %) the MEK solution 10 parts of solid constituent 60 quality %, (functional equivalent 153 for naphthalene type curing agent, DIC (strain) makes " HPC9500 ") the MEK solution 40 parts of solid constituent 60 % by weight, fire retardant (hydroxyl equivalent 162, (strain) three light system " HCA-HQ ", phosphorus content 9.5%) 8 parts, surface-treated spherical silicon dioxide (average grain diameter 1.0 μm has been carried out with amino silicone methane series coupling agent (Shin-Etsu Chemial Co., Ltd's system " KBM-573 "), (strain) ア De マ テ ッ Network ス system " SOC4 ") 250 parts, High Rotation Speed blender is utilized to disperse equably, prepare resin varnish.
(2) preparation of the prepreg 1 of carrier is with
The resin varnish obtained in above-mentioned (1) is infiltrated in fiber base material ((strain) has pool to make made 1027 glass cloth, thickness 19 μm), utilizes clothes closet type drying oven 110 DEG C of dryings 5 minutes, prepare prepreg.Resin composition content in prepreg is 81 quality %, the thickness of prepreg is 50 μm.Then, use batch-type vacuum pressed laminating machine ((strain) name mechanism is done made " MVLP-500 "), PET film (リ Application テ ッ Network (strain) makes " PET501010 ", thickness 38 μm) with release layer is laminated on the two sides of prepreg in the mode making release layer contact with prepreg, forms the prepreg 1 of band carrier.In the prepreg 1 of band carrier, the fiber base material in prepreg and the total content of inorganic filling material are 72 quality %.When making evaluation substrate, the PET film with release layer (diaphragm) of a side being peeled off and uses.
(production example 2)
(1) preparation of resin varnish
Resin varnish is prepared in the same manner as production example 1.
(2) preparation of the prepreg 2 of carrier is with
Except using fiber base material ((strain) has pool to make made 1000 glass cloth, thickness 14 μm) to replace except fiber base material ((strain) has pool to make made 1027 glass cloth, thickness 19 μm), other prepares the prepreg 2 being with carrier by the operation same with production example 1.Resin composition content in prepreg is 80 quality %, and the thickness of prepreg is 33 μm.In addition, in the prepreg 2 of band carrier, the fiber base material in prepreg and the total content of inorganic filling material are 72 quality %.
(production example 3)
(1) preparation of resin varnish
Stir while make liquid bisphenol A type epoxy resin (epoxide equivalent 180, Mitsubishi Chemical's (strain) system " jER828EL ") 15 parts, naphthylene ether type epoxy (epoxide equivalent 213, DIC (strain) make " EXA-7311G4 ") 80 parts and phenoxy resin (ジ ャ パ Application エ Port キ シ レ ジ Application (strain) makes " YL7553BH30 ") 8 parts of heating for dissolving in the mixed solvent of MEK20 part and cyclohexanone 20 parts.Mixing is containing the phenolic resins (hydroxyl equivalent 125 of triazine skeleton wherein, DIC (strain) makes " LA7054 ", nitrogen content about 12 % by weight) the MEK solution 10 parts of solid constituent 60 % by weight, (functional equivalent 215 for naphthalene type curing agent, Nippon Steel's (strain) system " SN485 ") the MEK solution 40 parts of solid constituent 60 % by weight, fire retardant (hydroxyl equivalent 162, (strain) three light system " HCA-HQ ", phosphorus content 9.5%) 8 parts, surface-treated preparing spherical SiO 2 (average grain diameter 1.0 μm has been carried out with amino silicone methane series coupling agent (Shin-Etsu Chemial Co., Ltd's system " KBM-573 "), (strain) ア De マ テ ッ Network ス system " SOC4 ") 240 parts, disperse equably with High Rotation Speed blender, prepare resin varnish.
(2) preparation of the prepreg 3 of carrier is with
Use the resin varnish obtained in above-mentioned (1), prepare the prepreg 3 being with carrier by the operation same with production example 1.Resin composition content in prepreg is 81 quality %, and the thickness of prepreg is 50 μm.In addition, in the prepreg 3 of band carrier, the fiber base material in prepreg and the total content of inorganic filling material are 71 quality %.
[table 1]
。
< embodiment 1 >
Use the prepreg 1 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 140 DEG C, and hot pressing temperature T2 is 140 DEG C.Each evaluation result is shown in table 2.
< embodiment 2 >
Use the prepreg 1 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 140 DEG C, and hot pressing temperature T2 is 120 DEG C.Each evaluation result is shown in table 2.
< embodiment 3 >
Use the prepreg 1 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 120 DEG C, and hot pressing temperature T2 is 120 DEG C.Each evaluation result is shown in table 2.
< embodiment 4 >
Use the prepreg 2 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 140 DEG C, and hot pressing temperature T2 is 120 DEG C.Each evaluation result is shown in table 2.
< embodiment 5 >
Use the prepreg 1 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 130 DEG C, and hot pressing temperature T2 is 110 DEG C.Each evaluation result is shown in table 2.
< embodiment 6 >
Use the prepreg 3 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 130 DEG C, and hot pressing temperature T2 is 110 DEG C.Each evaluation result is shown in table 2.
< embodiment 7 >
Use the prepreg 1 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 140 DEG C, and hot pressing temperature T2 is 140 DEG C, and hot pressing temperature T3 is 120 DEG C.Each evaluation result is shown in table 2.
< comparative example 1 >
Use the prepreg 1 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 140 DEG C, and hot pressing temperature T2 is 160 DEG C.Each evaluation result is shown in table 2.
< comparative example 2 >
Use the prepreg 1 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 140 DEG C, and hot pressing temperature T2 is 100 DEG C.Each evaluation result is shown in table 2.
< comparative example 3 >
Use the prepreg 1 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 120 DEG C, and hot pressing temperature T2 is 140 DEG C.Each evaluation result is shown in table 2.
< comparative example 4 >
Use the prepreg 1 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 120 DEG C, and hot pressing temperature T2 is 100 DEG C.Each evaluation result is shown in table 2.
< comparative example 5 >
Use the prepreg 1 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 100 DEG C, and hot pressing temperature T2 is 140 DEG C.Each evaluation result is shown in table 2.
< comparative example 6 >
Use the prepreg 1 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 100 DEG C, and hot pressing temperature T2 is 100 DEG C.Each evaluation result is shown in table 2.
< comparative example 7 >
Use the prepreg 3 of band carrier, according to the operation of above-mentioned (preparation of mensuration, evaluation substrate), substrate is evaluated in preparation.As shown in table 2, laminating temperature T1 is 140 DEG C, and hot pressing temperature T2 is 140 DEG C.Each evaluation result is shown in table 2.
[table 2]
。

Claims (9)

1. the manufacture method of multilayer printed circuit board, it comprises
(I) prepreg being formed with the band carrier of prepreg is on a carrier film laminated in the mode making prepreg and engage with internal layer circuit substrate the step on internal layer circuit substrate,
(II) by the prepreg hot pressing of the band carrier through lamination the step of smoothing and
(III) prepreg hot curing is formed the step of insulating barrier,
The feature of the manufacture method of described multilayer printed circuit board is,
When the total quality of prepreg is set to 100 quality %, the fiber base material in prepreg and the gross mass of inorganic filling material are more than 70 quality %,
The melt viscosity of the prepreg under the hot pressing temperature of step (II) is 300 ~ 10000 pools,
The maximum cross-section height (Rt) on the carrier film surface of the prepreg of the band carrier after step (I) is less than 5 μm, and
The laminating temperature of step (I) is set to T1 (DEG C), the hot pressing temperature of step (II) is when being set to T2 (DEG C), T1 and T2 meets the relation of T2≤T1+10.
2. method according to claim 1, wherein, T1 and T2 meets the relation of T2≤T1+5.
3. method according to claim 1, wherein, implements more than 2 times by step (II).
4. method according to claim 1, wherein, the maximum cross-section height (Rt) of the surface of insulating layer after step (III) is less than 3 μm.
5. method according to claim 1, wherein, prepreg is further containing epoxy resin and curing agent.
6. method according to claim 5, wherein, prepreg is formed in fiber base material by making the resin combination containing epoxy resin, curing agent and inorganic filling material infiltrate.
7. method according to claim 1, wherein, carrier film is stripped after step (III).
8. the method according to any one of claim 1 ~ 7, wherein, in step (III), configures prepreg with plumbness, carries out hot curing and form insulating barrier in heating furnace.
9. multilayer printed circuit board, it contains the insulating barrier of the condition meeting following (a) to (c):
When the total quality of this insulating barrier is set to 100 quality % by () a, the gross mass of fiber base material and inorganic filling material is more than 70 quality %;
B the maximum cross-section height (Rt) on the surface of () this insulating barrier is less than 3 μm; With
C the difference of the thickness of the base ends of () this insulating barrier and the thickness in substrate center portion is less than 2.5 μm.
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