CN104349614B - Multilayer printed circuit board and its manufacturing method - Google Patents

Multilayer printed circuit board and its manufacturing method Download PDF

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Publication number
CN104349614B
CN104349614B CN201410374825.XA CN201410374825A CN104349614B CN 104349614 B CN104349614 B CN 104349614B CN 201410374825 A CN201410374825 A CN 201410374825A CN 104349614 B CN104349614 B CN 104349614B
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China
Prior art keywords
prepreg
insulating layer
carrier
resin
mass
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CN201410374825.XA
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CN104349614A (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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    • 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 manufacturing method of present invention offer multilayer printed circuit board, wherein, even if the flatness that also may be implemented surface is excellent, the thickness of centre portion and base ends in a substrate difference is small, the thickness also good insulating layer of equilibrium when using the high prepreg of the total content of fiber base material and inorganic filling material to form insulating layer.The manufacturing method of multilayer printed circuit board, it includes: the prepreg with carrier for being formed with prepreg on a carrier film is laminated to the step on internal layer circuit substrate by (I) in a manner of engaging prepreg with internal layer circuit substrate, (II) the prepreg hot pressing by laminated with carrier and the step of smooth, the step of prepreg heat cure is formed insulating layer by (III), the manufacturing method of the multilayer printed circuit board is characterized in that, when the total quality of prepreg is set as 100 mass %, the gross mass of fiber base material and inorganic filling material in prepreg is 70 mass % or more, the melt viscosity of prepreg under the hot pressing temperature of step (II) is 300~10000 pools, the maximum cross-section height (Rt) of the carrier film surface of the prepreg with carrier after step (I) is less than 5 μm, and the laminating temperature of step (I) is set as T1 (DEG C), when the hot pressing temperature of step (II) is set as T2 (DEG C), T1 and T2 meet the relationship of T2≤T1+10.

Description

Multilayer printed circuit board and its manufacturing method
Technical field
The present invention relates to the manufacturing methods of multilayer printed circuit board.In detail, the present invention relates to used with the pre- of carrier Soak the manufacturing method of the multilayer printed circuit board of material.
Background technique
Manufacturing technology as multilayer printed circuit board, it is known that the stacking of alternately stacked insulating layer and conductor layer is utilized The manufacturing method of (ビ Le De ア ッ プ) mode.In the manufacturing method that stack manner is utilized, generally, insulating layer is by making Resin combination heat cure and formed.Such as following methods can be used: using foring resin composition layer on a carrier film Adhesive film forms insulating layer using vacuum laminator.In addition in recent years, wanted for the slimming of adjoint multilayer printed circuit board The mechanical strength of insulating layer is sought and improved, proposes using the prepreg with carrier, using vacuum laminator and forms insulating layer Method (patent document 1).
Existing technical literature
Patent document
Patent document 1: International Publication No. 2009/35014.
Summary of the invention
Technical problems to be solved by the inivention
On the other hand, with the slimming of multilayer printed circuit board, caused in order to prevent by the thermal expansion difference with conductor layer Crackle etc., the reduction of the thermal expansion coefficient of insulating layer becomes more and more important.As for making the thermal expansion coefficient of insulating layer Reduced method, can enumerate for example makes fiber base material in the prepreg used in the formation of insulating layer and/or inorganic fills out The content for filling material increases.But it when using the high prepreg of the content of fiber base material and/or inorganic filling material, is difficult to Form the tendency of the insulating layer of smooth surface.Such as in the technology that above patent document 1 is recorded, implement to use vacuum laminator After prepreg with carrier is pressed on internal layer circuit substrate, the surface of the laminated prepreg with carrier is utilized into metal Plate carry out hot pressing and the step of smooth, but when using the high prepreg of the content of fiber base material and/or inorganic filling material, in advance Leaching material is difficult to follow the concave-convex surface (due to the presence or absence of circuit conductor) of internal layer circuit substrate, the surface tool of resulting insulating layer There is fluctuating corresponding with the concave-convex surface of internal layer circuit substrate as ground, there is the insulating layer for being difficult to obtain smooth surface Tendency.
Such as the hot pressing temperature in smoothing step is being set as high value etc., the mobility of resin is made to get higher such item When carrying out hot pressing under part, prepreg can be improved to the trackability of the concave-convex surface of internal layer circuit substrate, the table of insulating layer can be made The fluctuating in face becomes smaller.But in this case, the inventors of the present invention's discovery has following tendencies: due to the exudation etc. of resin, causing absolutely The disturbance of equilibrium of the thickness of edge layer, centre portion and base ends, the thickness of resulting insulating layer generate big difference in a substrate.
The issue of the present invention is to provide the manufacturing methods of multilayer printed circuit board, wherein even if using fiber base material With the total content of inorganic filling material high prepreg it is excellent come flatness that surface when forming insulating layer, also may be implemented, The difference of the thickness of substrate center portion and base ends is small, the thickness also good insulating layer of equilibrium.
Solve the means of technical problem
The inventors of the present invention have carried out making great efforts research in view of the above subject, as a result, it has been found that using the prepreg shape with carrier When at insulating layer, the maximum cross-section height (Rt) of the carrier film surface of the prepreg with carrier after making lamination step maintains one Definite value hereinafter, and so that the difference of the laminating temperature of lamination step and the hot pressing temperature of smoothing step is maintained particular range, it is described Prepreg with carrier is that be formed with the total content of fiber base material and inorganic filling material on a carrier film be a certain amount of above, tool There is the prepreg of specific melt viscosity, it is possible thereby to solve the above subject, so as to complete the present invention.
That is, the present invention contains content below:
[1] manufacturing method of multilayer printed circuit board, it includes
(I) it will be formed with the prepreg with carrier of prepreg on a carrier film so that prepreg connects with internal layer circuit substrate The mode of conjunction is laminated to the step on internal layer circuit substrate,
(II) the prepreg hot pressing by laminated with carrier and the step of smooth and
(III) the step of prepreg heat cure being formed into insulating layer,
The manufacturing method of the multilayer printed circuit board is characterized in that,
When the total quality of prepreg is set as 100 mass %, fiber base material and inorganic filling material in prepreg it is total Quality is 70 mass % or more,
The melt viscosity of prepreg under the hot pressing temperature of step (II) is 300~10000 pools,
The maximum cross-section height (Rt) of the carrier film surface of the prepreg with carrier after step (I) less than 5 μm, and
The laminating temperature of step (I) is set as T1 (DEG C), when the hot pressing temperature of step (II) is set as T2 (DEG C), T1 and T2 are full The relationship of sufficient T2≤T1+10；
[2] method according to [1], wherein T1 and T2 meets the relationship of T2≤T1+5；
[3] method according to [1] or [2], wherein implement step (II) 2 times or more；
[4] method according to any one of [1]~[3], wherein the surface of insulating layer after step (III) is most Big depth of section (Rt) is less than 3 μm；
[5] method according to any one of [1]~[4], wherein prepreg further contains epoxy resin and solidification Agent；
[6] method according to any one of [1]~[5], wherein prepreg is by making containing epoxy resin, solidification The resin combination of agent and inorganic filling material is impregnated into fiber base material and is formed；
[7] method according to any one of [1]~[6], wherein carrier film is stripped after step (III)；
[8] method according to any one of [1]~[7], wherein in step (III), by prepreg in heating furnace It is interior to be configured with plumbness, it carries out heat cure and forms insulating layer；
[9] multilayer printed circuit board contains the insulating layer for meeting the condition of following (a) to (c):
(a) when the total quality of the insulating layer being set as 100 mass %, the gross mass of fiber base material and inorganic filling material For 70 mass % or more；
(b) the maximum cross-section height (Rt) on the surface of the insulating layer is less than 3 μm；With
(c) difference of the thickness of the base ends of the insulating layer and the thickness in substrate center portion is less than 2.5 μm.
Invention effect
According to the method for the present invention, even if carrying out shape using the high prepreg of the total content of fiber base material and inorganic filling material When at insulating layer, the flatness that can also manufacture surface is excellent, in a substrate centre portion and base ends have the difference of thickness it is small, The multilayer printed circuit board of the well-balanced insulating layer of thickness.
Specific embodiment
Before the manufacturing method for multilayer printed circuit board of the invention is described in detail, in the present invention Method used in " prepreg with carrier " be illustrated.
Prepreg > of the < with carrier
In the method for the invention, using the prepreg with carrier for being formed with prepreg on a carrier film.
As carrier film, the film being molded of plastic material, metal foil (copper foil, aluminium foil etc.), processing release paper can be enumerated, preferably Use the film being molded of plastic material.As plastic material, it is (sometimes simple below that such as polyethylene terephthalate can be enumerated Referred to as " PET "), the polyester such as polyethylene naphthalate (hereinafter sometimes referred to simply as " PEN "), polycarbonate (below sometimes referred to as For the acrylic acid series such as " PC "), polymethyl methacrylate (PMMA), cyclic polyolefin, tri acetyl cellulose (TAC), polyethers Sulfide (PES), polyether-ketone, polyimides etc..Wherein, preferably polyethylene terephthalate, polyethylene naphthalate, it is special Not preferably cheap polyethylene terephthalate.In suitable embodiment, carrier film is poly terephthalic acid second Diester film.
Delustring processing, sided corona treatment can be implemented to the face of carrier film engaged with prepreg.
In addition, the load with release layer on the face engaged with prepreg with release layer can be used as carrier film Body film.As release agent used in the release layer in the carrier film with release layer, can enumerate for example selected from alkyd resin, poly- The release agent of one or more of olefin resin, polyurethane resin and organic siliconresin.
In the present invention, commercially available product can be used in the carrier film with release layer.As commercially available product, such as リ Application can be enumerated " PET501010 ", " SK-1 ", " AL-5 ", " AL-7 " etc. of テ ッ Network (strain) system.
The thickness of carrier film is not particularly limited, preferably 10 μm~70 μm of range, more preferably 20 μm~60 μm Range, and then preferably 20 μm~50 μm of range.It should be noted that preferably band is de- when carrier film is the carrier film with release layer The thickness of the carrier film entirety of mold layer is within the above range.
Prepreg makes resin combination be impregnated into fiber base material and be formed.
Fiber base material is not particularly limited, can be used as glass cloth, aramid nonwoven fabric, liquid crystal polymer without The common fiber base material of the prepregs substrate such as woven fabric.It, can be preferred in the insulating layer for being used to form multilayer printed circuit board Using with a thickness of 50 μm of slim sheet-like fiber substrates below, in particular it is preferred to a thickness of 10 μm~40 μm of sheet-like fiber Substrate, more preferably with a thickness of 10 μm~30 μm of sheet-like fiber substrate.
It as the concrete example for the glass cloth that can be used as sheet-like fiber substrate, can enumerate: rising sun シ ュ エ ー ベ Le (strain) system " ス タ イ Le 1027MS " (75/25mm of warp count, 75/25mm of weft count, cloth weight 20g/m2, 19 μ of thickness M), rising sun シ ュ エ ー ベ Le (strain) system " ス タ イ Le 1037MS " (70/25mm of warp count, weft count 73/ 25mm, cloth weight 24g/m2, 28 μm of thickness), (strain) there is pool to make made " 1078 " (54/25mm of warp count, weft yarn are close Spend 54/25mm, cloth weight 48g/m2, 43 μm of thickness), (strain) have pool make made " 1037NS " (warp count 72/ 25mm, 69/25mm of weft count, cloth weight 23g/m2, 21 μm of thickness) (strain) have pool to make made " 1027NS " (warp thread 75/25mm of density, 75/25mm of weft count, cloth weight 19.5g/m2, 16 μm of thickness), (strain) have pool production it is made " 1015NS " (95/25mm of warp count, 95/25mm of weft count, cloth weight 17.5g/m2, 15 μm of thickness), (strain) have Pool makes made " 1000NS " (85/25mm of warp count, 85/25mm of weft count, cloth weight 11g/m2, 10 μ of thickness M) etc..Additionally as the concrete example of liquid crystal polymer non-woven fabrics, (strain) Network ラ レ, aromatic polyester non-woven fabrics can be enumerated " ベ Network Le ス " (6~15g/m of weight per unit area that meltblown is utilized2), " ベ Network ト ラ Application " etc..
For the resin combination for prepreg, as long as its solidfied material has sufficient hardness and insulating properties, do not have It is particularly limited to, may be used at known resin combination used in the formation of the insulating layer of multilayer printed circuit board.
Resin from the point of view of the thermal expansion coefficient of resulting insulating layer is suppressed to lower degree, for prepreg Composition preferably comprises inorganic filling material.
Inorganic filler can enumerate such as silica, silicon nitride, aluminium oxide, glass, cordierite, Si oxide, sulphur Sour barium, barium carbonate, talcum, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminium hydroxide, magnesium hydroxide, calcium carbonate, carbon Sour magnesium, magnesia, boron nitride, aluminium nitride, nitrogenized manganese, aluminium borate, barium titanate, strontium carbonate, strontium titanates, calcium titanate, magnesium titanate, titanium Sour bismuth, titanium oxide, zirconium oxide, metatitanic acid barium zirconate, barium zirconate, calcium zirconate, basic zirconium phosphate and phosphoric acid tungsten wire array etc..Wherein, amorphous The silica such as silica, fused silica, crystalline silica, synthetic silica, hollow silica are special Suitably.In addition silica is preferably spherical silicon dioxide.Inorganic filling material can be used alone, can also be by 2 kinds Combination of the above uses.As commercially available spheroidal fused silica, can enumerate (strain) ア De マ テ ッ Network ス system " SOC4 ", “SOC2”、“SOC1”。
The average grain diameter of inorganic filling material, from obtaining the angle of insulating reliability and the good insulating layer of surface smoothness Consider, preferably 2 μm hereinafter, more preferably 1 μm hereinafter, in turn be preferably 0.8 μm hereinafter, in turn be more preferably 0.6 μm or less. On the other hand, from the point of view of the dispersibility raising of inorganic filling material, the average grain diameter of inorganic filling material is preferably 0.01 μm or more, more preferably 0.05 μm or more, and then preferably 0.1 μm or more.The average grain diameter of inorganic filling material can be with It is measured using based on the laser diffraction-scattering method of Michaelis (Mie) scattering theory.Specifically, laser diffraction and scattering formula grain is utilized Distribution measurement device is spent, the size distribution of inorganic filling material is made with volume reference, its median diameter is set as average grain diameter, It is possible thereby to measure.Sample can it is preferable to use samples obtained by being dispersed in water inorganic filling material using ultrasonic wave for measurement Product.As laser diffraction and scattering formula particle size distribution device, Horiba Ltd LA-950 etc. can be used.
The content of inorganic filling material in resin combination, from by the thermal expansion coefficient of resulting insulating layer be suppressed to compared with From the point of view of low degree, preferably 40 mass % or more, more preferably 50 mass % or more, and then preferably 60 mass % or more. The upper limit of the content of inorganic filling material in resin combination is not particularly limited, from obtaining the good insulation of surface smoothness From the point of view of layer, preferably 90 mass % are hereinafter, more preferably 85 mass % or less.
It should be noted that in the present invention, the content of each ingredient in resin combination is to wave non-in resin combination Send out into value when being divided into 100 mass %.
In order to improve moisture-proof, inorganic filling material is preferably with epoxy silane system coupling agent, amino silicone methane series coupling agent, mercapto 1 kind or more of surface of base silane system coupling agent, silane series coupling agent, organic silazane hydride compounds, titanate esters system coupling agent etc. Inorganic agent is handled.In surface treating agent, amino silicone methane series coupling agent is due to moisture-proof, dispersibility, the characteristic of solidfied material It etc. excellent, therefore is suitable.Inorganic filling material can be preparatory with surface treating agent before being mixed in resin combination It is handled.Alternatively, inorganic filling material can be by adding inorganic filler and surface treating agent in resin combination (that is, utilizing integral blend method) and handled with surface treating agent.As the commercially available product of surface treating agent, SHIN-ETSU HANTOTAI can be enumerated Chemical industry (strain) makes " KBM403 " (3- glycidoxypropyltrime,hoxysilane), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM803 " (3-mercaptopropyi trimethoxy silane), SHIN-ETSU HANTOTAI's chemical industry (strain) make " KBE903 " (three ethoxy of 3- aminopropyl Base silane), SHIN-ETSU HANTOTAI's chemical industry (strain) make " KBM573 " (N- phenyl -3- TSL 8330), SHIN-ETSU HANTOTAI's chemistry work Industry (strain) makes " KBM103 " (phenyltrimethoxysila,e), SHIN-ETSU HANTOTAI's chemical industry (strain) system " SZ-31 " (hexamethyldisilazane) Deng.
When inorganic filling material is set as 100 mass %, the treating capacity of surface treating agent is preferably 0.01 matter of mass %~5 Measure %, more preferably 0.1 mass of mass %~3 %.
Resin combination for prepreg preferably contains epoxy resin and curing agent in turn.Therefore in suitable embodiment party In formula, prepreg in fiber base material by infiltrating the resin combination containing epoxy resin, curing agent and inorganic filling material And it is formed.
Epoxy resin-
There is no particular limitation for epoxy resin, has the epoxy resin of 2 or more epoxy groups preferably in 1 molecule. Specifically, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin and bisphenol AF type ring oxygen can be enumerated The bisphenol-type epoxy resins such as resin, novolac type epoxy resin, tert butyl-catechol type epoxy resin, naphthol type asphalt mixtures modified by epoxy resin Rouge, naphthalene type epoxy resin, naphthylene ether type epoxy, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, Cresol formaldehyde type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, has butadiene at biphenyl type epoxy resin Epoxy resin, alicyclic epoxy resin, hetero ring type epoxy resin, the epoxy resin containing loop coil, the cyclohexanedimethanol type of structure Epoxy resin, trihydroxy methyl type epoxy resin, halogenated epoxy resin etc..Epoxy resin can be used alone, can also be by 2 Kind combination of the above uses.
Wherein, from the point of view of heat resistance, insulating reliability and mobility, preferably bisphenol-type epoxy resin is (preferably 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, the asphalt mixtures modified by epoxy resin with butadiene structure Rouge.Particularly, epoxy resin is preferably comprised selected from bisphenol-type epoxy resin (preferably bisphenol A type epoxy resin, bisphenol F type epoxy Resin), naphthol type epoxy resin, naphthalene type epoxy resin, a kind in biphenyl type epoxy resin and naphthylene ether type epoxy with On.Specifically, such as bisphenol A type epoxy resin (Mitsubishi Chemical's (strain) makes " jER828EL ", " YL980 "), Bisphenol F can be enumerated Type epoxy resin (Mitsubishi Chemical's (strain) makes " jER806H ", " YL983U "), 2 functional epoxy resins of naphthalene type (DIC (strain) system " HP4032 ", " HP4032D ", " HP4032SS ", " EXA4032SS "), 4 functional epoxy resins of naphthalene type (DIC (strain) system " HP4700 ", " HP4710 "), naphthol type epoxy resin (Nippon Steel chemistry (strain) system " ESN-475V "), there is butadiene structure Epoxy resin (ダ イ セ Le chemical industry (strain) make " PB-3600 "), 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) make " YX8800 "), naphthylene ether type epoxy (DIC (strain) system " EXA-7310 ", " EXA-7311 ", " EXA-7311L ", " EXA-7311G3 ", " EXA-7311G4 "), glycidyl ester type epoxy Resin (Na ガ セ ケ system テ ッ Network ス (strain) makes " EX711 ", " EX721 ", (strain) プ リ Application テ ッ Network system " R540 ") etc..
Epoxy resin preferably comprises the epoxy resin in 1 molecule with 2 or more epoxy groups.By the non-of epoxy resin When volatile ingredient is set as 100 mass %, preferably at least 50 mass % or more are the rings in 1 molecule with 2 or more epoxy groups Oxygen resin.
From the point of view of improving trackability of the prepreg to the concave-convex surface of internal layer circuit substrate, epoxy resin preferably contains Have in the epoxy resin (hereinafter also referred to " liquid-state epoxy resin ") that 20 DEG C of temperature are liquid.From improve prepreg to internal layer electricity While the trackability of the concave-convex surface of base board, improve the solidification physical property for the insulating layer for forming prepreg heat cure Angle consider, epoxy resin preferably comprise liquid-state epoxy resin and 20 DEG C of temperature for solid epoxy resin (hereinafter also referred to " solid epoxy resin ").As liquid-state epoxy resin, there is the liquid epoxy of 2 or more epoxy groups preferably in 1 molecule Resin has the aromatic system liquid-state epoxy resin of 2 or more epoxy groups more preferably in 1 molecule.As solid epoxidic Resin has the solid epoxy resin of 3 or more epoxy groups preferably in 1 molecule, has 3 more preferably in 1 molecule The aromatic system solid epoxy resin of above epoxy group.In the present invention, the epoxy resin of aromatic system refers in its molecule The interior epoxy resin with aromatic rings.
As liquid-state epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac type ring can be enumerated Oxygen resin, glycidyl ester type epoxy resin, naphthalene type epoxy resin etc., preferably bisphenol A type epoxy resin, bisphenol F type epoxy Resin, naphthalene type epoxy resin.Liquid-state epoxy resin can be used alone, two or more can also be applied in combination.As solid State epoxy resin, can enumerate 4 functional epoxy resins of naphthalene type, Cresol formaldehyde 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 resin etc., more preferable 4 functional epoxy resins of naphthalene type, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type Epoxy resin.Solid epoxy resin can be used alone, two or more can also be applied in combination.
As epoxy resin, by liquid-state epoxy resin and solid epoxy resin and used time, from making consolidating for resulting insulating layer From the point of view of compound improves, their mixing ratio (liquid-state epoxy resin: solid epoxy resin) is preferred by quality ratio For 1: 0.1~1: 8 range, more preferable 1: 0.3~1: 7 range, and then preferably 1: 0.6~1: 6 range, and then more preferably 1: 0.9~1: 5.5 range.
The epoxide equivalent of epoxy resin is preferably 50~3000, and more preferably 80~2000, and then preferably 110~ 1000.It should be noted that epoxide equivalent can be measured according to JIS K7236, it is the matter of the resin of the epoxy group containing 1 equivalent Amount.
The content of epoxy resin in resin combination is preferably the 3 mass % of mass %~40, more preferably 5 mass %~35 Quality %, and then preferably 10 mass of mass %~30 %.From prepreg is improved to the trackability of the concave-convex surface of internal layer circuit substrate From the point of view of, the content of the liquid-state epoxy resin in resin combination is preferably the 1 mass % of mass %~35, more preferably 3 matter Measure the mass % of %~30, and then preferably 6 mass of mass %~25 %.
Curing agent-
As curing agent, as long as having the function of epoxy resin cure, there is no particular limitation, such as phenol can be enumerated It is curing agent, active ester system curing agent, cyanate system curing agent, benzoxazine system curing agent and acid anhydrides system curing agent.Curing agent It can be used alone, two or more can also be applied in combination.In suitable embodiment, curing agent is solid selected from phenol system One or more of agent, active ester system curing agent and cyanate system curing agent.
It as phenol system curing agent, is not particularly limited, but preferably biphenyl type curing agent, naphthalene type curing agent, line style phenolic aldehyde Type curing agent, naphthylene ether type curing agent, the skeleton containing triazine phenol system curing agent.Phenol system curing agent can be used alone, Two or more can be applied in combination.
As the commercially available product of phenol system curing agent, biphenyl type curing agent can enumerate MEH-7700, MEH-7810, MEH-7851 (bright and chemical conversion (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), and naphthylene ether type curing agent can enumerate EXB- 6000 (DIC (strain) systems), the phenol system curing agent of the skeleton containing triazine can enumerate LA3018, LA7052, LA7054, LA1356 (DIC (strain) system) etc..Wherein, the preferably phenol system curing agent of naphthalene type curing agent, the skeleton containing triazine.
Active ester system curing agent is not particularly limited, it is usually preferred to use phenolic ester class (phenol esters), benzenethiol Ester (thiophenol esters) class, N- hydroxylamine esters, esters of heterocycle hydroxyl compound etc. in 1 molecule have 2 with The compound of the high ester group of upper reactivity.The active ester system curing agent preferably passes through carboxylic acid compound and/or thiocarboxylic It closes the condensation reaction of object and hydroxy compounds and/or mercaptan compound and obtains.It is especially excellent from the viewpoint of improving heat resistance Select the active ester system curing agent obtained by carboxylic acid compound and hydroxy compounds.More preferably by carboxylic acid compound and oxybenzene compound And/or the active ester system curing agent that naphthol compound obtains.As carboxylic acid compound, it can be mentioned, for example: benzoic acid, acetic acid, amber Amber acid, maleic acid, itaconic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), Pyromellitic Acid etc..As phenol chemical combination Object or naphthol compound, it can be mentioned, for example: quinhydrones, resorcinol, bisphenol-A, Bisphenol F, bisphenol S, phenolphthalin, methylation bisphenol-A, Methylate Bisphenol F, methylation bisphenol S, phenol, o-cresol, metacresol, paracresol, catechol, alpha-Naphthol, betanaphthol, 1,5- bis- Hydroxyl naphthalene, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxy hexichol first Ketone, phloroglucin, benzenetriol (benzenetriol), dicyclopentadiene-type biphenol, linear phenol-aldehyde resin (phenol Novolac) etc..
As active ester system curing agent, preferably the active ester system curing agent containing dicyclopentadiene-type biphenol structure, Active ester system curing agent containing naphthalene structure, as linear phenol-aldehyde resin acetylate active ester system curing agent, as line Active ester system curing agent of the benzoylate of type phenolic resin etc., wherein from reducing the melt viscosity of prepreg, making internally From the aspect of the trackability of the concave-convex surface of layer circuit substrate improves, further preferably dicyclopentadiene-type biphenol structure Active ester system curing agent.It should be noted that in the present invention, " dicyclopentadiene-type biphenol structure " indicates to include phenylene-two The divalent structural unit of ring pentalene (ジ シ Network ロ ペ Application タ レ Application)-phenylene.Active ester system curing agent can be used alone 1 Kind, two or more can also be applied in combination.
As the commercially available product of active ester system curing agent, the active ester system curing agent containing dicyclopentadiene-type biphenol structure EXB9451, EXB9460, EXB9460S-65T, HPC8000-65T (DIC (strain) system) can be enumerated, as linear phenol-aldehyde resin The active ester system curing agent of acetylate can enumerate DC808 (Mitsubishi Chemical's (strain) system), the benzene as linear phenol-aldehyde resin The active ester system curing agent of formyl compound can enumerate YLH1026 (Mitsubishi Chemical's (strain) system), YLH1030 (Mitsubishi Chemical's (strain) System), YLH1048 (Mitsubishi Chemical's (strain) system) etc..
It as cyanate system curing agent, is not particularly limited, such as novalac-type (ノ ボ ラ ッ can be enumerated 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 they with a portion of The prepolymer etc. of triazine.The weight average molecular weight of cyanate system curing agent is not particularly limited, and preferably 500~4500, it is more excellent It is selected as 600~3000.
As the concrete example of cyanate system curing agent, it is (oligomeric that such as bisphenol A dicyanate, polyphenol cyanate can be enumerated (3- methylene -1,5- phenylenecyanate)), 4,4' methylene bis (2,6- 3,5-dimethylphenyl cyanate), 4,4'- ethylidene Bis- (4- cyanate) phenyl-propanes of dicyanate, hexafluoro bisphenol-a dicyanate, 2,2-, bis- (the 4- cyanate phenyl of 1,1- Methane), bis- (4- cyanate -3,5- 3,5-dimethylphenyl) methane, bis- (4- cyanate phenyl -1- (methyl the ethylidene)) benzene of 1,3-, The 2 function cyanate ester resins such as bis- (4- cyanate phenyl) thioethers and bis- (4- cyanate phenyl) ethers, by linear phenol-aldehyde resin, first Multifunctional cyanate ester resin, these cyanate resins derived from fluosite, phenolic resin containing bicyclopentadiene structure etc. A part of rouge is by the prepolymer etc. of triazine.Cyanate system curing agent can be used alone, can also be by two or more group It closes and uses.
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 are become the pre-polymerization of tripolymer by triazine Object can enumerate BA230 (ロ Application ザ ジ ャ パ Application (strain) system), and the cyanate ester resin containing bicyclopentadiene structure can be enumerated DT-4000, DT-7000 (ロ Application ザ ジ ャ パ Application (strain) system) etc..
As the specific example of benzoxazine system curing agent, can enumerate Showa macromolecule (strain) system " HFB2006M ", " P-d ", " F-a " of four countries' chemical conversion industry (strain) system.Benzoxazine system curing agent can be used alone, can also by 2 kinds with On be applied in combination.
As acid anhydrides system curing agent, such as phthalic anhydride, tetrabydrophthalic anhydride, hexahydro neighbour benzene two can be enumerated Formic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenating methyl receive enlightening Gram acid anhydrides, 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 two Acid anhydride, bibenzene tetracarboxylic dianhydride, naphthalenetetracarbacidic acidic dianhydride, two O-phthalic acid dianhydride of hydroxyl, 3,3'-4,4'- diphenyl sulfone tetraformic acid two Acid anhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydro -2,5- dioxo -3- furyl)-naphtho- [1,2-C] furans -1,3- diketone, Ethylene glycol bis- (trimellitate acid anhydrides) (エ チ レ Application グ リ コ ー Le ビ ス (ア Application ヒ De ロ ト リ メ リ テ ー ト)), styrene with The acid anhydrides etc. of the polymer-types such as styrene-maleic acid resin obtained by maleic acid copolymerized.Acid anhydrides system curing agent can be used alone 1 Kind, two or more can also be applied in combination.
When the compounding ratio of epoxy resin and curing agent is preferably the epoxy radix of epoxy resin being set as 1, curing agent The ratio for the range that reaction radix is 0.3~2.0, the ratio of more preferably 0.3~1.5 range, and then preferably 0.4~ The ratio of 1.1 range.It should be noted that the epoxy radix of epoxy resin refers to, for whole epoxy resin, each epoxy will be used Value obtained by the solid component quality of resin is amounted to divided by the resulting value of epoxide equivalent；The reaction radix of curing agent refers to, For whole curing agent, obtained being amounted to the solid component quality of each curing agent divided by the resulting value of reactive group equivalent Value.
For the resin combination of prepreg, as needed, thermoplastic resin, curing accelerator, resistance can be contained in turn Fire the additives such as agent and rubber particles.
Thermoplastic resin-
For the resin combination of prepreg, surface is roughened after making prepreg solidification and tool can be formed From the point of view of the insulating layer for having appropriate roughening face, thermoplastic resin can be contained.Thermoplastic resin can enumerate such as benzene Oxygen resin, polyvinyl acetal resin, polyolefin resin, polybutadiene, polyimide resin, polyamidoimide tree Rouge, polyethersulfone resin, polyphenylene oxide resin and polysulfone resin etc..Thermoplastic resin can be used alone, can also by 2 kinds with On be applied in combination.
The weight average molecular weight of the polystyrene conversion of thermoplastic resin is preferably 8000~70000 range, more preferably 10000~60000 range, and then preferably 15000~60000 range, and then more preferably 20000~60000 model It encloses.The weight average molecular weight of the polystyrene conversion of thermoplastic resin is measured with gel permeation chromatography (GPC) method.Specifically, thermoplastic Property resin polystyrene conversion weight average molecular weight can be used (strain) Shimadzu Seisakusho Ltd. LC-9A/RID-6A as measurement Device uses Showa electrician (strain) Shodex K-800P/K-804L/K-804L processed as pillar, uses chloroform as flowing Phase measures under 40 DEG C of column temperature, is calculated using the standard curve of standard polystyren.
Phenoxy resin can be enumerated for example with 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, enb skeleton, naphthalene skeleton, anthracene bone The phenoxy resin of the skeleton of one or more of frame, adamantane framework, terpenes skeleton and trimethyl-cyclohexane skeleton.Phenoxy resin End can be any functional group such as phenolic hydroxyl group, epoxy group.Phenoxy resin can be used alone or combine two or more It uses.As the concrete example of phenoxy resin, " 1256 " and " 4250 " that can enumerate Mitsubishi Chemical (strain) system (are containing bis-phenol The phenoxy resin of A skeleton), " YX8100 " (phenoxy resin containing bisphenol S skeleton) and " YX6954 " (contain bis-phenol acetophenone The phenoxy resin of skeleton), other " FX280 " and " FX293 " that can also enumerate Dongdu chemical conversion (strain) system, Mitsubishi Chemical's (strain) system " YL7553 ", " YL6794 ", " YL7213 ", " YL7290 " and " YL7482 " etc..
As the concrete example of polyvinyl acetal resin, the electrochemical Block チ ラ ー of electrochemically industrial (strain) system can be enumerated Le 4000-2,5000-A, 6000-C, 6000-EP, the エ ス レ ッ Network BH of ponding chemical industry (strain) system is serial, BX is serial, KS Series, BL series, BM series etc..
As the concrete example of polyimide resin, " the リ カ コ ー ト SN20 " and " リ of new Japan Chemical (strain) system can be enumerated カコートPN20".As the concrete example of polyimide resin, it in addition can enumerate 2 functional hydroxyl groups end polybutadiene, make (the Japanese Laid-Open 2006-37083 bulletin note of threadiness polyimides obtained by diisocyanate cpd and quaternary anhydride reaction The substance of load), polyimides (Japanese Laid-Open 2002-12667 bulletin and Japanese Laid-Open containing silicone matrix The substance recorded in 2000-319386 bulletin etc.) etc. modified polyimides.
As the concrete example of polyamide-imide resin, " the バ イ ロ マ ッ Network ス of Japan's weaving (strain) system can be enumerated HR11NN " and " バ イ ロ マ ッ Network ス HR16NN ".As the concrete example of polyamide-imide resin, Hitachi in addition can be enumerated The polyamidoimide " KS9100 " containing silicone matrix, modified polyamides acyl such as " KS9300 " of chemical conversion industry (strain) system Imines.
As the concrete example of polyethersulfone resin, " PES5003P " etc. of Sumitomo Chemical (strain) system can be enumerated.
As the concrete example of polysulfone resin, the polysulfones of ソ Le ベ イ ア De バ Application ス ト Port リ マ ー ズ (strain) system can be enumerated " P1700 ", " P3500 " etc..
The content of thermoplastic resin in resin combination is preferably the 0.1 mass % of mass %~60, more preferably 0.1 matter Measure the mass % of %~50, and then the preferably 0.5 mass % of mass %~30, and then more preferably 0.5 mass of mass %~10 %.
Curing accelerator-
From the viewpoint of the heat cure for swimmingly carrying out prepreg, the resin combination for prepreg can contain solidification Promotor.Curing accelerator can enumerate for example phosphorus system curing accelerator, amine system curing accelerator, imidazoles system curing accelerator, Guanidine system curing accelerator etc..Curing accelerator can be used alone, two or more can also be applied in combination.
The content of curing accelerator in resin combination, by the total amount of epoxy resin and the non-volatile component of curing agent When being set as 100 mass %, the preferably 0.01 mass % of mass %~3, the more preferably 0.01 mass % of mass %~2, and then preferably 0.01 mass of mass %~1 %.
Fire retardant-
Fire retardant can be contained from the point of view of improving anti-flammability for the resin combination of prepreg.As fire-retardant Agent can enumerate phosphorus compound, nitrogen compound, silicone flame retardant, gold that for example organic phosphorus flame retardant, organic system are nitrogenous Belong to hydroxide etc..Organic phosphorus flame retardant can enumerate the luxuriant and rich with fragrance type phosphatization such as HCA, HCA-HQ, HCA-NQ of three light (strain) system and close The phosphorous benzoxazine compound such as HFB-2006M, the monosodium glutamate Off ァ イ Application テ Network ノ (strain) of object, Showa macromolecule (strain) system The レ オ Off ォ ス 30 of system, 50,65,90,110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, north The phosphorus such as the PX200 that the OP930 of TPPO, PPQ, Network ラ リ ア Application ト (strain) system of emerging chemical industry (strain) system, big eight chemical (strains) are made Ester compound.The nitrogenous phosphorus compound of organic system can enumerate the phosphoric acid such as SP670, SP703 of four countries' chemical conversion industry (strain) system Esteramides compound, the SPB100, SPE100 of chemical (strain) society in big tomb, (strain) volt are shown in the phosphonitriles such as the made FP-series of pharmacy Compound etc..Metal hydroxides can enumerate the hydroxides such as UD65, UD650, UD653 of space portion マ テ リ ア Le ズ (strain) system Magnesium, aluminium hydroxides such as B-30, B-325, B-315, B-308, B-303, UFH-20 of bar industry (strain) society etc..Fire retardant can be with It is used alone a kind, two or more can also be applied in combination.The content of fire retardant in resin combination is not particularly limited, excellent It is selected as the 0.5 mass % of mass %~10, more preferably 1 mass of mass %~9 %.
Rubber particles-
For the resin combination of prepreg, surface is roughened after making prepreg solidification and tool can be formed From the point of view of the insulating layer for having appropriate roughening face, rubber particles can be contained.As rubber particles, it can be used and for example exist Do not dissolved in following organic solvents, with above-mentioned epoxy resin, curing agent and thermoplastic resin etc. also incompatible rubber granule Son.Such rubber particles are generally by making the molecular weight of rubber constituent increase to the undissolved water in organic solvent or resin It puts down, form particle shape to prepare.
Rubber particles can enumerate such as core-sheath-type rubber particles, crosslink propylene nitrile butadiene rubber particle, crosslinking benzene second Alkene butadiene rubber particle, acrylic rubber particle etc..Core-sheath-type rubber particles are the rubber particles with sandwich layer and sheaths, For example, 2 layers of structure that the sheaths of outer layer are made of glassy polymers, the sandwich layer of internal layer is made of rubber-like polymer；Alternatively, The sheaths of outer layer are made of glassy polymers, middle layer is made of rubber-like polymer, sandwich layer is made of glassy polymers 3-tier architecture rubber particles etc..Glassy polymeric nitride layer is for example made of polymer of methyl methacrylate etc., rubber-like Polymeric layer is for example made of butyl acrylate object (butyl rubber) etc..It, can as the concrete example of core-sheath-type rubber particles Enumerate: ス タ Off ィ ロ イ De AC3832, AC3816N, IM-401 change 1, IM-401 and change 7-17 (ガ Application Star is melted into (strain) system), メ タ Block レ Application KW-4426 (Mitsubishi's レ イ ヨ Application (strain) system).As the specific of crosslink propylene nitrile butadiene rubber (NBR) particle Example can enumerate XER-91 (0.5 μm of average grain diameter, JSR (strain) system) etc..As cross-linked styrene butadiene rubber (SBR) particle Concrete example, XSK-500 (0.5 μm of average grain diameter, JSR (strain) system) etc. can be enumerated.As the concrete example of acrylic rubber particle, It can enumerate: メ タ Block レ Application W300A (0.1 μm of average grain diameter), W450A (0.2 μm of average grain diameter) (Mitsubishi's レ イ ヨ Application (strain) System).Rubber particles can be used alone, two or more can also be applied in combination.
The average grain diameter of rubber particles is preferably 0.005 μm~1 μm of range, more preferably 0.2 μm~0.6 μm of model It encloses.The average grain diameter of rubber particles can be used dynamic light scattering method and be measured.Such as make rubber particles using ultrasonic wave etc. It is evenly dispersed in suitable organic solvent, uses dense system's particle size analyzer (FPAR-1000；Big tomb electronics (strain) system), With the size distribution of quality criteria production rubber particles, using its median diameter as average grain diameter, it is possible thereby to measure.Resin group The content for closing the rubber particles in object is preferably the 1 mass % of mass %~10, more preferably 2 mass of mass %~5 %.
Other ingredients-
Resin combination for prepreg can according to need and cooperate other ingredients.As other ingredients, Ke Yilie Citing is as vinyl benzyl based compound, acrylic compounds, maleimide compound, blocked isocyanate compounds The thickeners, silicone such as organic fillers, オ Le ベ Application, the ベ Application ト Application such as heat-curing resin, silicon powder, nylon powder, fluorine powder The defoaming agent or levelling agent of class, fluorine system, high score subclass, imidazoles system coupling agent, thiazole system coupling agent, triazole system coupling agent, silane It is colorants such as the green adaptations such as coupling agent imparting agent, phthalocyanine blue, phthalocyanine green, iodine, dual-azo yellow, carbon black etc..
Resin combination for prepreg can utilize mixed by properly mixing above-mentioned each ingredient, according further to needs It refines equipment (three rollers, ball mill, ball mill, sand mill etc.) or mixing plant (super mixer, planetary stirring machine etc.) carries out It is kneaded or mixes to manufacture.
The manufacturing method of prepreg with carrier is not particularly limited, and can enumerate solvent method, hot melt etc., selected from following The method of one or more of method (i)~(iv) is suitable.
(i): resin combination not dissolved in organic solvent but resin combination is temporarily coated on carrier film On, the method that is laminated on fiber base material
(ii): resin combination being coated directly onto fiber base material using chill coating machine (ダ イ コ ー タ ー) etc. On, prepreg is formed, is then laminated the method for prepreg on a carrier film
(iii): fiber base material is immersed in by preparation by resin varnish obtained by resin combination dissolution in organic solvent In resin varnish, makes its infiltration, drying, form prepreg, be then laminated the method for prepreg on a carrier film
(iv): it is directly coated with resin varnish on a carrier film using chill coating machine etc., forms resin composition layer, it will The method that the resin composition layer is laminated from the two sides of fiber base material.
When using resin varnish, organic solvent can enumerate the ketone such as acetone, methyl ethyl ketone and cyclohexanone, acetic acid The acetate esters such as ethyl ester, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether and carbitol acetate, molten fibre The aromatic hydrocarbon, dimethylformamides such as the carbitols such as agent and butyl carbitol class, toluene and dimethylbenzene, dimethyl acetamide and Acid amides series solvents such as N-Methyl pyrrolidone etc..Organic solvent can be used alone, or two or more is applied in combination.
The drying of resin varnish can use drying means well known to heating, blowing hot-air etc. to implement.Drying condition does not have It is particularly limited to, in the manufacturing method of following multilayer printed circuit boards, prepreg is needed with mobility (flow) and cementability. Therefore, in the drying of resin varnish, it is important that as far as possible without the solidification of resin combination.On the other hand, it is presoaking In material in large quantities residual organic solvent when, become after hardening generate expansion the reason of.Therefore, it is dried, so that prepreg In residual organic solvent amount be usually 5 mass % or less, preferably 2 mass % or less.Although according to organic molten in resin varnish The boiling point of agent and it is different, but for example using the varnish of the organic solvent containing 30 mass of mass %~60 % when, usually 80 DEG C~180 DEG C drying 3 minutes~20 minutes be suitable.
Prepreg used in method of the invention with carrier is as described above, by the way that prepreg is arranged on a carrier film And it is formed.Therefore, in one embodiment, the prepreg with carrier contains: carrier film and the preimpregnation engaged with the carrier film Material.In the prepreg with carrier, very thin resin layer can be contained between carrier film and prepreg.Therefore, in other implementations In mode, the prepreg with carrier contains: carrier film, the very thin resin layer engaged with the carrier film and with the very thin resin layer The prepreg of engagement.Wherein, very thin resin layer refers to resin layer with a thickness of 1~10 μm, without containing fiber base material (insulation Layer).
It, can be in the face of prepreg not engaged with carrier film (that is, with carrier film opposite side in the prepreg with carrier Face) on be laminated the protective film mutually fitted with carrier film in turn.By being laminated protective film, dust etc. can be prevented on the surface of prepreg On attachment or scar.When manufacturing multilayer printed circuit board, can be used by removing protective film.
In the prepreg with carrier, the slimming of multilayer printed circuit board is sought from keeping the thickness of insulating layer thinning Angle consider, the thickness of prepreg be preferably 100 μm hereinafter, more preferably 90 μm hereinafter, in turn be preferably 80 μm hereinafter, in turn More preferably 70 μm hereinafter, particularly preferably 60 μm or less or 50 μm or less.It is desired mechanical strong as prepreg from ensuring From the point of view of degree, the lower limit of the thickness of prepreg is preferably 20 μm or more, and more preferably 30 μm or more.
Fiber base in the prepreg with carrier, when the total quality of prepreg is set as 100 mass %, in prepreg The gross mass of material and inorganic filling material is 70 mass % or more.As described above, the inventors of the present invention have found the fiber base in prepreg When the total content of material and inorganic filling material is high, the thermal expansion coefficient of resulting insulating layer can be suppressed to lower degree, but On the other hand it is difficult to obtain the insulating layer of smooth surface.Details is as described below, but multilayered printed circuit according to the present invention The manufacturing method of plate, even if being up to the prepreg of 70 mass % or more in the total content using fiber base material and inorganic filling material In the case where, the insulating layer of smooth surface can also be advantageously carried out.
For the prepreg with carrier, the containing ratio (fiber base of fiber base material and inorganic filling material in prepreg Material/inorganic filling material mass ratio), from the point of view of the mechanical strength and slimming for realizing prepreg, it is preferably controlled to 0.2~2.5.In turn, from by filling a large amount of inorganic filling material in the gap of fiber base material, and the heat of insulating layer can be made From the point of view of the coefficient of expansion is effectively reduced, above-mentioned containing ratio be more preferably 2.3 hereinafter, in turn be preferably 2.1 hereinafter, into And more preferably 1.9 hereinafter, particularly preferably 1.7 or less or 1.5 or less.In addition, from the melt viscosity for preventing resin combination Raising, inorganic filling material can expeditiously enter from the point of view of the gap of fiber base material, and above-mentioned containing ratio is more preferably 0.25 or more, and then preferably 0.3 or more, and then more preferably 0.35 or more.
For the prepreg with carrier used in the method for the invention, prepreg is in following temperature T2 (that is, this hair The hot pressing temperature of step (II) in the manufacturing method of bright multilayer printed circuit board) when, the melting with 300~10000 pools Viscosity.Pass through the melt viscosity range of prepreg when making temperature T2, it can be advantageous to which realizing has smooth surface While, the difference of the thickness of centre portion and base ends is small in a substrate, well-balanced insulating layer of thickness.When temperature T2 The melt viscosity of prepreg, from the angle for the further small insulating layer of difference for obtaining the thickness of centre portion and base ends in a substrate Degree considers, more than preferably 600 pools, more than more preferably 900 pools, and then more than preferably 1000 pools, and then more preferably More than 1200 pools, particularly preferably 1400 pools are above, 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 moor above or 3000 pools or more.In addition, from obtaining with the surface further smoothed Insulating layer angle and from the point of view of preventing being involved in of air, hole being inhibited to generate, the melting of prepreg when temperature T2 Viscosity is preferably 9000 pools hereinafter, more preferably 8000 moor hereinafter, being in turn preferably 7000 pools hereinafter, being more preferably 6000 in turn Pool is hereinafter, particularly preferably 5000 pools are following.The melt viscosity of prepreg when temperature T2 can be by carrying out dynamic viscoelastic Measurement is to obtain.For example, the melt viscosity of prepreg when temperature T2 can obtain as follows: in 60 DEG C of initial temperature of measurement, rising Dynamic is carried out under conditions of 5 DEG C/min of warm speed, vibration number 1Hz, degree of skewness (ひ ず body) 1deg, 2.5 DEG C of measuring temperature interval Determination of viscoelasticity, melt viscosity when by the drawing of temperature and melt viscosity, reading temperature T2 (DEG C).It is surveyed as dynamic viscoelastic Determine device, " Rheosol-G3000 " of such as (strain) UBM society can be enumerated.
The present invention explained in detail below.
[manufacturing method of multilayer printed circuit board]
The manufacturing method of multilayer printed circuit board of the invention includes: the band that (I) will be formed with prepreg on a carrier film The prepreg of carrier is laminated to step on internal layer circuit substrate, (II) in a manner of engaging prepreg with internal layer circuit substrate Prepreg heat cure is formed insulating layer by the step of laminated prepreg hot pressing with carrier is smoothed and (III) The step of, which is characterized in that when the total quality of prepreg is set as 100 mass %, the fiber base material in prepreg is filled out with inorganic The gross mass for filling material is 70 mass % or more, the melt viscosity of the prepreg under the hot pressing temperature of step (II) is 300~ 10000 moor, and the maximum cross-section height (Rt) of the carrier film surface of the prepreg with carrier after step (I) is incited somebody to action less than 5 μm When the laminating temperature of step (I) is set as T1 (DEG C), the hot pressing temperature of step (II) is set as T2 (DEG C), T1 and T2 meet T2≤T1+ 10 relationship.
< step (I) >
In step (I), the prepreg with carrier of prepreg will be formed on a carrier film so that prepreg and internal layer The mode of circuit substrate engagement is laminated on internal layer circuit substrate.
About the prepreg with carrier, as described above.The prepreg used in the method for the invention is characterized in that, is incited somebody to action When the total quality of prepreg is set as 100 mass %, the gross mass of fiber base material and inorganic filling material in prepreg is 70 matter % or more is measured, the melt viscosity under the hot pressing temperature of step (II) is 300~10000 pools.
In the manufacturing method of multilayer printed circuit board of the invention, " internal layer circuit substrate " refers to intermediate manufacture object, With in glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermohardening type polyphenyl ether The conductor layer (circuit conductor) that pattern processing has been carried out on the one or both sides of the substrates such as plate, in manufacture multilayer printed circuit board When, to be further formed insulating layer and conductor layer.
The thickness of circuit conductor that pattern processing has been carried out on the one or both sides of substrate is not particularly limited, but from more Layer printed wiring board slimming from the point of view of, preferably 70 μm hereinafter, more preferably 60 μm hereinafter, in turn be preferably 50 μm Hereinafter, being more preferably 40 μm in turn hereinafter, particularly preferably 30 μm or less, 20 μm or less, 15 μm or less or 10 μm or less.Circuit The lower limit of the thickness of conductor is not particularly limited, preferably 1 μm or more, more preferably 3 μm or more, so preferably 5 μm with On.
Line width/spacing ratio (ラ イ Application/ス ペ of the circuit conductor of pattern processing has been carried out on the one or both sides of substrate ー ス ratio) it is not particularly limited, but the angle of the excellent insulating layer of surface smoothness is obtained from the fluctuating for inhibiting surface of insulating layer Degree consider, usually 900/900 μm hereinafter, preferably 700/700 μm hereinafter, more preferably 500/500 μm hereinafter, in turn preferably For 300/300 μm hereinafter, being more preferably 200/200 μm or less in turn.The line width of circuit conductor/spacing ratio lower limit is not special Limitation, but in order to make prepreg between spacing in embedment it is good, preferably 1/1 μm or more.
In addition, circuit conductor occupation rate ((area of circuit conductor part)/(the internal layer electricity on the surface of internal layer circuit substrate The surface area of base board) × 100 [%]) it can be determined according to required characteristic.Circuit conductor occupation rate is in circuit conductor copper shape At when be also referred to as " residual copper ratio ".Circuit conductor occupation rate can be distributed on the surface of internal layer circuit substrate.Shape can be used for example At the internal layer circuit substrate in the region with the 1st circuit conductor occupation rate and the region with the 2nd circuit conductor occupation rate.Make For general tendency, circuit conductor occupation rate is lower, the thickness on the circuit conductor of the insulating layer formed on internal layer circuit substrate It spends thinner.Particularly, the thickness for being used to form the prepreg of insulating layer is thinner, and the tendency is more significant.Wherein, " insulating layer Thickness on circuit conductor " refers to the thickness in the insulating layer of the surface of circuit conductor.In the present invention, due to realizing in base The small insulating layer of the difference of plate end and substrate center portion thickness, even if in the case where using the thin prepreg of thickness, it can also be with The insulating layer for showing desired insulating reliability is realized in the range of entire substrate.It should be noted that in the present invention, edge of substrate The thickness of the insulating layer in portion refers to the thickness on the circuit conductor of the insulating layer of base ends, the thickness of the insulating layer in substrate center portion Degree refers to the thickness on the circuit conductor of the insulating layer in substrate center portion.
The lamination treatment of step (I) for example can be by reduced pressure conditions, be engaged with internal layer circuit substrate with prepreg Mode, the prepreg with carrier is heated on internal layer circuit substrate crimping to carry out.Exist as by the prepreg with carrier The component (hereinafter also referred to " heating crimping component ") that heating crimping is carried out on internal layer circuit substrate, can enumerate for example heated Metal plate (SUS end plate etc.) or metallic roll (SUS roller) etc..It should be noted that it is preferred that not by heating crimping component with carrier Direct weighting on prepreg, but pressurize via heat resistant rubber elastomeric material, so that prepreg sufficiently follows internal layer electricity The concave-convex surface of base board.Prepreg with carrier can be laminated in the one side of internal layer circuit substrate, can also be laminated to interior On the two sides of layer circuit substrate.
Heating temperature (hereinafter also referred to " laminating temperature ") when lamination treatment, from prepreg is improved to internal layer circuit substrate Concave-convex surface trackability and from the point of view of obtaining the insulating layer of smooth surface, preferably 60 DEG C or more, more preferably 70 DEG C or more, and then preferably 80 DEG C or more, and then more preferably 90 DEG C or more, particularly preferably 100 DEG C or more, 110 DEG C or more Or 120 DEG C or more.In addition, from the exudation for preventing resin, from the point of view of obtaining the well-balanced insulating layer of thickness, lamination temperature The upper limit of degree be preferably 160 DEG C hereinafter, more preferably 150 DEG C hereinafter, in turn be preferably 140 DEG C hereinafter, in turn be more preferably 130 DEG C or less.It should be noted that laminating temperature refers to the surface temperature of heating crimping component, add via heat resistant rubber elastomeric material When pressure, refer to the temperature on the surface of the elastic material engaged with the prepreg with carrier.
Crimping pressure when lamination treatment, from improve prepreg for the concave-convex surface of internal layer circuit substrate trackability and From the point of view of obtaining the insulating layer of smooth surface, preferably 0.098MPa or more, more preferably 0.29MPa or more, Jin Eryou It is selected as 0.40MPa or more, and then more preferably 0.49MPa or more.In addition, from preventing the exudation of resin, obtaining the equilibrium of thickness From the viewpoint of good insulating layer, the upper limit of crimping pressure be preferably 1.77MPa hereinafter, more preferably 1.47MPa hereinafter, into And preferably 1.10MPa or less.
It crimping time when lamination treatment, is examined from the viewpoint for the concave-convex surface for making prepreg sufficiently follow internal layer circuit substrate Consider, preferably 10 seconds or more, more preferably 15 seconds or more, and then preferably 20 seconds or more, and then more preferably 25 seconds or more.Separately Outside, from the viewpoint of productivity, crimp the time the upper limit be preferably 300 seconds hereinafter, more preferably 250 seconds hereinafter, excellent in turn It is selected as 200 seconds hereinafter, being more preferably 150 seconds in turn hereinafter, particularly preferably 100 seconds or less or 50 seconds or less.
Vacuum degree when lamination treatment, from the viewpoint of it effectively can implement lamination treatment, preferably 0.01hPa with On, more preferably 0.05hPa or more, and then preferably 0.1hPa or more.In addition, from the viewpoint for the insulating layer for obtaining smooth surface From the viewpoint of preventing intrusion of the air to insulating layer, hole inhibited to generate, the upper limit of vacuum degree be preferably 27hPa hereinafter, More preferably 22hPa hereinafter, be preferably 17hPa hereinafter, being more preferably 13hPa or less in turn in turn.It should be noted that from hole is inhibited From the viewpoint of gap generates, the pumpdown time is preferably 20 seconds or more, and more preferably 30 seconds or more, 40 seconds or more, 50 seconds or more Or 60 seconds or more.
Using step (I), can obtain containing internal layer circuit substrate and the side engaged with prepreg with the internal layer circuit substrate The laminated body of the prepreg with carrier of formula setting.In the present invention, the excellent insulating layer of surface smoothness in order to obtain, it is important Be implementation steps (I) so that the maximum cross-section height (Rt) of the carrier film surface of the prepreg with carrier after step (I) Less than 5 μm.Such as the composition according to the prepreg and carrier film that use, type, operate above-mentioned laminating temperature, crimping pressure, pressure The lamination treatments condition such as time, vacuum degree, implementation steps (I) are connect, so that the maximum cross-section height (Rt) of carrier film surface is less than 5 μm。
From the point of view of obtaining the excellent insulating layer of surface smoothness, the prepreg with carrier after step (I) The maximum cross-section height (Rt) of carrier film surface be preferably 4.5 μm hereinafter, more preferably 4 μm hereinafter, in turn be preferably 3.5 μm with Under.The lower limit of the maximum cross-section height (Rt) is not particularly limited, but from the exudation for preventing resin, the equilibrium for obtaining thickness is good From the point of view of good insulating layer, usually 0.1 μm or more.
The maximum cross-section height (Rt) of carrier film surface can be used non-contact type surface roughness meter and be measured.As The specific example of non-contact type surface roughness meter can enumerate " the WYKO of ビ ー U イ Application ス Star Le メ Application Star NT9300”。
As long as it should be noted that conductor layer (circuit layout) is arranged in carrier film on the insulating layer obtained by solidifying prepreg It removes, such as can be removed between following steps (II) and step (III) before step, it can also be in following steps (III) it is removed after.In suitable embodiment, carrier film is removed after following steps (III).Carrier film can be used Removing manually also can use automatic stripper and carry out mechanical stripping.
The lamination treatment of step (I) can use commercially available vacuum laminator and carry out.It, can as commercially available vacuum laminator To enumerate the vacuum pack system that such as (strain) name mechanism makees made vacuum pressure type laminating machine, ニ チ ゴ ー モ ー ト Application (strain) system Device etc..
< step (II) >
In step (II), the laminated prepreg hot pressing with carrier is smoothed.
Smoothing techniques in step (II) can for example be implemented by that will heat crimping component from the pressurization of carrier film side.Make Component is crimped for heating, can be used with the component illustrated in step (I) is same component.
Obtain surface smoothness it is excellent, the difference of base ends and substrate center portion thickness is small, thickness equilibrium is good When the insulating layer got well, it is important that make the defined range of hot pressing temperature of step (II).In detail, in the layer for making step (I) Pressing temperature be T1 (DEG C), when the hot pressing temperature of step (II) is T2 (DEG C), it is important that set T2 so that T1 and T2 meet T2≤ The relationship of T1+10.From the point of view of obtaining both the balanced more excellent insulating layer of surface smoothness and thickness, T1 and T2 preferably satisfies the relationship of T2≤T1+5, more preferably meets the relationship of T2≤T1.As long as meet the relational expression with T1 and The melt viscosity of prepreg under T2 is above-mentioned specific range, and T2 is just not particularly limited, but usually its lower limit is 70 DEG C, The upper limit is 160 DEG C.It should be noted that the hot pressing temperature of step (II) refers to the surface temperature of heating crimping component, via heat-resisting rubber Glue elastomeric material under pressure, refers to the temperature on the surface of the elastic material engaged with the prepreg with carrier.
Crimping pressure and crimping time when smoothing techniques can be same as the lamination treatment condition in step (I).In addition, Smoothing techniques are suitble to implement (under atmospheric pressure) under normal pressure.
It the smoothing techniques of step (II) implementable 1 time, also can be implemented 2 times or more.By smoothing techniques implement 2 times with It when upper, can implement under the same conditions 2 times or more, and can also implement under different conditions 2 times or more.Such as by step (II) In the case that smoothing techniques are implemented 2 times, the hot pressing temperature in the 1st smoothing techniques is being set as T2 (DEG C), the 2nd time When hot pressing temperature in smoothing techniques is set as T3 (DEG C), T2 and T3 preferably satisfy T2-30≤T3≤T2+20 relationship, more excellent Be full sufficient T2-20≤T3≤T2+10 relationship.
The smoothing techniques of step (II) can use commercially available laminating machine and carry out.It should be noted that step (I) and step (II) above-mentioned commercially available vacuum laminator can be used continuously to carry out.Such as the peace of Room the 1st for having lamination treatment can be used The vacuum laminator of Room 2nd of cunningization processing, continuously implementation steps (I) and step (II).By the smoothing of step (II) In the case where processing implementation 2 times or more, 2 times or more smoothing techniques can be implemented repeatedly in above-mentioned Room 2nd, or can be used And then have the vacuum laminator of the room (such as Room the 3rd, Room the 4th) for implementing the 2nd later smoothing techniques, implement 2 The secondary above smoothing techniques.
< step (III) >
In step (III), prepreg heat cure is formed into insulating layer.
The condition of heat cure is not particularly limited, and can be used and usually adopts when forming the insulating layer of multilayer printed circuit board Condition.
For example, composition of heat cure condition resin combination according to used in prepreg of prepreg etc. and it is different, can So that range (preferably 150 DEG C~210 DEG C of range, more preferably 170 DEG C~190 that solidification temperature is 120 DEG C~240 DEG C DEG C range), make curing time 5 minutes~90 minutes range (preferably 10 minutes~75 minutes, more preferably 15 minutes~ 60 minutes).
Before carrying out heat cure, prepreg can be preheated at a temperature of lower than solidification temperature.Such as in thermosetting It, can more than and less than 120 DEG C, (preferably 60 DEG C or more and 110 DEG C be hereinafter, more preferably 70 DEG C or more and 100 at 50 DEG C before change DEG C or less) at a temperature of, by prepreg progress 5 minutes or more (preferably 5 minutes~150 minutes, more preferably 15 minutes~120 Minute) preheating.In the case of carrying out preheating, the preheating is also contained in step (III).
The heat cure of prepreg in step (III) carries out (under normal pressure) preferably under atmospheric pressure.
Heating furnace can be used to implement in the heat cure of step (III).When implementing the heat cure of prepreg using heating furnace, Prepreg is configured in heating furnace with plumbness, heat cure is carried out and forms insulating layer, it is possible thereby to disposably will be a large amount of Number put into heating furnace, can with from step (II) to the continuation mode of step (III) carry out smoothly operation, help It is improved in productivity.As heating furnace, such as cleaning oven (ヤ マ ト scientific (strain) system " ク リ ー ン オ ー Block Application can be used DE610 ") etc..
It is available to contain internal layer circuit substrate and the insulating layer engaged with the internal layer circuit substrate using step (III) Laminated body.As described above, when using the high prepreg of the total content of fiber base material and inorganic filling material, it can be exhausted by gained The thermal expansion coefficient of edge layer is suppressed to low degree, on the other hand, the surface of resulting insulating layer have with as in ground The corresponding fluctuating of concave-convex surface of layer circuit substrate, it is difficult to obtain the insulating layer of smooth surface.If surface of insulating layer rises Fu great has the case where as obstacle then when forming conductor layer on the surface of insulating layer with fine Wiring pattern.By that will put down Hot pressing is carried out under the conditions of as hot pressing temperature in cunningization step is set as higher degree etc., the mobility of resin is got higher, it can How much to improve the surface smoothness of insulating layer, but in this case, due to the exudation etc. of resin, lead to the layer of insulating layer Thick disturbance of equilibrium, centre portion and base ends, the thickness of rewarding insulating layer generate the tendency of big difference in a substrate.Root According to the tendency in recent years being also in progress with the slimming of multilayer printed circuit board, the slimming of insulating layer, the thickness The balanced bad reduction for being attributed to local insulating reliability sometimes.In contrast, multi-sheet printed line according to the present invention The manufacturing method of road plate, even if the prepreg high using the total content of fiber base material and inorganic filling material, can also form table The flatness in face is excellent and the difference of base ends and substrate center portion thickness is small, the also good insulation of equilibrium of thickness Layer.Therefore the present invention is to manufacture multi-sheet printed line using the high prepreg of the total content of fiber base material and inorganic filling material When the plate of road, the fine wiringization of multilayer printed circuit board and the invention of both slimmings are significantly assisted in.Using of the invention The multilayer printed circuit board of method manufacture is characterized in that, containing insulating layer, which is fiber base material and inorganic fill material The total content of material is high, the maximum cross-section height (Rt) on surface is low, in the small insulation of base ends and substrate center portion difference in thickness Layer.The difference in thickness of the maximum cross-section height (Rt) on the surface of insulating layer, the base ends of insulating layer and substrate center portion it is detailed Details condition is as described below.In one embodiment, which is characterized in that, containing meeting following (a) to (c) Condition insulating layer: when the total quality of the insulating layer (a) being set as 100 mass %, fiber base material and inorganic filling material Gross mass is 70 mass % or more；(b) the maximum cross-section height (Rt) on the surface of the insulating layer is less than 3 μm；(c) insulating layer Base ends thickness and substrate center portion thickness difference less than 2.5 μm.
The maximum cross-section height (Rt) of surface of insulating layer after step (III) is from can be in the surface of insulating layer with fine Wiring pattern formed conductor layer from the point of view of, preferably smaller than 3 μm, more preferably 2.8 μm hereinafter, in turn be preferably 2.6 μm with Under, and then more preferably 2.5 μm or less.The lower limit of the maximum cross-section height (Rt) is not particularly limited, usually 0.1 μm with It is first-class.
The maximum cross-section height (Rt) of surface of insulating layer, can for removing carrier film after insulating layer exposing surface, It is measured using non-contact type surface roughness meter.
The difference of the thickness of after step (III), the insulating layer of base ends thickness and the insulating layer in substrate center portion, from Entire substrate range realize needed for insulating reliability from the point of view of, preferably smaller than 2.5 μm, more preferably 2.4 μm with Under, so preferably 2.2 μm hereinafter, in turn be more preferably 2.0 μm hereinafter, particularly preferably 1.8 μm or less or 1.6 μm or less. The lower limit of the difference of the thickness of the insulating layer of the thickness and substrate center portion of the insulating layer of base ends is not particularly limited, can be with It is 0 μm.In the present invention, due to may be formed so that the insulating layer small in the difference of base ends and substrate center portion thickness, Insulating reliability even the therefore thin situation of insulating layer, needed for can also being realized in the range of entire substrate.
The difference of the thickness of the insulating layer of the thickness and substrate center portion of the insulating layer of base ends, can be for step (III) central portion of laminated body obtained in and each section of end, use the insulation right above measurement microscope circuit conductor Layer thickness and calculate.As microscopical specific example, " the microscope VK-8510 " of KEYENCE (strain) system can be enumerated.
< other step >
The manufacturing method of multilayer printed circuit board of the invention can include: in turn (IV) on the insulating layer aperture the step of, (V) the step of being roughened the insulating layer, (VI) are formed on roughened surface of insulating layer using plating and are led The step of body layer.These steps (IV) to (VI) can according to used in the manufacture in multilayer printed circuit board, this field skill Various methods well known to art personnel are implemented.It should be noted that when removing carrier film after step (III), the removing of the carrier film It can implement between step (III) and step (IV) or between step (IV) and step (V).
The step of step (IV) is aperture on the insulating layer, it is possible thereby to which through-hole etc. is formed on the insulating layer.Through-hole in order to The electrical connection of interlayer and be set, it is contemplated that the characteristic of insulating layer, can be by using drill bit, laser, plasma etc. Known method formed.Such as there are in the case where carrier film, laser can be irradiated from carrier film, and formed in insulating layer Through-hole.
As laser light source, can enumerate such as carbon dioxide laser, YAG laser, excimer laser.Its In, from the point of view of process velocity, cost, preferably carbon dioxide laser.
Commercially available laser device can be used to implement in aperture processing.As commercially available carbon dioxide laser device, Can enumerate such as Hitachi's ビ ア メ カ ニ Network ス (strain) system LC-2E21B/1C, Mitsubishi Electric's (strain) system ML605GTWII, Panasonic welds the substrate aperture laser machine of シ ス テ system (strain) system.
Step (V) is the step of being roughened insulating layer.Process, the condition of roughening treatment are no particularly It limits, it can be using the well known process usually used when forming the insulating layer of multilayer printed circuit board, condition.Such as it can be with Successively implement that the swelling process of swelling liquid is utilized, the roughening treatment that oxidant is utilized, be utilized at the neutralization of neutralizer Reason, and insulating layer is roughened.It as swelling liquid, is not particularly limited, aqueous slkali, surface-active can be enumerated Agent solution etc., preferably aqueous slkali, the aqueous slkali are more preferably sodium hydroxide solution, potassium hydroxide solution.As commercially available swollen Moisten liquid, ス ウ ェ リ Application グ デ ィ ッ プ セ キ ュ リ ガ Application ス P, the ス of such as ア ト テ ッ Network ジ ャ パ Application (strain) system can be enumerated ウ ェ リ Application グ デ ィ ッ プ セ キ ュ リ ガ Application ス SBU etc..The swelling process that swelling liquid is utilized is not particularly limited, such as can To be carried out by the way that insulating layer is impregnated 1 minute~20 minutes in 30~90 DEG C of swelling liquid.From by the resin of insulating layer Swelling is suppressed to from the point of view of suitable level, and insulating layer is preferably made to impregnate 5 seconds~15 points in 40~80 DEG C of swelling liquid Clock.Oxidant is not particularly limited, and can enumerate and for example dissolve potassium permanganate, sodium permanganate in the aqueous solution of sodium hydroxide Alkaline permanganic acid solution.The roughening treatment of the oxidants such as alkaline permanganic acid solution is utilized preferably by adding insulating layer 10 minutes~30 minutes are impregnated in the oxidizing agent solution of heat to 60 DEG C~80 DEG C to carry out.In addition, in alkaline permanganic acid solution The concentration of permanganate is preferably 5 mass of mass %~10 %.As commercially available oxidant, such as ア ト テ ッ Network ジ ャ can be enumerated The U Application セ Application ト レ ー ト U 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 etc. of パ Application (strain) system Alkaline permanganic acid solution.In addition, preferably acid aqueous solution can enumerate such as ア ト as commercially available product as neutralizer The リ ダ Network シ ョ Application ソ リ ュ ー シ ョ Application セ キ ュ リ ガ Application ト P of テ ッ Network ジ ャ パ Application (strain) system.The processing of neutralizer is utilized It can be by impregnating the process face for having carried out roughening treatment using oxidizing agent solution 5 minutes in 30~80 DEG C of neutralizer It carries out within~30 minutes.Consider from operability etc., the object of roughening treatment will have preferably been carried out using oxidizing agent solution Object impregnates 5 minutes~20 minutes methods in 40~70 DEG C of neutralizer.
Step (VI) is to utilize plating the step of forming conductor layer on roughened surface of insulating layer.
Conductor material used in conductor layer is not particularly limited.In suitable embodiment, conductor layer, which contains, to be selected from The metal of one or more of gold, platinum, palladium, silver, copper, aluminium, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium.Conductor layer can be list Metal layer or alloy-layer can enumerate the alloy (example for example by the metal of more than two kinds selected from above-mentioned metal as alloy-layer Such as nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) formed layer.Wherein, versatility, the cost, pattern formed from conductor layer The easiness of change angularly considers, preferably 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 alloy-layer, 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 the single metal layer of preferably copper.
Conductor layer can be single layer structure, be also possible to 2 layers or more of the Dan Jin comprising different types of metal or alloy Belong to multilayered structure obtained by layer or alloy layer laminate.When conductor layer is multilayered structure, the layer to connect with insulating layer is preferably chromium, zinc Titanium single metal layer or nickel-chromium alloy alloy-layer.
The thickness of conductor layer depends on the design of required multilayer printed circuit board, but generally 3 μm~35 μm, preferably 5 μm~30 μm.
Conductor layer can use plating to be formed.Such as the known skill such as can use semi-additive process, full additive method Art carries out plating on the surface of insulating layer, forms the conductor layer with required Wiring pattern.Semi-additive process is utilized hereinafter, showing Form the example of conductor layer.
Firstly, conformal at plating layer (め っ き シ ー De layer) using electroless plating on the surface of insulating layer.Then, in shape At plating layer on, corresponding to required Wiring pattern, form the mask pattern for exposing a part of plating layer.In exposing On plating layer, after forming metal layer using plating, mask pattern is removed.Then, unwanted plating layer is removed using etching etc., The conductor layer with required Wiring pattern can be formed.It, can be in the manufacturing method of multilayer printed circuit board of the invention The excellent insulating layer of surface smoothness is formed, therefore conductor layer can be formed with fine Wiring pattern on which insulating layer.
By using the multilayer printed circuit board manufactured using method of the invention, semiconductor device can be manufactured.Pass through Semiconductor chip is installed at the conducting position of multilayer printed circuit board of the invention, semiconductor device can be manufactured." conducting portion Position " refers to " position of the electric signal in conduction multilayer printed circuit board ", which can be appointing for the position of surface or landfill One.In addition, as long as semiconductor chip is not particularly limited using semiconductor as the electrical circuit components of material.
As long as the installation method of semiconductor chip when manufacturing semiconductor device of the invention makes semiconductor chip effectively It functions, is not particularly limited, specifically, wire bonding installation method, flip-chip installation method, benefit can be enumerated With the installation method of bumpless build up layer (プ layers of バ Le プ な ビ Le De ア ッ, BBUL), utilize anisotropic conductive film (ACF) installation method utilizes installation method of non-conductive film (NCF) etc..
Embodiment
Hereinafter, being based on embodiment and comparative example, the present invention is further illustrated, but the present invention is not limited to implementations below Example.It should be noted that " part " in following record refers to " mass parts ".
It is illustrated firstly, for measuring method, the evaluation method in the evaluation of physical property of this specification.
(preparation that substrate is used in measurement, evaluation)
(1) production of internal layer circuit substrate
On glass cloth base material epoxy resin two sides copper foil covered lamination (35 μm of the thickness of copper foil, substrate thickness 0.8mm, Matsushita Electrician (strain) system " R5715ES ") on form the pattern of IPC MULTI-PURPOSE TEST BOARD NO. IPC C-25 (comb teeth pattern (residual copper ratio 48%) of the line width/spacing than=600/660 μm).Then, by the two sides of substrate micro-etching agent (メ ッ Network (strain) system " CZ8100 ") it is roughened, make internal layer circuit substrate.
It should be noted that using the glass cloth base material epoxy resin two that the thickness of copper foil is changed into 7 μm about embodiment 4 The copper foil covered lamination in face.
(2) lamination of the prepreg with carrier
Using the laminating machine (name machine (strain) makes " MVLP500/600-IIB ") with the pressurization of Room 2, will be made in following production examples The prepreg with carrier made is laminated to the two sides of internal layer circuit substrate in a manner of engaging prepreg with internal layer circuit substrate On.After lamination treatment makes air pressure 13hPa or less and depressurizing 30 seconds, the laminating temperature T1 (DEG C) shown in table 2 and pressure Make its crimping under conditions of power 0.74MPa 30 seconds to carry out.It should be noted that being laminated to Room the 1st of the laminating machine with the pressurization of Room 2 Middle implementation.
(3) smoothing of the prepreg with carrier
By the laminated prepreg with carrier it is above-mentioned have Room 2 pressurization laminating machine Room the 2nd in carry out hot pressing and Smoothing.Smoothing techniques pass through under atmospheric pressure (normal pressure), hot pressing temperature T2 (DEG C) and pressure 0.55MPa shown in table 2 Under conditions of carry out its crimping 90 seconds.
It should be noted that implementing 2 smoothings in Room the 2nd of the above-mentioned laminating machine for having the pressurization of Room 2 for embodiment 7 Processing.1st smoothing techniques pass through under atmospheric pressure (normal pressure), hot pressing temperature T2 (DEG C) and pressure shown in table 2 Make its crimping under conditions of 0.55MPa 90 seconds to carry out.2nd smoothing techniques by under atmospheric pressure (normal pressure), in table 2 Shown in make its crimping under conditions of hot pressing temperature T3 (DEG C) and pressure 0.55MPa 90 seconds to carry out.
(4) heat cure of prepreg
After smoothing, substrate is heated 30 minutes at 180 DEG C, prepreg heat cure is formed into insulating layer.
The measurement > of the melt viscosity of < prepreg
The prepreg that 20 are overlapped and forms 1mm thickness is punched to diameter 20mm, preparation measurement sample.For the survey of preparation Random sample product measure melt viscosity using measurement of dynamic viscoelasticity device ((strain) UBM system " Rheogel-G3000 ").In heating speed It spends under the determination condition of 5 DEG C/min, 2.5 DEG C of measuring temperature interval, vibration frequency 1Hz and measures dynamic viscoelastic rate, acquire 2 institute of table Melt viscosity (pool) when temperature T2 (DEG C) shown.Cone-plate is used in the fixture of measurement.
The measurement > of the maximum cross-section height (Rt) of carrier film surface after < lamination step
After prepreg with carrier is pressed on internal layer circuit substrate, the evaluation substrate of 200mm × 200mm is cut out, is surveyed The maximum cross-section height (Rt) of the carrier film surface of the fixed prepreg with carrier.Maximum cross-section height (Rt) benefit of carrier film surface It is acquired with following numerical value, the numerical value is using non-contact type surface roughness meter (ビ ー U イ Application ス ツルメン Star society system " WYKO NT9300 "), using VSI contact mode, 10 times of lens, make numerical value obtained by measurement range 0.82mm × 1.1mm. Measurement is that exposing surface in the state that carrier film is attached on prepreg, for carrier film carries out.
The measurement > of the maximum cross-section height (Rt) of < surface of insulating layer
After prepreg is carried out heat cure, the demoulding PET film as carrier film is removed, for the exposing table of insulating layer Face measures maximum cross-section height (Rt).The maximum cross-section height (Rt) of surface of insulating layer is acquired using following numerical value, the numerical value It is to be connect using non-contact type surface roughness meter (ビ ー U イ Application ス ツルメン Star society's system " WYKO NT9300 ") using VSI Touch formula, 10 times of lens, make numerical value obtained by measurement range 0.82mm × 1.1mm.It should be noted that measurement reality as so following Apply: for be provided with comb teeth pattern (residual copper ratio 48%) of the line width/spacing than=600/660 μm circuit layout region, with across The more part with circuit layout and not no mode as the part of circuit layout, acquire the average value at 3.
In table 2, by Rt less than 2.5 μm the case where is set as "○", by Rt be 2.5 μm more than and less than 3 μm the case where set For " △ ", the Rt situation for being 3 μm or more is set as "×".It should be noted that for comparative example 1,3 and 5, due to being based on internal layer circuit The generation of the fluctuating of the concave-convex surface of substrate and generate fold, therefore omit maximum cross-section height (Rt) measurement.In addition, about Comparative example 6 omits the measurement of maximum cross-section height (Rt) due to generating hole.
The evaluation > of the appearance of < surface of insulating layer
After prepreg heat cure, the demoulding PET film as carrier film is removed, for the exposing surface of insulating layer, is seen Examine appearance.For the appearance of surface of insulating layer, insulated using microscope (KEYENCE (strain) makes " microscope VK-8510 ") observation The surface 3cm of layer2。
In table 2, will not have to be denoted as the case where being denoted as " 〇 " the case where fold or hole, will have fold or hole “×”。
The measurement > of the difference of the thickness of < base ends and the insulating layer in substrate center portion
After prepreg heat cure, the demoulding PET film as carrier film is removed, measures base ends and substrate center portion Insulating layer thickness difference.In detail, for each region (1cm of base ends and substrate center portion2), make to cut by grinding After the smoothing of face, the insulating layer right above microscope (KEYENCE (strain) makes " microscope VK-8510 ") measurement circuit conductor is used Thickness.
In table 2, by the difference of base ends and the thickness of the insulating layer in substrate center portion less than 2.5 μm the case where is denoted as Situation for 2.5 μm or more is denoted as "×" by " 〇 ".
(production example 1)
(1) preparation of resin varnish
Make liquid bisphenol A type epoxy resin (epoxide equivalent 180, Mitsubishi Chemical's (strain) system while stirring " jER828EL ") 15 parts, 25 parts of 4 functional epoxy resins of naphthalene type (epoxide equivalent 163, DIC (strain) system " HP4710 "), naphthylene ether 45 parts of type epoxy resin (epoxide equivalent 213, DIC (strain) system " EXA-7311G4 ") and phenoxy resin (ジ ャ パ Application エ Port キ シ レ ジ Application (strain) makes " YL7553BH30 ") 8 parts dissolve by heating in MEK30 parts and 30 parts of cyclohexanone of in the mixed solvent.Thereto Mix consolidating for phenol system curing agent (hydroxyl equivalent 125, DIC (strain) the making " LA7054 ", about 12 mass % of nitrogen content) of the skeleton containing triazine The solid of 10 parts of the MEK solution of 60 mass % of body ingredient, naphthalene type curing agent (functional equivalent 153, DIC (strain) system " HPC9500 ") 40 parts of MEK solution, the fire retardant (hydroxyl equivalent 162, (strain) three light system " HCA-HQ ", phosphorus content 9.5%) 8 of 60 weight % of ingredient Part, spherical two be surface-treated with amino silicone methane series coupling agent (Shin-Etsu Chemial Co., Ltd's system " KBM-573 ") 250 parts of silica (1.0 μm of average grain diameter, (strain) ア De マ テ ッ Network ス system " SOC4 "), equably using high speed rotation mixer Dispersion, prepares resin varnish.
(2) preparation of the prepreg 1 with carrier
Resin varnish obtained in above-mentioned (1) is infiltrated in fiber base material, and ((strain) has pool to make made 1027 glass cloth, thickness 19 μm of degree) in, it is 5 minutes dry at 110 DEG C using clothes closet type drying oven, prepare prepreg.Resin combination in prepreg contains Amount be 81 mass %, prepreg with a thickness of 50 μm.Then, using batch-type vacuum pressed laminating machine, ((strain) name mechanism is made made " MVLP-500 "), by the PET film (リ Application テ ッ Network (strain) makes " PET501010 ", 38 μm of thickness) with release layer so that release layer The mode contacted with prepreg is laminated on the two sides of prepreg, forms the prepreg 1 with carrier.In the prepreg 1 with carrier In, the total content of fiber base material and inorganic filling material in prepreg is 72 mass %.When substrate is evaluated in production, by a side PET film (protective film) with release layer remove to use.
(production example 2)
(1) preparation of resin varnish
Resin varnish is prepared as with production example 1.
(2) preparation of the prepreg 2 with carrier
In addition to using fiber base material ((strain) has pool to make made 1000 glass cloth, 14 μm of thickness) to replace fiber base material Other than ((strain) has pool to make made 1027 glass cloth, 19 μm of thickness), other process preparation band carriers same as production example 1 Prepreg 2.Resin composition content in prepreg is 80 mass %, prepreg with a thickness of 33 μm.In addition, in band carrier Prepreg 2 in, the total content of fiber base material and inorganic filling material in prepreg is 72 mass %.
(production example 3)
(1) preparation of resin varnish
Make liquid bisphenol A type epoxy resin (epoxide equivalent 180, Mitsubishi Chemical's (strain) system while stirring " jER828EL ") 15 parts, 80 parts of naphthylene ether type epoxy (epoxide equivalent 213, DIC (strain) system " EXA-7311G4 ") and 8 parts of phenoxy resin (ジ ャ パ Application エ Port キ シ レ ジ Application (strain) makes " YL7553BH30 ") is dissolved by heating in MEK20 parts and hexamethylene The in the mixed solvent that 20 parts of ketone.Phenolic resin (hydroxyl equivalent 125, DIC (strain) system of the skeleton containing triazine are mixed thereto About 12 weight % of " LA7054 ", nitrogen content) 10 parts of the MEK solution of 60 weight % of solid component, naphthalene type curing agent (functional equivalent 215, Nippon Steel's (strain) system " SN485 ") 40 parts of the MEK solution of 60 weight % of solid component, fire retardant (hydroxyl equivalent 162, (strain) three light system " HCA-HQ ", phosphorus content 9.5%) 8 parts, with amino silicone methane series coupling agent (Shin-Etsu Chemial Co., Ltd's system " KBM-573 ") preparing spherical SiO 2 (1.0 μm of the average grain diameter, (strain) ア De マ テ ッ Network ス system that are surface-treated " SOC4 ") 240 parts, it is uniformly dispersing with high speed rotation mixer, prepare resin varnish.
(2) preparation of the prepreg 3 with carrier
Using resin varnish obtained in above-mentioned (1), the prepreg 3 with carrier is prepared with process same as production example 1. Resin composition content in prepreg is 81 mass %, prepreg with a thickness of 50 μm.In addition, in the prepreg 3 with carrier In, the total content of fiber base material and inorganic filling material in prepreg is 71 mass %.
[table 1]
。
1 > of < embodiment
Using the prepreg 1 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.As shown in table 2, laminating temperature T1 is 140 DEG C, and hot pressing temperature T2 is 140 DEG C.Respectively evaluation result is shown in table 2.
2 > of < embodiment
Using the prepreg 1 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.As shown in table 2, laminating temperature T1 is 140 DEG C, and hot pressing temperature T2 is 120 DEG C.Respectively evaluation result is shown in table 2.
3 > of < embodiment
Using the prepreg 1 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.As shown in table 2, laminating temperature T1 is 120 DEG C, and hot pressing temperature T2 is 120 DEG C.Respectively evaluation result is shown in table 2.
4 > of < embodiment
Using the prepreg 2 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.As shown in table 2, laminating temperature T1 is 140 DEG C, and hot pressing temperature T2 is 120 DEG C.Respectively evaluation result is shown in table 2.
5 > of < embodiment
Using the prepreg 1 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.As shown in table 2, laminating temperature T1 is 130 DEG C, and hot pressing temperature T2 is 110 DEG C.Respectively evaluation result is shown in table 2.
6 > of < embodiment
Using the prepreg 3 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.As shown in table 2, laminating temperature T1 is 130 DEG C, and hot pressing temperature T2 is 110 DEG C.Respectively evaluation result is shown in table 2.
7 > of < embodiment
Using the prepreg 1 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.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 It is shown in table 2.
1 > of < comparative example
Using the prepreg 1 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.As shown in table 2, laminating temperature T1 is 140 DEG C, and hot pressing temperature T2 is 160 DEG C.Respectively evaluation result is shown in table 2.
2 > of < comparative example
Using the prepreg 1 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.As shown in table 2, laminating temperature T1 is 140 DEG C, and hot pressing temperature T2 is 100 DEG C.Respectively evaluation result is shown in table 2.
3 > of < comparative example
Using the prepreg 1 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.As shown in table 2, laminating temperature T1 is 120 DEG C, and hot pressing temperature T2 is 140 DEG C.Respectively evaluation result is shown in table 2.
4 > of < comparative example
Using the prepreg 1 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.As shown in table 2, laminating temperature T1 is 120 DEG C, and hot pressing temperature T2 is 100 DEG C.Respectively evaluation result is shown in table 2.
5 > of < comparative example
Using the prepreg 1 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.As shown in table 2, laminating temperature T1 is 100 DEG C, and hot pressing temperature T2 is 140 DEG C.Respectively evaluation result is shown in table 2.
6 > of < comparative example
Using the prepreg 1 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.As shown in table 2, laminating temperature T1 is 100 DEG C, and hot pressing temperature T2 is 100 DEG C.Respectively evaluation result is shown in table 2.
7 > of < comparative example
Using the prepreg 3 with carrier, according to the process of above-mentioned (preparation that substrate is used in measurement, evaluation), preparation evaluation base Plate.As shown in table 2, laminating temperature T1 is 140 DEG C, and hot pressing temperature T2 is 140 DEG C.Respectively evaluation result is shown in table 2.
[table 2]
。

Claims (9)

1. the manufacturing method of multilayer printed circuit board, it includes
(I) prepreg with carrier of prepreg will be formed on a carrier film so that prepreg was engaged with internal layer circuit substrate Mode be laminated to step on internal layer circuit substrate,
(II) the prepreg hot pressing by laminated with carrier and the step of smooth and
(III) the step of prepreg heat cure being formed into insulating layer,
The manufacturing method of the multilayer printed circuit board is characterized in that,
When the total quality of prepreg is set as 100 mass %, the gross mass of fiber base material and inorganic filling material in prepreg For 70 mass % or more,
The melt viscosity of prepreg under the hot pressing temperature of step (II) is 300~10000 pools,
The maximum cross-section height (Rt) of the carrier film surface of the prepreg with carrier after step (I) less than 5 μm, and
The laminating temperature of step (I) is set as T1 (DEG C), when the hot pressing temperature of step (II) is set as T2 (DEG C), T1 and T2 meet T2 The relationship of≤T1+10.
2. according to the method described in claim 1, wherein, T1 and T2 meet the relationship of T2≤T1+5.
3. according to the method described in claim 1, wherein, step (II) is implemented 2 times or more.
4. according to the method described in claim 1, wherein, the maximum cross-section height of the surface of insulating layer after step (III) (Rt) less than 3 μm.
5. according to the method described in claim 1, wherein, prepreg further contains epoxy resin and curing agent.
6. according to the method described in claim 5, wherein, prepreg is by making containing epoxy resin, curing agent and inorganic fill The resin combination of material is impregnated into fiber base material and is formed.
7. according to the method described in claim 1, wherein, carrier film is stripped after step (III).
8. method according to any one of claims 1 to 7, wherein in step (III), by prepreg in heating furnace It is interior to be configured with plumbness, it carries out heat cure and forms insulating layer.
9. multilayer printed circuit board contains the insulating layer for meeting the condition of following (a) to (c):
(a) when the total quality of the insulating layer being set as 100 mass %, the gross mass of fiber base material and inorganic filling material is 70 Quality % or more；
(b) the maximum cross-section height (Rt) on the surface of the insulating layer is less than 3 μm；With
(c) difference of the thickness of the base ends of the insulating layer and the thickness in substrate center portion is less than 2.5 μm.
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