CN101977765A - Insulating resin sheet and method for manufacturing multilayer printed wiring board using the insulating resin sheet - Google Patents
Insulating resin sheet and method for manufacturing multilayer printed wiring board using the insulating resin sheet Download PDFInfo
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- CN101977765A CN101977765A CN2009801103534A CN200980110353A CN101977765A CN 101977765 A CN101977765 A CN 101977765A CN 2009801103534 A CN2009801103534 A CN 2009801103534A CN 200980110353 A CN200980110353 A CN 200980110353A CN 101977765 A CN101977765 A CN 101977765A
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- insulating resin
- resin sheet
- layer
- sheet
- solidfied material
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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
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4661—Adding a circuit layer by direct wet plating, e.g. electroless plating; insulating materials adapted therefor
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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
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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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/14—Related to the order of processing steps
- H05K2203/1476—Same or similar kind of process performed in phases, e.g. coarse patterning followed by fine patterning
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
Abstract
Disclosed is an insulating resin sheet composed of a prepreg, which is used for forming an insulating layer of a multilayer printed wiring board. By using this insulating resin sheet, a sheet-like fiber base contained in the prepreg is not exposed from the surface of the insulating layer. In the insulating resin sheet, a layer of a cured product of a thermosetting resin composition is formed on one side of the prepreg. Preferably, the insulating resin sheet additionally has a supporting layer on the cured product layer. An insulating resin sheet having such a structure can be obtained by bonding a cured product sheet, wherein a cured product layer of a thermosetting resin composition is formed on a supporting body, onto one side of a prepreg.
Description
Technical field
The present invention relates to the preparation method that the insulating barrier for multilayer printed-wiring board is formed with the insulating resin sheet of usefulness and uses the multilayer printed-wiring board of this insulating resin sheet.
Background technology
The technology of preparing of known multilayer printed-wiring board was the preparation method by compound (build-up) mode of intermeshing insulating barrier and conductor layer on core substrate in the past.Insulating barrier uses the adhesive film that forms the heat-curing resin layer on plastic sheeting specially when forming, adhesive film is laminated to (stacked) on the internal layer circuit substrate, peels off plastic sheeting, makes the heat-curing resin heat cure then, forms insulating barrier thus.Have the tendency of day by day slimming because the demand of electronic instrument and electronic unit miniaturization in multilayer printed-wiring board, for example requires core substrate slimming or simplification etc. this year.Like this, in the process of seeking the multilayer printed-wiring board slimming, in order to keep the mechanical strength of multilayer printed-wiring board, adopting prepreg is effective as the material that forms interlayer insulating film.
For example disclose in patent documentation 1 and the patent documentation 2 and on a face of prepreg, formed the B-stage resin composition sheet of addition with the resin combination layer.
Patent documentation 1: TOHKEMY 2003-249764 communique
Patent documentation 2: TOHKEMY 2003-313324 communique
Summary of the invention
When prepreg was applied to interlayer insulating film, via lamination or the thermal cure step to the internal layer circuit substrate, the expansion mobile or glass cross that contains the resin combination that is immersed in the prepreg made the resin combination layer attenuation on prepreg surface.Therefore, when making the surface of insulating layer roughening treatment in order to form conductor layer by plating with oxidant etc., the fibrous pieces base material exposed problems in the prepreg takes place.Therefore, the inventor finds: in the preparation method of the multilayer printed-wiring board of complex method, above-mentioned patent documentation 1 and 2 described hot curing resin composition layers attempt adopting stacked insulating resin sheet on a face of prepreg.That is, when being laminated to this insulating resin sheet on the internal layer circuit substrate by vacuum laminator, insulating resin sheet is fully followed the concavo-convex place of circuit of internal layer circuit substrate, and the concavo-convex imbedibility of circuit is also good.And concavo-convex by the circuit of the insulating resin sheet of lamination reflection internal layer circuit substrate, its surperficial concave-convex surface.Therefore, with metallic plate insulating resin sheet is heated under normal pressure in order to make the insulating resin sheet surface smoothingization and pressurize, when making surface smoothing, the hot curing resin composition laminar flow of finding the insulating resin sheet surface is moving, the reflection circuit is concavo-convex, and the thickness of a part of hot curing resin composition layer has the phenomenon of attenuation.Find also that in addition after making the insulating resin sheet heat cure, forming insulating barrier, make the surface of insulating layer alligatoring, when forming conductor layer by plating, the fibrous pieces base material of prepreg exposes from the part of thickness attenuation, is going wrong aspect the conductor layer formation.
Therefore, problem of the present invention is to provide the insulating resin sheet that above-mentioned fibrous pieces base material exposes problem, has the fibrous pieces base material to occur when using this material preparation multilayer printed-wiring board.
The inventor addresses the above problem to have carried out deep research, the result, when the insulating resin sheet of solidfied material layer that will contain hot curing resin composition and prepreg layer is used for the preparation of multilayer printed-wiring board, even make the surface of insulating layer alligatoring, also can suppress exposing of above-mentioned fibrous pieces base material, thereby finish the present invention.
That is, the present invention comprises following content.
[1] insulating resin sheet, this insulating resin sheet are the insulating resin sheets that has the solidfied material layer of hot curing resin composition on a face of prepreg.
[2] above-mentioned [1] described insulating resin sheet wherein, further has support body layer on the solidfied material layer.
[3] above-mentioned [2] described insulating resin sheet, this insulating resin sheet are that the face that the solidfied material sheet that will be formed with the solidfied material layer of hot curing resin composition on supporter is adhered to prepreg obtains.
[4] above-mentioned [2] or [3] described insulating resin sheet, wherein, solidfied material layer one side of support body layer carried out demoulding processing.
[5] each described insulating resin sheet in above-mentioned [2]-[4], wherein, support body layer is a plastic sheeting.
[6] each described insulating resin sheet in above-mentioned [1]-[5], wherein, the prepreg face of insulating resin sheet is protected with protective film.
[7] each described insulating resin sheet in above-mentioned [1]-[6], wherein, the thickness of prepreg is 10-70 μ m.
[8] each described insulating resin sheet in above-mentioned [1]-[7], wherein, the solidfied material layer of hot curing resin composition is 1-30 μ m.
[9] each described insulating resin sheet in above-mentioned [1]-[8], this insulating resin sheet is used to comprise the preparation method of the multilayer printed-wiring board of following steps: (1) lamination step, insulating resin sheet is arranged on the circuit substrate, it is contacted with two faces or a face of circuit substrate, under reduced pressure, heat and pressurize via elastomeric material, thus insulating resin sheet is laminated on the circuit substrate; (2) smoothing step heats and pressurizes by metallic plate or the metallic roll insulating resin sheet after to lamination, makes insulating resin sheet level and smooth; And (3) thermal cure step, the insulating resin sheet after level and smooth is carried out heat cure.
[10] above-mentioned [9] described insulating resin sheet, wherein, the solidfied material layer of hot curing resin composition does not have flowability basically in lamination step and smoothing step.
[11] multilayer printed-wiring board, this multilayer printed-wiring board forms insulating barrier by each described insulating resin sheet in above-mentioned [1]-[10].
[12] preparation method of multilayer printed-wiring board, the method includes the steps of: (1) lamination step, each described insulating resin sheet in above-mentioned [1]-[10] is arranged on the internal layer circuit substrate, prepreg layer is contacted with two faces or a face of internal layer circuit substrate, under reduced pressure, heat and pressurize via elastomeric material, insulating resin sheet is laminated on the internal layer circuit substrate thus; (2) smoothing step heats and pressurizes by metallic plate or the metallic roll insulating resin sheet after to lamination; And (3) thermal cure step, the insulating resin sheet after level and smooth is carried out heat cure.
[13] above-mentioned [12] described method, wherein, the heating of the insulating resin sheet of lamination step and smoothing step and pressurization are carried out from support body layer.
[14] above-mentioned [12] or [13] described method, this method further comprises: the opening step of perforate on insulating barrier; This insulating barrier is carried out the alligatoring step of roughening treatment; By plating, on the surface of insulating layer after the alligatoring, form the plating step of conductor layer; And the circuit that forms circuit on conductor layer forms step.
According to insulating resin sheet of the present invention, on the internal layer circuit substrate during lamination, it is concavo-convex that insulating resin sheet can fully be followed the circuit of internal layer circuit substrate by vacuum laminator, and the concavo-convex imbedibility of circuit is good.In addition, when making behind the lamination, can reflect that also circuit is concavo-convex, suppress the phenomenon of the thickness attenuation of resin combination layer the insulating resin sheet surface smoothing.Therefore, behind heat cure formation insulating barrier, even make the surface of insulating layer alligatoring, the fiber base material of prepreg can not expose, and can carry out the formation of conductor layer by plating well, can prepare the high multilayer printed-wiring board of reliability.
The specific embodiment
Following according to its preferred embodiment explanation the present invention.
The prepreg of using among the present invention is hot curing resin composition to be contained be dipped in the fibrous fiber base material, obtains by heat drying.
As long as hot curing resin composition is applied to the insulating barrier of multilayer printed-wiring board, be not particularly limited, all can use, the object lesson of described hot curing resin composition can be to contain at least: the heat-curing resin of epoxy resin, cyanate ester resin, phenolic resins, BMI/cyanate resin, polyimide resin, acrylic resin, vinyl benzyl resin etc. and the composition of curing agent thereof.Wherein, heat-curing resin preferably contains the composition of epoxy resin, for example preferably contains the composition of epoxy resin, thermoplastic resin and curing agent.
Epoxy resin for example has: bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol f type epoxy resin, phosphorous epoxy resin, bisphenol-s epoxy resin, alicyclic epoxy resin, aliphatic series chain epoxy resin, phenolic resin varnish type epoxy resin, the cresols phenolic resin varnish type epoxy resin, bisphenol-A phenolic varnish type epoxy resin, epoxy resin with butadiene structure, the diglycidyl ether thing of bis-phenol, the diglycidyl ether thing of naphthalene glycol, the glycidyl etherificate thing of phenols, and the diglycidyl ether thing of alcohols, and the alkyl substituent of these epoxy resin, halide and hydride etc.These epoxy resin can only use any a kind, also can use mixing more than 2 kinds.
Wherein, from hear resistance, insulating reliability, consider, the preferred bisphenol A type epoxy resin of epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, has the epoxy resin of butadiene structure with the angle of the stickiness of metal film.The object lesson of described epoxy resin has: aqueous bisphenol A type epoxy resin (" the Epicote 828EL " of Japanese epoxy (strain) preparation), naphthalene type bifunctional epoxy resin (" HP4032 " of big Japanese ink chemical industry (strain) preparation, " HP4032D "), naphthalene type four sense epoxy resin (" HP4700 " of big Japanese ink chemical industry (strain) preparation), naphthol type epoxy resin (Dongdu changes into " ESN-475V " of (strain) preparation), epoxy resin (" PB-3600 " of Daicel chemical industry (strain) preparation) with butadiene structure, epoxy resin (" NC3000H " of Japanese chemical drug (strain) preparation with biphenyl structural, " NC3000L ", " YX4000 " of japan epoxy resin (strain) preparation) etc.
In order to make cured composition have appropriate flexibility etc., can cooperate thermoplastic resin in the hot curing resin composition.Described thermoplastic resin for example has: phenoxy resin, polyvinyl acetal resin, polyimides, polyamidoimide, polyether sulfone, polysulfones etc.These thermoplastic resins can only use wherein a kind separately, also can will be used in combination more than 2 kinds.When being 100% weight with the nonvolatile component of hot curing resin composition, this thermoplastic resin preferably cooperates with the ratio of 0.5-60% weight, and more preferably the ratio with 3-50% weight cooperates.
The commercial goods of phenoxy resin for example has: Dongdu changes into (strain) preparation FX280, FX293, japan epoxy resin (strain) preparation YX8100, YL6954, YL6974 etc.
Polyvinyl acetal resin preferably polyethylene butyral resin, the commercial goods of polyvinyl acetal resin for example has: electrochemical Butyral 4000-2,5000-A, 6000-C, the 6000-EP of electrochemical industry (strain) preparation, the S-REC BH series of ponding chemical industry (strain) preparation, BX series, KS series, BL series, BM series etc.
The commercial goods of polyimides for example has: polyimides " RICACOAT SN20 " and " the RICACOAT PN20 " of new Japanese physics and chemistry (strain) preparation.Make the modified polyimide of the wire polyimides (TOHKEMY 2006-37083 communique is described) that difunctionality C-terminal polybutadiene, diisocyanate cpd and tetra-atomic acid anhydride reactant obtain, the polyimides (described in TOHKEMY 2002-12667 communique, the TOHKEMY 2000-319386 communique etc.) that contains the polysiloxanes skeleton etc. in addition.
The commercial goods of polyamidoimide for example has: the polyamidoimide " Vylomax HR11NN " of Japan's weaving (strain) preparation and " Vylomax HR16NN " etc.Also have Hitachi to change into the modified polyamide imide of the polyamidoimide that contains the polysiloxanes skeleton " KS9100 ", " KS9300 " etc. of industry (strain) preparation.
The commercial goods of polyether sulfone for example has: the polyether sulfone " PES5003P " of Sumitomo Chemical (strain) society preparation etc.
The commercial goods of polysulfones for example has: the polysulfones " P1700 " of Solvay Advanced Polymers (strain) preparation, " P3500 " etc.
Curing agent for example has: amine is that curing agent, guanidine are that curing agent, imidazoles are that curing agent, phenol are that curing agent, naphthols are that curing agent, acid anhydrides are curing agent or their epoxy adduct or microencapsulation product, cyanate ester resin etc.Wherein preferred phenol is that curing agent, naphthols are curing agent, cyanate ester resin.These curing agent can be only to use a kind arbitrarily separately, also can will be used in combination more than 2 kinds.
Phenol is that curing agent, naphthols are that the commercial goods of curing agent for example has: MEH-7700, MEH-7810, MEH-7851 (bright and change into (strain) preparation), NHN, CBN, GPH (Japanese chemical drug (strain) preparation), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (Dongdu changes into (strain) preparation), LA7052, LA7054, LA3018, LA1356 (big Japanese ink chemistry (strain) prepares) etc.
Cyanate ester resin for example has bisphenol-A two cyanates, polyhydric phenols cyanate (oligomeric (3-methylene-1,5-phenylene cyanate)), 4,4 '-di-2-ethylhexylphosphine oxide (2,6-3,5-dimethylphenyl cyanate), 4,4 '-ethylene phenyl, two cyanates, hexafluoro bisphenol-a two cyanates, 2, two (4-cyanate) phenyl-propanes of 2-, 1,1-two (4-cyanate propyl group methane), two (4-cyanates-3, the 5-3,5-dimethylphenyl) methane, 1, two (4-cyanate phenyl-1-(methyl the ethylidene)) benzene of 3-, two (4-cyanate phenyl) thioether, difunctionality cyanate ester resins such as two (4-cyanate phenyl) ether, by novolaks, the multifunctional cyanate ester resin that cresols novolaks etc. are derived, the prepolymer that these cyanate ester resins are obtained by the part triazineization etc.The object lesson of described cyanate ester resin for example has: phenolic varnish type multifunctional cyanate ester resin (the husky Japan of dragon (strain) " PT30 ", cyanate equivalent 124) or part or all of bisphenol-A two cyanates formed trimerical prepolymer (the husky Japan of dragon (strain) " BA230 ", cyanate equivalent 232) etc. by triazineization.
About the cooperate ratio of epoxy resin with curing agent, using phenol is that curing agent or naphthols are when being curing agent, with respect to the epoxide equivalent 1 of epoxy resin, the ratio of the preferred 0.4-2.0 scope of phenolic hydroxyl equivalent of these curing agent, the more preferably ratio of 0.5-1.0 scope.When using cyanate ester resin, with respect to the epoxide equivalent 1 of epoxy resin, the ratio of the preferred 0.3-3.3 scope of cyanate equivalent, the more preferably ratio of 0.5-2.0 scope.
Except curing agent, can further contain curing accelerator in the hot curing resin composition.Described curing accelerator for example has imidazole compound, organic phosphine based compound etc., and object lesson has: glyoxal ethyline, triphenyl phasphine etc.When using curing accelerator, preferably use in the scope of 0.1-3.0% weight with respect to epoxy resin.When using cyanate ester resin as epoxy curing agent, in order to shorten hardening time, can in the past with the organo-metallic compound that adds in composition epoxy resin and the system that cyanate esters is used in combination as the curing catalysts use.Above-mentioned organo-metallic compound for example has: organic cobalt compound of the organic zinc compound of the organocopper compound of acetylacetone copper (II) etc., zinc acetylacetonate (II) etc., acetylacetone cobalt (II), acetylacetone cobalt (III) etc. etc.These organo-metallic compounds can only use a kind of arbitrarily separately, also can be used in combination two or more.The addition of organo-metallic compound is scaled the metal common preferably scope of 10-500ppm, the more preferably scope of 25-200ppm with respect to cyanate ester resin.
In order to make the cured composition low-thermal-expansion, can contain inorganic filler in the hot curing resin composition.Inorganic filler for example has: silica, aluminium oxide, mica, mica, silicate, barium sulfate, magnesium hydroxide, titanium oxide etc., preferred silica, aluminium oxide, preferred especially silica.Consider from the angle of insulating reliability, below the preferred 3 μ m of the average grain diameter of inorganic filler, below the preferred especially 1.5 μ m.When being 100% quality with the nonvolatile component of thermohardening type resin combination, the content of inorganic filler is preferably the 20-60% quality, more preferably the 20-50% quality.
Can contain other composition as required in the hot curing resin composition.Other composition for example has: the fire retardant of organic phosphorus flame retardant, the phosphorus compound that contains organic system nitrogen, nitrogen compound, silicone flame retardant, metal hydroxides etc.; Organic fillers such as organosilicon powder, nylon powder, fluororesin powder; The thickener of オ Le ベ Application (organic complex of colloid aluminium hydrosilicate), modified alta-mud etc.; The macromolecular defoamer or the levelling agent of silicon-type, fluororesin system etc.; The plastering agent of imidazoles system, thiazole system, triazole system, silane series coupling agent etc.; Phthalocyanine blue, phthalocyanine green, iodine are green, the colouring agent of dual-azo yellow, carbon black etc. etc.
The sheet-like fiber base material that uses in the prepreg is not particularly limited, for example can use glass cross, aromatic polyamides non-weaving cloth, liquid crystal polymer non-weaving cloth etc. as prepreg with base material material commonly used.Particularly when the insulating barrier that is used for multilayer printed-wiring board forms, the following slim base material of preferred used thickness 50cm, the slim base material of preferred especially 10-40 μ m.In the object lesson of sheet-like fiber base material, the glass cross base material for example has STYLE 1027MS (75/25mm of warp count, 75/25mm of weft count, the cloth weight 20 gram/m of ASAHI-SCHWEBEL (strain) preparation
2, thickness 19 μ m), STYLE1037MS (70/25mm of warp count, 73/25mm of weft count, the cloth weight 24 gram/m of ASAHI-SCHWEBEL (strain) preparation
2, thickness 28 μ m), (strain) have the pool to make prepared 1037NS (72/25mm of warp count, 69/25mm of weft count, cloth weight 23 gram/m
2, thickness 21 μ m), (strain) have the pool to make prepared 1027NS (75/25mm of warp count, 75/25mm of weft count, cloth weight 19.5 gram/m
2, thickness 16 μ m), (strain) have the pool to make prepared 1015NS (95/25mm of warp count, 95/25mm of weft count, cloth weight 17.5 gram/m
2, thickness 15 μ m), (strain) have the pool to make prepared 1000NS (85/25mm of warp count, 85/25mm of weft count, cloth weight 11 gram/m
2, thickness 10 μ m) etc.Liquid crystal polymer is non-woven to be furnished with VECLS (the order amount of paying 6～15g/m that the melt flows method of the aromatic polyester non-weaving cloth of (strain) Kuraray preparation obtains
2) or VECTRAN etc.
The sheet-like fiber base material uses glass cross usually.The glass cross that is used for multilayer printed-wiring board normally prepares by the yarn that automatic loom etc. is made into continuous glass fibre tens of-hundreds of bunchys, during usually with the yarn bunchy, in order to prevent the scattering of yarn, grain raising and twist.Therefore, in prepreg, the inhomogeneous arrangement of a part of glass cross, but there is position overlapped in the part.Compare this glass cross lap position and other position, and glass cross thickness is big.In the prepreg preparation process, because glass cross is sagging etc., glass cross is not the center of prepreg, but is present near surface.Usually the sheet-like fiber base material in the insulating resin sheet expose in the position that the local big part of the thickness of sheet-like fiber base material as mentioned above or a part of sheet-like fiber base material are positioned near surface remarkable especially.
Prepreg can be by preparations such as known hot melt or solvent methods.Hot melt is not that resin combination is dissolved in the organic solvent, but temporarily resin combination is coated on the good processing release paper of the fissility of resin combination on, it is laminated on the sheet-like fiber base material; Perhaps directly be coated with the method for preparing prepreg that waits by the die head coating machine.Solvent method is the sheet-like fiber base material to be immersed in resin combination is dissolved in the resin combination varnish that obtains in the organic solvent, resin combination varnish is contained be immersed in the sheet-like fiber base material, then Gan Zao method.Can be by being laminated in two sides under heating pressurized conditions the Continuous Heat lamination preparation of adhesive film on the supporter, that contain hot curing resin composition by sheet reinforcement base material.
Organic solvent during preparation varnish for example has: ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, Glycol Monomethyl ether acetic acid esters, carbitol acetic acid esters, carbitol such as cellosolve, BC class, aromatic hydrocarbons such as toluene, dimethylbenzene, dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone etc.Organic solvent can be a kind, also can will be used in combination more than 2 kinds.
Drying condition is not particularly limited, and in order to be laminated on the internal layer circuit substrate, must be under the temperature of lamination step, and hot curing resin composition has flowability and adhesivity.The curing of hot curing resin composition is not very important as far as possible when therefore, dry.And in prepreg more residual organic solvent, then become the reason that expands after the curing, therefore be dried to usually organic solvent in the hot curing resin composition to contain proportional be below 5% quality, below preferred 2% quality.Therefore, set drying condition by the two angle, its condition is according to the curing of hot curing resin composition or the organic solvent amount in the varnish and difference, for example in the varnish that contains 30-60% weight organic solvent, usually can 80-180 ℃ about dry 3-13 minute down.Those skilled in the art can set preferred drying condition by simple test.
The thickness of prepreg is according to the thickness of the conductor layer of internal layer circuit substrate and difference, the thickness of conductor layer is generally 10-30 μ m, the thickness of prepreg is generally the scope of 10-70 μ m, consider from the cost of glass cross and as the angle of the required thickness of insulating resin sheet, 12-50 μ m more preferably, further preferred 12-40 μ m.Exposing of the big more then fiber base material of the thickness of prepreg has the tendency of mitigation, but unfavorable for the slimming of multilayer printed-wiring board.According to insulating resin sheet of the present invention, can realize suppressing the slimming with multilayer printed-wiring board of exposing of fiber base material simultaneously.The thickness of prepreg can easily be controlled by the impregnation amount of regulating hot curing resin composition.But prepreg must be not form the space and has the flowability of lamination in the wiring portion of internal layer circuit substrate, and preferred lowest melt viscosity is in the scope of 200-7000 pool, particularly preferably in the scope of 400-3000 pool.
" the solidfied material layer of hot curing resin composition " of the present invention obtains the hot curing resin composition heat cure.As long as hot curing resin composition can be applicable to the insulating barrier of multilayer printed-wiring board, be not particularly limited, all can use, also can use same material with the hot curing resin composition that in prepreg, uses of above-mentioned explanation.Hot curing resin composition that uses in prepreg and the hot curing resin composition that uses in cured layer can be the same or different.
Heat cure thing layer in the insulating resin sheet of the present invention for example can be by making the bonding sheet that on supporter, has formed the hot curing resin composition layer the method for hot curing resin composition heat cure obtain.Promptly, bonding sheet can be according to method well known in the art, for example prepare hot curing resin composition is dissolved in the resin varnish that organic solvent obtains, this resin varnish of coating on supporter, by heating such as blowing hot-airs, make the organic solvent drying, forming the hot curing resin composition layer prepares, make the hot curing resin composition heat cure of the bonding sheet that obtains like this, make the solidfied material sheet, a face step for adhering via with itself and prepreg can obtain insulating resin sheet of the present invention.It should be noted that, in the preparation of bonding sheet, by being coated on the resin varnish heating on the supporter, simultaneously or carry out drying and curing successively, can obtain the solidfied material sheet, the solidfied material sheet that obtains like this via with a face step for adhering of prepreg, can obtain insulating resin sheet of the present invention.
Organic solvent during the preparation resin varnish for example has: ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, Glycol Monomethyl ether acetic acid esters, carbitol acetic acid esters, carbitol such as cellosolve, BC class, aromatic hydrocarbons such as toluene, dimethylbenzene, dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone etc.Organic solvent can will be used in combination more than 2 kinds.
The drying condition of preparation during bonding sheet is not particularly limited, be dried to usually containing of organic solvent in the hot curing resin composition layer proportional be 10% quality following, below preferred 5% quality.Dry according to the organic solvent amount in the resin varnish and difference for example can contain the resin varnish of 30-60% quality organic solvent at 50-150 ℃ time about dry 3-10 minute.When the hot curing resin composition layer of this bonding sheet is solidified successively, or will be coated on supporter resin varnish drying with solidify when carrying out simultaneously, condition of cure is not particularly limited, for example in the varnish that contains 30-60% quality organic solvent, by heating under the temperature about 50-200 ℃ about 10 minutes-10 hours, can form the solidfied material layer.It should be noted that dry and condition of cure can be set suitable, desirable condition by simple test by those skilled in the art.
Supporter preferably uses plastic sheeting.Outside the plastic sheeting, can also use metal formings such as processing release paper or Copper Foil, aluminium foil etc. as supporter.Plastic sheeting has: the polyester of PETG (hereinafter to be referred as " PET "), PEN etc., Merlon, acrylic resin, cyclic polyolefin, tri acetyl cellulose, polyethers thioether, polyether-ketone, polyimides etc.Wherein preferred pet film, PEN film, preferred especially low-cost pet film.When using plastic sheeting especially in the supporter, can peel off the therefore preferred supporter that uses the face that is formed of hot curing resin composition layer to carry out demoulding processing, has release layer from the solidfied material of hot curing resin composition layer.Metal forming can be removed by etching solution, but when making the hot curing resin composition heat cure with plastic sheeting as supporter, if there is not release layer, then is difficult to peel off plastic sheeting from solidfied material.As long as the releasing agent that uses during the demoulding is handled can make solidfied material peel off from supporter, be not particularly limited, for example have: silicon-type releasing agent, alkyd resins are releasing agent etc.Can also use the commercially available plastic sheeting that has release layer, preferably for example have: with alkyd resins is the PET film with release layer of releasing agent as main component---SK-1, the AL-5 of Lintec (strain) preparation, AL-7 etc.Plastic sheeting can be implemented delustring processing, sided corona treatment, also can form release layer on this treated side.When using Copper Foil, can not peel off and utilize this Copper Foil as conductor layer as supporter.The thickness of supporter is not particularly limited, and is generally 10-150 μ m, preferably uses in the scope of 25-50 μ m.
In the solidfied material layer of insulating resin sheet of the present invention, hot curing resin composition may not need complete heat cure, can be cured to the degree that can bring into play effect of the present invention.Promptly, the common bonding sheet that forms middle use at interlayer insulating film, contains supporter and hot curing resin composition layer, must be by carrying out imbedding of circuit with the internal layer circuit substrate layer is incompatible, therefore must have enough flowabilities, and the solidfied material layer of the hot curing resin composition in the insulating resin sheet of the present invention exposing for the sheet-like fiber that suppresses prepreg, in lamination step and smoothing step, has flowability hardly, this is very important, does not more preferably have flowability basically.For example, use vacuum laminator, under the condition identical with the smoothing step with the lamination step of reality, be pressed in the solidfied material of 12cm * 15cm hot curing resin composition on the FR4 substrate that 20cm is square, 0.8mm is thick layer by layer and carry out smoothing, the maximum of this moment is oozed out length and is preferably below the 0.3mm, below the further preferred 0.2mm, below the further preferred 0.1mm, especially preferably be essentially 0 solid state.For example the maximum of measuring can be oozed out the index of the curing degree of the preferred solidfied material layer that length uses in as the present invention under following representative of conditions.That is, use vacuum laminator, the cured layer of the hot curing resin composition of 12cm * 15cm (planar dimension is the rectangle solidfied material layer of 12cm * 15cm) was vacuumized 30 seconds under 80 ℃ of temperature, then at 80 ℃ of temperature, pressure 7.0kgf/cm
2Condition under, via heat resistant rubber pressurization 60 seconds, carry out lamination thus, further under atmospheric pressure, use the SUS mirror board, at 80 ℃ of temperature, pressure 5.5kgf/cm
2Condition under pressurization 90 seconds, implement smoothing and handle, the maximum of measuring the resin of this moment is oozed out length, this maximum is oozed out below the preferred 0.3mm of length, below the further preferred 0.2mm, below the further preferred 0.1mm, especially preferably is essentially 0.
The state of cure of hot curing resin composition can be estimated by glass transition temperature.Among the present invention, preferred consolidation is to the degree that can observe the glass transition temperature of solidfied material at least.Usually bonding sheet that use, that contain supporter and hot curing resin composition has flowability as mentioned above in interlayer insulating film forms, even hot curing resin composition layer second rank for example, degree of reaction also significantly reduces, usually can't measure glass transition temperature, even measure, also be to be at least the following glass transition temperature of room temperature.When being cured to the degree that can observe glass transition temperature usually, in the scope of the temperature of conventional lamination step and the temperature of smoothing step (about 70 ℃-140 ℃), hot curing resin composition does not have flowability basically, perhaps has flowability hardly.Can clearly distinguish conventional bonding sheet and solidfied material sheet of the present invention from this point.More preferably the glass transition temperature of solidfied material is more than 80 ℃.The upper limit of glass transition temperature is not particularly limited, and the glass transition temperature of the hot curing resin composition that solidifies is limited to the scope below 300 ℃ mostly usually.
Glass transition temperature described here is the stable on heating value of expression, determines according to the described method of JIS K7179, specifically, is to use thermo-mechanical analysis (TMA), dynamic mechanical analysis (DMA) to wait and measure.Thermo-mechanical analysis (TMA) for example has: TMA-SS6100 (SeikoInstruments (strain) manufacturing), TMA-8310 ((strain) is of science makes) etc., dynamic mechanical analysis (DMA) for example has: DMS-6100 (Seiko Instruments (strain) manufacturing) etc.Glass transition temperature is than decomposing the temperature height, when in fact not observing glass transition temperature, decomposition temperature can being considered as glass transition temperature of the present invention.Rate of mass reduction when decomposition temperature described here is defined as and measures according to the described method of JIS K7120 is 5% o'clock a temperature.
The thickness of the solidfied material layer of hot curing resin composition is generally the scope of 1-30 μ m, more preferably 1-20 μ m.Cross thinly, the preparation difficulty of solidfied material layer is then arranged or suppress the tendency that effect that fiber base material exposes reduces.Blocked up, then unfavorable for the slimming of multilayer printed-wiring board.Thickness can easily be controlled by regulating the coating weight of hot curing resin composition on supporter.
Insulating resin sheet of the present invention can be by solidfied material layer and the bonding acquisition of above-mentioned prepreg with above-mentioned hot curing resin composition.Following method is for example arranged: will contain the solidfied material sheet of solidfied material layer of supporter and hot curing resin composition and a surface layer of prepreg and press and bonding method; Prepreg is laminated on the solidfied material layer of this solidfied material sheet and bonding method.Respectively solidfied material sheet and prepreg are rolled into web-like, can continuous laminating; Also can be with two cuttings of web-like, one chip ground carries out lamination.
In the insulating resin sheet of the present invention, the aggregate thickness of the solidfied material layer of prepreg layer and hot curing resin composition is generally the scope of 11 μ m-100 μ m, more preferably the scope of 13-70 μ m, the especially preferably scope of 13-55 μ m.The thickness of insulating resin sheet is thin excessively, is then having circuit to imbed inadequate tendency aspect the formation insulating barrier, and preparation is difficulty also.The thickness of insulating resin sheet is blocked up, and is then unfavorable for the slimming of multilayer printed-wiring board.
In the insulating resin sheet of the present invention, for prevent depression in the surface or injured, prevent that impurity from adhering to etc., preferably do not protect with protective film with the bonding prepreg face of solidfied material layer.Protective film can use and at the same material of plastic sheeting described in the explanation of above-mentioned supporter, the thickness of protective film is generally 1-40 μ m, preferably uses in the scope of 10-30 μ m.
The preparation method of multilayer printed-wiring board of the present invention is included in lamination insulating resin sheet of the present invention on face of internal layer circuit substrate or two faces, and insulating resin sheet is solidified, and forms the step of insulating barrier, comprises the step of following (1)-(3) usually.
(1) lamination step, insulating resin sheet is arranged on the internal layer circuit substrate, its prepreg is contacted, under reduced pressure with two faces or a face of internal layer circuit substrate, heat and pressurize via elastomeric material, insulating resin sheet is laminated on the internal layer circuit substrate thus; (2) smoothing step heats the insulating resin sheet after laminated and pressurizes by metallic plate or metallic roll; And (3) thermal cure step, the insulating resin sheet after level and smooth is carried out heat cure, form insulating barrier thus.
Here, the thickness of insulating barrier is followed the solidfied material layer of hot curing resin composition and the aggregate thickness of prepreg basically.Therefore, the thickness of insulating barrier is generally 11-100 μ m, preferred 13-70 μ m, more preferably 13-55 μ m.
Below lamination step is described.Lamination normally under reduced pressure with heating of insulating resin sheet and internal layer circuit substrate and pressurization, is laminated to insulating resin sheet on the internal layer circuit substrate and carries out.Decompression is meant down presses the atmosphere that is reduced to below the 20mmHg (26.7hPa) with air.In the lamination step, heating and pressurization can be undertaken by by supporter one side the metallic plates such as SUS mirror board that heat being pressurizeed, be not that metallic plate is directly pressurizeed, but pressurize via the elastomeric material of heat resistant rubber etc., like this, it is concavo-convex that insulating resin sheet can fully be followed the circuit of circuit substrate.Preferred 70 ℃-140 ℃ of pressed temperature (more preferably 80 ℃-130 ℃), pressure is preferably at 1-11kgf/cm
2(9.8 * 10
4-107.9 * 10
4N/cm
2) scope carry out.
After the lamination step, carry out the smoothing of the insulating resin sheet of lamination.This smoothing step is (under the atmospheric pressure) normally under normal pressure, by the metallic plate or the metallic roll such as SUS mirror board of heating, insulating resin sheet is heated and pressurizes carry out, and smoothing is more preferably undertaken by metallic plate.Heating can be adopted the condition identical with above-mentioned lamination step with pressurized conditions.
Lamination step of the present invention and smoothing step can be carried out continuously by commercially available vacuum laminator.Commercially available vacuum laminator for example has (strain) name mechanism to make the vacuum pressure type laminating machine of manufacturing, NICHIGO-MORTON (strain) system Vacuum Applicator etc.
Carry out thermal cure step after lamination step or the smoothing step.In the thermal cure step,, form insulating barrier with the insulating resin sheet heat cure.Mainly be that prepreg layer is by heat cure in the thermal cure step.And different, solidification temperature is 150-200 ℃ to the heat cure condition usually according to the kind of hot curing resin composition etc., and be 15-60 minute hardening time.
Among the preparation method of multilayer printed-wiring board of the present invention, can further be included in the opening step of perforate on the insulating barrier and the alligatoring step of this insulating barrier being carried out roughening treatment.These steps can be carried out according to the whole bag of tricks that uses in the multilayer printed-wiring board preparation well known in the art.Can further comprise the step of peeling off supporter from the insulating resin sheet of heat cure among the preparation method of multilayer printed-wiring board of the present invention.Peeling off preferably of supporter carried out after the thermal cure step or after the opening step.Peeling off of supporter can be manually to peel off also to pass through the automatic stripper mechanical stripping.When using metal forming, can remove by the etching solution etching as supporter.
Opening step for example can form holes such as via, all-pass via and carry out on insulating barrier by laser, plasmas etc. such as brill, carbon dioxide laser, YAG laser.In the multilayer printed-wiring board, the formation of all-pass via is normally carried out on core substrate, and compound insulating barrier is normally to come conducting by via.Power auger is adopted in the formation of all-pass via usually.
The alligatoring step for example can be undertaken by with oxidants such as the alkaline permanganic acid aqueous solution surface of insulating layer being handled.This alligatoring step may have the desmearing step in holes such as via, all-pass via concurrently.Before the alkaline permanganic acid aqueous solution, preferably carry out swelling treatment by swelling solution.Swelling solution for example has: Swelling Dip Securiganth P, the Swelling Dip Securiganth SBU etc. of Atotech Japan (strain) preparation.Swelling treatment normally is immersed in insulating barrier about swelling solution 5-10 minute that is heated to about 60-80 ℃ carries out.The alkalescence permanganic acid aqueous solution for example has: the solution of dissolving potassium permanganate or sodium permanganate gained in sodium hydrate aqueous solution.The roughening treatment of being undertaken by the alkaline permanganic acid aqueous solution is carried out about 10-30 minute normally at 60-80 ℃.The commercial goods of the alkalescence permanganic acid aqueous solution has: コ Application セ Application ト レ one ト コ Application パ Network ト CP, the De one ジ Application グ ソ リ ユ one シ ヨ Application セ キ ユ リ ガ Application ス P etc. of Atotech Japan (strain) preparation.
Among the preparation method of multilayer printed-wiring board of the present invention, can further comprise, form the plating step of conductor layer at the surface of insulating layer of further alligatoring by plating; After conductor layer forms, circuit substrate is carried out the step of annealing in process by heating; And the circuit that forms circuit on conductor layer forms step.These steps can be carried out according to the whole bag of tricks that uses in the multilayer printed-wiring board preparation well known in the art.
The plating step for example adopts the method with electroless plating and electrolysis plating combination, forms conductor layer and carry out on the surface of insulating layer that has formed concavo-convex anchor through roughening treatment.At this moment, in via, also can form coating.Conductor layer is preferably copper coating.The common employing of copper coating is with the method for electrolytic copper free plating and cathode copper plating combination, and the plating resist layer of formation and conductor layer opposite pattern only relies on the electrolytic copper free plating and can form conductor layer.The preferred 0.1-3 μ of the thickness of electroless plating layer m, more preferably 0.3-2 μ m.The thickness that adds up to 3-35 μ m of the thickness of the thickness of electro deposition preferred itself and electroless plating layer, the more preferably thickness of 5-20 μ m.Via can form the filling via by plating.
The annealing in process step for example can be by carrying out circuit substrate heating under 150-200 ℃ in 20-90 minute after forming at conductor layer.By annealing in process, can make the peel strength of conductor layer further improve and stablize.
Circuit forms step for example can adopt relief method, semi-additive process etc.In the formation of fine-line, preferred semi-additive process forms the pattern resist layer on the electroless plating layer, form the electro deposition of desired thickness, peels off the pattern resist layer then, removes the electroless plating layer by dodging ablation, forms circuit thus.
" internal layer circuit substrate " described in the present invention is meant on a face of glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermohardening type polyphenylene oxide substrate or two faces to have the conductor layer that has carried out pattern processing (formation circuit), should further form the intermediate preparation thing of insulating barrier and conductor layer when the preparation multilayer printed-wiring board.Roughening treatment is implemented in advance by melanism processing etc. in the conductor layer surface, and this angle from the stickiness of insulating barrier and internal layer circuit substrate is considered preferred.
Below provide embodiment and comparative example, be described more specifically the present invention.
In the following record, " part " is meant " mass parts ".
Embodiment 1
(making of resin varnish)
Under 60 ℃, polyvinyl butyral resin (ponding chemical industry (strain) preparation " KS-1 ") is dissolved in the solvent that ethanol and toluene mixes according to the ratio of 1: 1 (mass ratio), make solid formation be divided into 15%, obtain polyvinyl butyral resin solution.Then, with 28 parts of aqueous bisphenol A type epoxy resin (epoxide equivalents 180, japan epoxy resin (strain) prepares " Epicote 828EL ") and 28 parts of naphthalene type four sense epoxy resin (epoxide equivalents 163, big Japanese ink chemical industry (strain) preparation " HP4700 ") heating for dissolving while stirring in the mixed solvent that contains 15 parts of methyl ethyl ketones (being designated hereinafter simply as " MEK ") and 15 parts of cyclohexanone, to wherein mixing 110 parts of naphthols is that (Dongdu changes into (strain) preparation " SN-485 " to curing agent, phenolic hydroxyl equivalent 215) solid formation is divided into 50% MEK solution, 0.1 (four countries change into industry (strain) preparation to part curing catalysts, " 2E4MZ "), 70 parts of preparing spherical SiO 2 (average grain diameters 0,5 μ m, " SOC2 ", Admatechs company prepares) and 30 parts of above-mentioned polyvinyl butyral resin solution, evenly disperse the preparation resin varnish by rotating refiner at a high speed.
(preparation of solidfied material sheet)
By the die head coating machine, being coated on above-mentioned resin varnish with alkyd equably is on the demoulding treated side of the PET film (38 μ m) handled of releasing agent, the thickness that makes dry after heat cured resin composition layer is 15 μ m, by 80-120 ℃ (average 100 ℃) dry 6-8 minute down, the lowest melt viscosity that obtains the hot curing resin composition layer is the bonding sheets of 1300 pools.At the polypropylene film of the surface of this bonding sheet applying, be rolled into web-like simultaneously as the thick 15 μ m of protective film.Bonding sheet with web-like is cut into wide 502mm then, obtains 50 volume bonding sheets.The protective film of release adhesive sheet; 150 ℃ 15 minutes, 160 ℃ 15 minutes, 170 ℃ 15 minutes, 180 ℃ following heat cures in 15 minutes, the glass transition temperature that obtains the solidfied material of hot curing resin composition is respectively 86 ℃, 99 ℃, 113 ℃, 129 ℃ solidfied material sheet respectively.On the other hand; according to the thickness that obtains the hot curing resin composition layer with quadrat method is the web-like bonding sheet of 10 μ m, 5 μ m; peel off protective film; 180 ℃ of following heat cures 15 minutes, the glass transition temperature that obtains the solidfied material of hot curing resin composition was two kinds of solidfied material sheets of 129 ℃.
(preparation of prepreg)
Resin varnish contained be immersed in (strain) and have the pool to make in the 1015NS glass cross (thick 16 μ m) of made, the residual solvent amount that is dried in the resin is 0.6%, obtains the prepreg of thick 35 μ m.Then, the polypropylene film of laminate thickness 15 μ m on a face of prepreg, the PET film of lamination 38 μ m on another face.
(preparation of insulating resin sheet)
It at the glass transition temperature of the solidfied material of hot curing resin composition the above-mentioned prepreg that polypropylene film has been peeled off in configuration on 86 ℃ the curing object plane of solidfied material sheet, use (strain) name mechanism to make the vacuum pressure type laminating machine of manufacturing, under 120 ℃ of temperature, vacuumized 30 seconds, then at 120 ℃ of temperature, pressure 7.0kg/cm
2Condition under, by on the PET film via heat resistant rubber lamination 30 seconds.Then, under atmospheric pressure, use the SUS mirror board, at 120 ℃ of temperature, pressure 5kg/cm
2Condition under the pressurization 60 seconds, obtain insulating resin sheet.
(lamination of insulating resin sheet)
The gained insulating resin sheet is laminated on two faces of internal layer circuit substrate (IPC MULTI-PURPOSETESTBOARD No.IPC-B-25, the thick 18 μ m of conductor, thick 0.8mm).Described lamination is to use (strain) name mechanism to make vacuum pressure type laminating machine MVLP-500 of manufacturing, vacuumizes 30 seconds under 80 ℃ of the temperature, then at 80 ℃ of temperature, pressure 7.0kg/cm
2Condition under, by on the PET film via heat resistant rubber pressurization 60 seconds.Then, under atmospheric pressure, use the SUS mirror board, at 80 ℃ of temperature, pressure 5.5kg/cm
2Condition under the pressurization 90 seconds.
(curing of resin combination)
Peel off the PET film from the insulating resin sheet of lamination, use recirculation furnace, hot curing resin composition (prepreg) is solidified, form insulating barrier.Obtain on two surfaces of internal layer circuit substrate, to have formed the laminate of insulating barrier thus.
(roughening treatment)
Implement roughening treatment for the gained laminate by permanganic acid liquid.At first, as swelling treatment, be under 60 ℃, in the Swelling Dip Securiganth P solution of Atotech Japan (strain) preparation, soaked 5 minutes, then, as oxidation processes, be under 80 ℃, in the mixed liquor of the コ Application セ Application ト レ one ト コ Application パ Network ト CP of Atotech Japan (strain) preparation and De one ジ Application グ ソ リ ユ one シ ヨ Application セ キ ユ リ ガ Application ト P, soaked 20 minutes, then, handle as reduction, under 40 ℃, in the Reduction solution SecuriganthP500 of Atotech Japan (strain) preparation, soaked 5 minutes.
(forming conductor layer) by plating
Use contains the ア Network チ ベ one タ ネ オ ガ Application ト 834 of the Atotech Japan preparation of palladium, on the surface of insulating layer of gained laminate, apply the catalyst of electroless plating copper, use the プ リ Application ト ガ Application ト MSK-DK of Atotech Japan (strain) preparation that contains tartrate to carry out electroless plating then.Then, use copper sulphate to carry out the electrolysis plating, make the about 20 μ m of copper thickness.Under 180 ℃, carry out then solidifying in 30 minutes, obtain multilayer printed-wiring board.
Embodiment 2
The glass transition temperature that uses solidfied material be 99 ℃ solidfied material sheet (thickness of hot curing resin composition layer (solidfied material layer) is 15 μ m) as the solidfied material sheet, in addition implement similarly to Example 1, obtain multilayer printed-wiring board.
Embodiment 3
The glass transition temperature that uses solidfied material be 113 ℃ solidfied material sheet (thickness of hot curing resin composition layer (solidfied material layer) is 15 μ m) as the solidfied material sheet, in addition implement similarly to Example 1, obtain multilayer printed-wiring board.
Embodiment 4
Is 100 ℃ with insulating resin sheet to the temperature of internal layer circuit substrate lamination and smoothing step, in addition implements similarly to Example 1, obtains multilayer printed-wiring board.
Embodiment 5
The glass transition temperature that uses solidfied material is that 99 ℃ solidfied material layer (thickness of hot curing resin composition layer (solidfied material layer) is 15 μ m) is as the solidfied material sheet, is 100 ℃ with insulating resin sheet to the temperature of internal layer circuit substrate lamination and smoothing step, in addition implement similarly to Example 1, obtain multilayer printed-wiring board.
Embodiment 6
The glass transition temperature that uses solidfied material is that 113 ℃ solidfied material layer (thickness of hot curing resin composition layer (solidfied material layer) is 15 μ m) is as the solidfied material sheet, is 100 ℃ with insulating resin sheet to the temperature of internal layer circuit substrate lamination and smoothing step, in addition implement similarly to Example 1, obtain multilayer printed-wiring board.
Embodiment 7
Is 120 ℃ with insulating resin sheet to the temperature of internal layer circuit substrate lamination and smoothing step, in addition implements similarly to Example 1, obtains multilayer printed-wiring board.
Embodiment 8
The glass transition temperature that uses solidfied material is that 99 ℃ solidfied material layer (thickness of hot curing resin composition layer (solidfied material layer) is 15 μ m) is as the solidfied material sheet, is 120 ℃ with insulating resin sheet to the temperature of internal layer circuit substrate lamination and smoothing step, in addition implement similarly to Example 1, obtain multilayer printed-wiring board.
Embodiment 9
The glass transition temperature that uses solidfied material is that 113 ℃ solidfied material layer (thickness of hot curing resin composition layer (solidfied material layer) is 15 μ m) is as the solidfied material sheet, is 120 ℃ with insulating resin sheet to the temperature of internal layer circuit substrate lamination and smoothing step, in addition implement similarly to Example 1, obtain multilayer printed-wiring board.
Embodiment 10
The glass transition temperature that uses solidfied material is that 129 ℃ solidfied material layer (thickness of hot curing resin composition layer (solidfied material layer) is 15 μ m) is as the solidfied material sheet, is 100 ℃ with insulating resin sheet to the temperature of internal layer circuit substrate lamination and smoothing step, in addition implement similarly to Example 1, obtain multilayer printed-wiring board.
Embodiment 11
The glass transition temperature that uses solidfied material is that 129 ℃ solidfied material layer (thickness of hot curing resin composition layer (solidfied material layer) is 10 μ m) is as the solidfied material sheet, is 100 ℃ with insulating resin sheet to the temperature of internal layer circuit substrate lamination and smoothing step, in addition implement similarly to Example 1, obtain multilayer printed-wiring board.
Embodiment 12
The glass transition temperature that uses solidfied material is that 129 ℃ solidfied material layer (thickness of hot curing resin composition layer (solidfied material layer) is 5 μ m) is as the solidfied material sheet, is 100 ℃ with insulating resin sheet to the temperature of internal layer circuit substrate lamination and smoothing step, in addition implement similarly to Example 1, obtain multilayer printed-wiring board.
Embodiment 13
The glass transition temperature that uses solidfied material is that 129 ℃ solidfied material layer (thickness of hot curing resin composition layer (solidfied material layer) is 15 μ m) is as the solidfied material sheet, is 120 ℃ with insulating resin sheet to the temperature of internal layer circuit substrate lamination and smoothing step, in addition implement similarly to Example 1, obtain multilayer printed-wiring board.
Embodiment 14
The glass transition temperature that uses solidfied material is that 129 ℃ solidfied material layer (thickness of hot curing resin composition layer (solidfied material layer) is 10 μ m) is as the solidfied material sheet, is 120 ℃ with insulating resin sheet to the temperature of internal layer circuit substrate lamination and smoothing step, in addition implement similarly to Example 1, obtain multilayer printed-wiring board.
Embodiment 15
The glass transition temperature that uses solidfied material is that 129 ℃ solidfied material layer (thickness of hot curing resin composition layer (solidfied material layer) is 5 μ m) is as the solidfied material sheet, is 120 ℃ with insulating resin sheet to the temperature of internal layer circuit substrate lamination and smoothing step, in addition implement similarly to Example 1, obtain multilayer printed-wiring board.
Comparative example 1
The prepreg layer of used thickness 50 μ m replaces insulating resin sheet, in addition implements similarly to Example 1, obtains multilayer printed-wiring board.The prepreg of described thickness 50 μ m is similarly to Example 1 resin varnish to be contained be immersed in (strain) and have the pool to make in the 1015NS glass cross (thickness 16 μ m) of manufacturing, the thickness that makes the gained prepreg is 50 μ m, obtains in dry 10 minutes down at 80-150 ℃.
Comparative example 2
Except using bonding sheet (bonding sheet that uses in the solidfied material sheet preparation in embodiment 1) to replace implementing similarly to Example 1 the solidfied material sheet, obtain multilayer printed-wiring board.
Following the carrying out of evaluation that carries out for above embodiment and the resulting solidfied material sheet of comparative example, prepreg, insulating resin sheet and multilayer printed-wiring board.Its result goes into shown in the following table 1.
(fluidity evaluating)
Use (strain) name mechanism to make the vacuum pressure type laminating machine of manufacturing, the solidfied material sheet is cut into planar dimension 12cm * 15cm rectangle, its concentric ground carried be placed at the thick FR4 substrate of the square 0.8mm of 20cm, with the identical condition of each embodiment and comparative example under carry out lamination and smoothing, estimate mobile by oozing out length.Lamination is at 80 ℃ of temperature, pressure 7.0kg/cm vacuumize 30 seconds under 80 ℃ of temperature after
2Condition under by on the PET film via heat resistant rubber pressurization 60 seconds, carry out lamination; Smoothing is under atmospheric pressure used the SUS mirror board, at 80 ℃ of temperature, pressure 5.5kg/cm
2Condition under carry out 90 seconds the pressurization.Pressurization back mensuration is oozed out length by the maximum of the resin that four limits are oozed out.
Ooze out length and be meant the resin that oozes out by the end (end limit) of PET film length, measure by the length measurment instrument of CCD type microscope ((strain) Keyence corporate system VH6300) with respect to this end (end limit) vertical direction of resin.
(mensuration of glass transition temperature)
As sample, use DMS-6100 with the small pieces of the solidfied material layer of hot curing resin composition in the cured sheets of gained in embodiment and the comparative example as thermo-mechanical analysis device (DMA), stretch mode " under measure.Described mensuration is to carry out in 25 ℃-240 ℃ scope with 2 ℃/minute intensification.First of the peaked decimal point of the loss tangent (pan) that the ratio of measuring the storage elastic modelling quantity (E ') of gained and loss elastic modulus (E ") is obtained rounds up, with income value as glass transition temperature.Be considered as and measure when it should be noted that uncured can't mensuration.
(mensuration of lowest melt viscosity)
The model Rheosol-G3000 that uses (strain) UPM to make, amount of resin is 1 gram.Use the parallel-plate of diameter 18mm, to measure 60 ℃ of initial temperatures, 5 ℃/minute of programming rates, concussion number 1Hz/deg mensuration.With MV minium viscosity value (η) as lowest melt viscosity.
About 1500 pools of the lowest melt viscosity of the hot curing resin composition of the prepreg layer of in embodiment and comparative example, using.The melt viscosity of the cured layer of embodiment is more than 500,000 pools, can't measure.About 1600 pools of the lowest melt viscosity of the hot curing resin composition layer of comparative example 2.
(Determination of thickness of insulating resin sheet, solidfied material lamella, prepreg)
((strain) MITUTOYO system MCD-25MJ) is measured to use the agent of contact thickness.
(exposing with copper facing of glass cross is residual)
Peel off the electroplated film on the P model (coupon) of internal layer circuit substrate, use CCD type microscope (Keyence corporate system VH6300) having or not of sight glass silk screen to expose.When exposing glass cross, copper facing is slipped into wherein when copper facing, so the coating epithelium is still residual after peeling off that copper facing arranged.
[evaluation]
Zero: glass cross is not exposed to the resin surface of P model, and it is residual not have copper facing.
*: glass cross is exposed to the resin surface of P model, perhaps has copper facing residual at this place.
(to the imbedibility of circuit)
Whether cut out the cross section of the difference in height part of P model part in the circuit substrate, the gained laminate is observed with sweep electron microscope (SEM), confirming has resin to imbed between circuit.
[evaluation]
Zero: resin is imbedded between circuit.
*: voids left is arranged between circuit, imbed insufficient.
[table 1]
As shown in Table 1, even the insulating resin sheet that comprises the prepreg of embodiment 1 to 15 and solidfied material is implemented roughening treatment being laminated on the internal layer circuit substrate and solidifying the back, glass cross can not expose at resin surface yet, does not have copper facing residual.On the other hand, use separately in the comparative example 2 of the comparative example 1 of prepreg and the insulating resin sheet that use contains prepreg and hot curing resin composition layer (uncured), all observe exposing of glass cross that roughening treatment causes.
Industrial applicability
The present invention relates to be formed with for the insulating barrier of multilayer printed-wiring board the preparation method of the insulating resin sheet of usefulness, by using the insulating resin sheet that is obtained by this preparation method, even make the surface of insulating layer alligatoring, the fiber base material of insulating resin sheet can not expose yet, and can prepare the much higher layer of reliability printed wiring board. And, the gained multilayer printed-wiring board for example can be used as the high density, compact printed wiring board that is equipped with semiconductor chip and uses, in addition, also can expect to use as the constituent material small-sized, that the novel semi-conductor of light weight is packed of the slimming of having passed through core substrate or simplification.
The application is willing to that based on the spy who submits in Japan its content is completely contained in this specification 2008-078624 number.
Claims (14)
1. insulating resin sheet, this insulating resin sheet is the insulating resin sheet that has the solidfied material layer of hot curing resin composition on a face of prepreg.
2. the described insulating resin sheet of claim 1 wherein, further has support body layer on the solidfied material layer.
3. the described insulating resin sheet of claim 2, this insulating resin sheet are that the face that the solidfied material sheet that will be formed with the solidfied material layer of hot curing resin composition on supporter is adhered to prepreg obtains.
4. claim 2 or 3 described insulating resin sheets, wherein, solidfied material layer one side of support body layer carried out demoulding processing.
5. each described insulating resin sheet among the claim 2-4, wherein, support body layer is a plastic sheeting.
6. each described insulating resin sheet among the claim 1-5, wherein, the prepreg face of insulating resin sheet is protected with protective film.
7. each described insulating resin sheet among the claim 1-6, wherein, the thickness of prepreg is 10-70 μ m.
8. each described insulating resin sheet among the claim 1-7, wherein, the solidfied material layer of hot curing resin composition is 1-30 μ m.
9. each described insulating resin sheet among the claim 1-8, this insulating resin sheet is used to comprise the preparation method of the multilayer printed-wiring board of following steps: (1) lamination step, insulating resin sheet is arranged on the internal layer circuit substrate, it is contacted with two faces or a face of internal layer circuit substrate, under reduced pressure, heat and pressurize via elastomeric material, insulating resin sheet is laminated on the internal layer circuit substrate thus; (2) smoothing step heats the insulating resin sheet after laminated and pressurizes by metallic plate or metallic roll, makes insulating resin sheet level and smooth; And (3) thermal cure step, the insulating resin sheet after level and smooth is carried out heat cure.
10. the described insulating resin sheet of claim 9, wherein, the solidfied material layer of hot curing resin composition does not have flowability basically in lamination step and smoothing step.
11. multilayer printed-wiring board, this multilayer printed-wiring board forms insulating barrier by each described insulating resin sheet among the claim 1-10.
12. the preparation method of multilayer printed-wiring board, the method includes the steps of: (1) lamination step, each described insulating resin sheet among the claim 1-10 is arranged on the internal layer circuit substrate, prepreg layer is contacted with two faces or a face of internal layer circuit substrate, under reduced pressure, heat and pressurize via elastomeric material, insulating resin sheet is laminated on the internal layer circuit substrate thus; (2) smoothing step heats the insulating resin sheet after laminated and pressurizes by metallic plate or metallic roll; And (3) thermal cure step, the insulating resin sheet after level and smooth is carried out heat cure.
13. the described method of claim 12, wherein, the heating of the insulating resin sheet of lamination step and smoothing step and pressurization are carried out from support body layer.
14. claim 12 or 13 described methods, this method further comprises: the opening step of perforate on insulating barrier; This insulating barrier is carried out the alligatoring step of roughening treatment; By plating, on the surface of insulating layer after the alligatoring, form the plating step of conductor layer; And the circuit that forms circuit on conductor layer forms step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310652193.4A CN103625051B (en) | 2008-03-25 | 2009-03-25 | Insulating resin sheet and use the preparation method of multilayer printed-wiring board of this insulating resin sheet |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-078624 | 2008-03-25 | ||
| JP2008078624 | 2008-03-25 | ||
| PCT/JP2009/055876 WO2009119621A1 (en) | 2008-03-25 | 2009-03-25 | Insulating resin sheet and method for manufacturing multilayer printed wiring board using the insulating resin sheet |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310652193.4A Division CN103625051B (en) | 2008-03-25 | 2009-03-25 | Insulating resin sheet and use the preparation method of multilayer printed-wiring board of this insulating resin sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101977765A true CN101977765A (en) | 2011-02-16 |
| CN101977765B CN101977765B (en) | 2014-07-02 |
Family
ID=41113813
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310652193.4A Active CN103625051B (en) | 2008-03-25 | 2009-03-25 | Insulating resin sheet and use the preparation method of multilayer printed-wiring board of this insulating resin sheet |
| CN200980110353.4A Active CN101977765B (en) | 2008-03-25 | 2009-03-25 | Insulating resin sheet and method for manufacturing multilayer printed wiring board using the insulating resin sheet |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310652193.4A Active CN103625051B (en) | 2008-03-25 | 2009-03-25 | Insulating resin sheet and use the preparation method of multilayer printed-wiring board of this insulating resin sheet |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP5678657B2 (en) |
| KR (1) | KR101590780B1 (en) |
| CN (2) | CN103625051B (en) |
| TW (2) | TWI478810B (en) |
| WO (1) | WO2009119621A1 (en) |
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| CN113141702A (en) * | 2020-01-17 | 2021-07-20 | 广东生益科技股份有限公司 | Insulating sheet, printed circuit board comprising insulating sheet, semiconductor device and embedded component |
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- 2009-03-25 WO PCT/JP2009/055876 patent/WO2009119621A1/en active Application Filing
- 2009-03-25 KR KR1020107023321A patent/KR101590780B1/en active IP Right Grant
- 2009-03-25 CN CN201310652193.4A patent/CN103625051B/en active Active
- 2009-03-25 JP JP2010505695A patent/JP5678657B2/en active Active
- 2009-03-25 CN CN200980110353.4A patent/CN101977765B/en active Active
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2015
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104602465A (en) * | 2013-10-31 | 2015-05-06 | 味之素株式会社 | Manufacturing method for laminated plate |
| CN104602465B (en) * | 2013-10-31 | 2019-01-01 | 味之素株式会社 | The manufacturing method of laminated plate |
| CN113141702A (en) * | 2020-01-17 | 2021-07-20 | 广东生益科技股份有限公司 | Insulating sheet, printed circuit board comprising insulating sheet, semiconductor device and embedded component |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101590780B1 (en) | 2016-02-02 |
| JP6004017B2 (en) | 2016-10-05 |
| WO2009119621A1 (en) | 2009-10-01 |
| TW201002519A (en) | 2010-01-16 |
| TWI478810B (en) | 2015-04-01 |
| JP2015111579A (en) | 2015-06-18 |
| CN101977765B (en) | 2014-07-02 |
| JPWO2009119621A1 (en) | 2011-07-28 |
| CN103625051B (en) | 2016-01-13 |
| TW201515829A (en) | 2015-05-01 |
| TWI611922B (en) | 2018-01-21 |
| JP5678657B2 (en) | 2015-03-04 |
| CN103625051A (en) | 2014-03-12 |
| KR20110008044A (en) | 2011-01-25 |
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