CN101679612B - Resin composition for interlayer insulation of multilayer printed wiring board - Google Patents

Resin composition for interlayer insulation of multilayer printed wiring board Download PDF

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Publication number
CN101679612B
CN101679612B CN2008800200655A CN200880020065A CN101679612B CN 101679612 B CN101679612 B CN 101679612B CN 2008800200655 A CN2008800200655 A CN 2008800200655A CN 200880020065 A CN200880020065 A CN 200880020065A CN 101679612 B CN101679612 B CN 101679612B
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composition
resin
weight
epoxy
resin combination
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CN101679612A (en
Inventor
相坂刚充
织壁宏
横田忠彦
一之濑荣寿
石田英之
村上晃一
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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
    • H05K3/4635—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials laminating flexible circuit boards using additional insulating adhesive materials between the boards
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Epoxy Resins (AREA)

Abstract

Disclosed is a resin composition suitable for interlayer insulation of a flexible multilayer printed wiring board. Specifically disclosed is a resin composition for interlayer insulation of a multilayer printed wiring board, which contains the following components (A), (B) and (C). (A) a polyimide resin having a polybutadiene structure, a urethane structure and an imide structure in a molecule, while having a phenol structure at an end of the molecule (B) an epoxy resin (C) an inorganic filler having a specific surface area of 18-50 m2/g.

Description

The resin composition for interlayer insulation of multilayer printed circuit board
Technical field
The layer insulation that the present invention relates to be suitable as multilayer printed circuit board is with, the resin combination used of the layer insulation of flexible multi-layer printed circuit board (PCB) particularly.In addition, the invention still further relates to the bonding film that utilizes this resin combination interlayer insulating film preparation, that be used to form multilayer printed circuit board and the multilayer printed circuit board that has been formed interlayer insulating film by this resin combination.
Background technology
Even the flexible multi-layer printed circuit board (PCB) also can be installed by bending for narrow space, therefore for the medium instrument that just advances miniaturization, slimming etc., be absolutely necessary.As the material that in the layer insulation of flexible multi-layer printed circuit board (PCB), uses, for example special opening discloses the resin combination that comprises polyimide with polybutadiene configuration and Resins, epoxy etc. in the 2006-037083 communique, discloses the interlayer insulating film that is obtained by this resin combination in addition and had excellent flexibility, physical strength, dielectric characteristics etc.
Summary of the invention
The invention provides the resin combination that the layer insulation that is suitable for the flexible multi-layer printed circuit board (PCB) is used.
The spy opens the polyimide that contains in the resin combination of 2006-037083 communique, its terminal anhydride group or carboxyl of forming, but owing to these groups and epoxy reaction generate the ester bond that is easy to hydrolysis, thereby in using it for accurate electronic unit the time, consider from the angle of insulating reliability, preferably these groups in minimizing or the eliminating resin combination.Given this, the inventor is in having the polyimide resin of polybutadiene configuration, in order to reduce or to get rid of carboxyl and use the polyimide resin of having introduced the phenol structure endways, and resin combination estimated, found that to obtain excellent interlayer insulating film such as flexibility, physical strength, dielectric characteristics equally.On the other hand, using resin combination as aspect the interlayer insulating film, in order to suppress coefficient of thermal expansion and viscosity etc., known have that to contain with silicon-dioxide be the method for the inorganic filling material of representative, but contain in the composition of the terminal polyimide of phenol and Resins, epoxy at this, inorganic filling material is easy to sedimentation, produces the problem that is difficult to obtain even resin combination.The inventor and then carried out making great efforts research found that by using and compares the material with very little specific surface area zone with normally used inorganic filling material, can obtain inorganic filling material and be easy to the dispersed uniform resin combination.
The inventor has finished the present invention based on above discovery.That is, the present invention includes following content.
The resin composition for interlayer insulation of multilayer printed circuit board, it contains following composition (A), (B), (C):
(A) have polybutadiene configuration, carboxylamine ester structure, imide structure at intramolecularly, and the polyimide resin that has the phenol structure in molecular end;
(B) Resins, epoxy;
(C) specific surface area is 18～50m 2The inorganic filler of/g.
The resin composition for interlayer insulation of multilayer printed circuit board, it contains following composition (A), (B), (C):
(A) has the polyimide resin of phenol structure in molecular end, it is by making [a] have the polybutadiene polyol compound of 2 above alcohol hydroxyl groups in 1 molecule and the reaction of [b] diisocyanate cpd generating diisocyanate prepolymer, and further the multifunctional phenolic compound that has 2 above phenol hydroxyls with [c] tetraprotic acid dianhydride and [d] in 1 molecule reacts and obtains;
(B) Resins, epoxy;
(C) specific surface area is 18～50m 2The inorganic filler of/g.
Above-mentioned [1] or [2] described resin combination, wherein, the specific surface area of the inorganic filling material of composition (C) is 18～40m 2/ g.
Above-mentioned [1] or [2] described resin combination, wherein, the specific surface area of the inorganic filling material of composition (C) is 18～35m 2/ g.
Above-mentioned [1] or [2] described resin combination, wherein, the specific surface area of the inorganic filling material of composition (C) is 20～30m 2/ g.
Above-mentioned [1] or [2] described resin combination, wherein, inorganic filler is silicon-dioxide.
Above-mentioned [1] or [2] described resin combination, wherein, phenol system compound is lacquer resins.
Above-mentioned [1] or [2] described resin combination, wherein, the polybutadiene polyol compound is the hydrogenated butadiene polymer polyol compound.
Above-mentioned [2] described resin combination, wherein, in the polyimide resin of composition (A), with the hydroxyl that has the polybutadiene polyol of 2 above alcohol hydroxyl groups with respect to reacted constituent [a] in 1 molecule, functional group's equivalence ratio of the isocyanate group of reacted constituent [b] diisocyanate cpd is that 1: 1.5～1: 2.5 ratio reacts.
Above-mentioned [1] or [2] described resin combination wherein, further contain composition [D] has 2 above phenol hydroxyls in 1 molecule multifunctional phenolic compound.
Above-mentioned [10] described resin combination, wherein, with respect to the total 100 weight % of composition (A) polyimide resin, composition (B) Resins, epoxy and the multifunctional phenolic compound of composition (D), contain composition (A) 40～85 weight %, composition (B) 15～40 weight % and composition (D) 0～20 weight %.
Be used to form the adhering film of the interlayer insulating film of multilayer printed circuit board, it forms above-mentioned [1] or [2] described resin combination form layers on supporter.
Multilayer printed circuit board wherein uses the described resin combination in above-mentioned [1] or [2] to form interlayer insulating film.
According to the present invention, excellences such as flexibility, physical strength, dielectric characteristics can be provided, be suitable for the resin combination of the layer insulation of flexible multi-layer printed circuit board (PCB).
Embodiment
The polyimide resin of composition among the present invention (A) has polybutadiene configuration, carboxylamine ester structure, imide structure at intramolecularly, and has the phenol structure in molecular end.This can use reacted constituent [a]～[d] at the polyimide resin that molecular end has the phenol structure, obtains by following method.Namely, by making [a] in 1 molecule, have the polybutadiene polyol compound of 2 above alcohol hydroxyl groups and the reaction of [b] diisocyanate cpd generates diisocyanate prepolymer, and then react with [c] tetraprotic acid dianhydride and [d] have 2 above phenol hydroxyls in 1 molecule multifunctional phenolic compound and obtain.
Have the polybutadiene polyol compound of 2 above alcohol hydroxyl groups as [a] in 1 molecule, preferably its number-average molecular weight is 300～5000.When number-average molecular weight is 300 when following, there is modified polyimide resin to lack the tendency of flexibility.When being 5000 when above, there are modified polyimide resin and thermosetting resin to lack the tendency of consistency, the tendency that also has thermotolerance, chemical-resistant also to be short of in addition.
In the present invention, number-average molecular weight is the value of measuring with gel permeation chromatography (GPC) method (polystyrene conversion).The number-average molecular weight of utilizing the GPC method to obtain specifically can be as the calculating of getting off, namely, use clear and the Shodex GPC processed System 21 of electrician's (strain) society as determinator, use clear and the Shodex LF-804/KF-803/KF-804 processed of electrician's (strain) society as chromatographic column, with NMP as moving phase, under 40 ℃ column temperature, measure, and use the typical curve of polystyrene standard to calculate.As this polybutadiene polyol, also can be used alone or as a mixture the hydrogenated butadiene polymer polyvalent alcohol that intramolecular unsaturated link(age) is hydrogenated.This polybutadiene polyol preferably has the polybutadiene diol of hydroxyl in molecular end in addition.Alcohol hydroxyl group refers to the hydroxyl that exists with the form that the hydrogen atom of aliphatic hydrocarbon structure is replaced by hydroxyl (hydroxy).The object lesson of this polybutadiene polyol can be enumerated for example G-1000, G-2000, G-3000, GI-1000, GI-2000 (above material is produced by Japanese Cao Da (strain)), R-45EPI (production of bright dipping petroleum chemistry (strain) society) etc.
[b] diisocyanate cpd is the compound that has 2 isocyanate group at intramolecularly, can enumerate for example Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, vulcabond such as 6-vulcabond, HDI, xylylene vulcabond, diphenylmethanediisocyanate, isophorone diisocyanate etc.
[c] tetraprotic acid dianhydride is the compound that has 2 anhydride group at intramolecularly, can enumerate for example pyromellitic acid dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-cyclohexyl alkene-1,2-dicarboxylic anhydride, 3,3 '-4,4 '-sulfobenzide tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-C] furans-1,3-diketone etc.
In 1 molecule, have the multifunctional phenolic compound of 2 above phenol hydroxyls as [d], can enumerate for example dihydroxyphenyl propane, Bisphenol F, bisphenol S, biphenyl, lacquer resins, alkyl lacquer resins, bisphenol A-type novolac resin, the lacquer resins that contains the Dicyclopentadiene (DCPD) structure, the lacquer resins that contains triazine structure, the lacquer resins that contains biphenyl backbone, the lacquer resins that contains phenyl, terpene modified resol, polyvinyl phenols etc.Special preferred alkyl lacquer resins.The phenol hydroxyl refers to the hydroxyl that exists with the form that the hydrogen atom of aromatic ring structure is replaced by hydroxyl (hydroxy).
In order to obtain polyimide resin of the present invention efficiently, preferably carry out according to following order.At first make reacted constituent [a] polybutadiene polyol and reacted constituent [b] diisocyanate cpd, react greater than 1 ratio with the isocyanate group of the diisocyanate cpd functional group's equivalent with respect to the hydroxyl of this polybutadiene polyol.For the reaction ratio of polybutadiene polyol and diisocyanate cpd, be that 1: 1.5～1: 2.5 ratio is reacted with the isocyanate group of diisocyanate cpd with respect to functional group's equivalence ratio of the hydroxyl of this polybutadiene polyol preferably.
When reacted constituent [a] is when molecular end has the polybutadiene polyol of hydroxyl, this polybutadiene polyol can be represented with following formula (a ').
Figure G2008800200655D00041
(R1 represents to have the divalent organic group of polybutadiene configuration.)
Reacted constituent [b] diisocyanate cpd can be used following formula (b) expression.
OCN-R2-NCO (b)
(R2 represents the organic group of divalent.)
The tetraprotic acid dianhydride of reacted constituent [c] can be used following formula (c) expression.
Figure G2008800200655D00051
(R3 represents the organic group of 4 valencys.)
Make above-mentioned molecular end have the polybutadiene polyol of hydroxyl and diisocyanate cpd react resulting diisocyanate prepolymer can with following formula (a '-b) represent.
(R1 is identical with above-mentioned definition with R2, and n represents the integer of (1≤n≤100) below 100 more than 1.N is preferably the integer of (1≤n≤10) below 10 more than 1.)
Then, the diisocyanate prepolymer that obtains in reacted constituent [c] tetraprotic acid dianhydride and the multifunctional phenolic compound of reacted constituent [d] and the above-mentioned reaction is reacted.Reaction ratio is not particularly limited, and preferably making does not have isocyanate group residual as far as possible in the composition.For residual isocyanate base not in reaction system as far as possible, preferably in reaction, use FT-IR to wait to confirm the disappearance of isocyanate group.According to reaction sequence, can enumerate at first and tetraprotic acid two anhydride reactants, then with the method for multifunctional phenolic compound reaction with add the tetraprotic acid dianhydride simultaneously and method that multifunctional phenolic compound reacts.When adding simultaneously, think to form imide bond by the preferential and isocyanic ester radical reaction of anhydride group.Residual isocyanate group can be introduced the phenol structure endways with multifunctional phenolic compound reaction.
When functional group's equivalent note of the hydroxyl of reacted constituent [a] polybutadiene polyol is done W, with functional group's equivalent note of the isocyanate group of reacted constituent [b] diisocyanate cpd do X, with functional group's equivalent note of reacted constituent [c] tetraprotic acid dianhydride make Y, when functional group's equivalent note of the multifunctional phenolic compound of reacted constituent [d] is made Z, reacted constituent [c] and [d] are preferably to satisfy the ratio use of Y＜X-W＜Y+Z relation.
When using the polybutadiene diol that has a hydroxyl in molecular end during as reacted constituent [a], composition of the present invention (A) polyimide has following formula (1-a) and structure (1-b).
Figure G2008800200655D00061
As concrete reaction conditions, for example the reaction of reacted constituent [a] polybutadiene polyol and reacted constituent [b] diisocyanate cpd can be in organic solvent, temperature of reaction is below 80 ℃, the reaction times is generally under 2～8 hours the condition and carries out.Also can in the presence of catalyzer, carry out as required in addition.Then, can add tetraprotic acid dianhydride and multifunctional phenolic compound in this reaction soln, be that 120～160 ℃, reaction times are to react under 5～24 hours the condition in temperature of reaction.Reaction is carried out in the presence of catalyzer usually.Also can further add organic solvent in addition carries out.
In this reaction, when forming imide bond by the reaction of isocyanate group and anhydride group, produce carbonic acid gas, so the weight reduction by the assaying reaction front and back and obtain the mole number of carbonic acid gas, can calculate the mole number of the imide of formation.
Reaction as required, in order to remove insolubles, also can be carried out the filtration of reaction soln after finishing.Like this, can obtain polyimide resin of the present invention with the varnish shape.Quantity of solvent when the quantity of solvent in the varnish can be by conditioned reaction or after reaction, add solvent etc. and suitably regulate.Polyimide resin of the present invention can be directly used in the preparation composition with above-mentioned varnish shape usually.When separating, for example by being added on the varnish that obtains in the poor solvent methyl alcohol bit by bit, make the polyimide precipitation, can obtain polyimide resin of the present invention with solid form.
The organic solvent that uses in above-mentioned each reaction can be enumerated for example N, N '-dimethyl formamide, N, N '-diethylformamide, N, N '-diethyl acetamide, dimethyl sulfoxide (DMSO), diethyl sulfoxide, N-N-methyl-2-2-pyrrolidone N-, tetramethyl-urea, gamma-butyrolactone, pimelinketone, diglyme, triglyme, Trivalin SF acetic ester, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate isopolarity solvent.These solvents can mix use more than 2 kinds.In addition, as required also suitably non-polar solvent such as BTX aromatics use.
The catalyzer that uses in above-mentioned each reaction can be enumerated for example tetramethyl butane diamine, benzyl dimethyl amine, trolamine, triethylamine, N, organo-metallic catalysts such as tertiary amine, dibutyl tin laurate, dimethyltin chloride, cobalt naphthenate, zinc naphthenate such as N '-lupetidine, α-Jia Jibianji dimethyl amine, N-methylmorpholine, triethylenediamine etc.These catalyzer can mix use more than 2 kinds.Catalyzer most preferably uses triethylenediamine.
As Resins, epoxy of the present invention, the epoxide, triglycidyl group isocyanuric acid ester, alicyclic epoxy resin etc. of condenses that can enumerate for example bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac-type Resins, epoxy, bisphenol-s epoxy resin, alkyl novolac-type Resins, epoxy, bisphenol-type epoxy resin, naphthalene type Resins, epoxy, dicyclopentadiene-type epoxy resin, phenol and have an aromatic aldehyde of phenol hydroxyl has the Resins, epoxy of 2 above functional groups in 1 molecule.These Resins, epoxy can mix use more than 2 kinds.Further preferably use bisphenol A type epoxy resin.
In composition of the present invention, also can cooperate epoxy hardener as required.Epoxy hardener for example can enumerate that amine is that solidifying agent, guanidine are that solidifying agent, imidazoles are that solidifying agent, phenol are that solidifying agent, acid anhydrides are solidifying agent, perhaps material of obtaining of their epoxy adduct or microencapsulation etc.Consider from the viscosity stability equal angles when resin combination is made varnish that particularly preferred phenol is solidifying agent.Epoxy hardener also can mix use more than 2 kinds.
The object lesson of epoxy hardener for example can be enumerated as amine and be the Dyhard RU 100 of solidifying agent, is imidazoles silane, the 2 phenyl 4 methyl 5 hydroxy methylimidazole, 2 of solidifying agent as imidazoles, 4-diamino-6-[2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine cyamelide affixture, be the lacquer resins that contains triazine structure (Off エ ノ ラ イ ト 7050 series for example: big Japanese ink chemical industry (strain) society system) etc. of solidifying agent as phenol.
As polyimide resin composition of the present invention, in order to control composition (A) polyimide resin and composition (B) the Resins, epoxy cross-linking density when solidifying etc., preferred using ingredient (D) has the multifunctional phenolic compound of 2 above phenol hydroxyls in 1 molecule.By using ingredient (D), can improve the cross-linking density of composition (A) and composition (B), the thermal expansion in the time of can being reduced in the temperature more than the second-order transition temperature thus etc.In order to improve above-mentioned cross-linking density, to reduce thermal expansion etc., cooperation ratio for composition in the resin combination (A), composition (B) and composition (D), preferably with respect to their total 100 weight %, composition (A) is 40～85 weight %, composition (B) is 15～40 weight %, and composition (D) is 0～20 weight %.In addition, the mol ratio (x+z)/(y) of the total of the phenol hydroxyl (x) in the composition (A) and the phenol hydroxyl (z) in the composition (D) and the epoxy group(ing) (y) in the composition (B) is preferably 0.7～1.3.
In 1 molecule, have the example of the multifunctional phenolic compound of 2 above phenol hydroxyls as composition (D), can enumerate the material identical with above-mentioned reacted constituent [d].
Thermocurable polyimide resin composition of the present invention can and be used curing catalyst as required.Can enumerate for example trimeric cyanamide, Dyhard RU 100, guanamine or derivatives thereof, amine, the phenols with 1 hydroxyl, organic phosphine Lei, phosphonium salt class, quaternary ammonium salt, multi-anhydride, light cationic catalyst, cyanate esters, isocyanate compound, block isocyanate compound etc.
Containing specific surface area in resin combination of the present invention is 18～50m 2The inorganic filling material of/g.The example of inorganic filling material can be enumerated silicon-dioxide, aluminum oxide etc.Preferred especially silicon-dioxide.Inorganic filling material can mix use more than 2 kinds.The use level of inorganic filling material is not particularly limited, and preferably the scope with 10～50 weight % is added in resin combination.When less than 10 weight %, the tendency that is difficult to obtain effects such as coefficient of thermal expansion and viscosity improvement is arranged.If greater than 50 weight %, not only laser processing variation then, and have the spring rate of cured article to uprise, form the tendency of hard and crisp material.
In addition, the specific surface area of inorganic filling material is with 18～50m 2The scope of/g is used.If beyond this scope, the tendency of filling settlement is then arranged, be difficult to make varnish to keep stable for a long time.The lower limit of the scope of specific surface area is 20m more preferably 2More than/the g.The upper limit of the scope of specific surface area is preferably 40m 2/ g, more preferably 35m 2/ g, and then preferred 30m 2/ g.For example, the scope of specific surface area is preferably 18～40m 2/ g, more preferably 18～35m 2The scope of/g, further preferred 20～30m 2The scope of/g.
The analysis of specific surface area can be obtained with so-called BET method, and described BET method is to make the known molecular adsorption of absorption occupied area under liquid nitrogen temperature on the powder particle surface, is tried to achieve the method for specific area of sample by its amount.Most preferably the method for Shi Yonging is the BET method of having utilized the physical adsorption of rare gas element low temperature and low humidity.
In the scope that can bring into play effect of the present invention, can cooperate various resin additives in the resin combination of the present invention or except composition (A) with the resinous principle (B) etc.The example of resin additive can be enumerated オ Le ベ Application, modified alta-mud tackifier such as (ベ Application ト Application), silicone, fluorine class or acrylic acid or the like defoamer, flow agent, imidazoles, thiazoles, adaptation imparting agents such as triazole species, surface treatment agents such as silane coupling agent, phthalocyanine blue, phthalocyanine green, iodine is green, two diazonium Huangs, tinting materials such as carbon black, P contained compound, bromine-containing compound, aluminium hydroxide, fire retardants such as magnesium hydroxide, Phosphorus antioxidant, antioxidants such as phenol antioxidant.
Resin combination of the present invention especially preferably uses as the interlayer insulating film of multi-layer flexible printed circuit board (PCB).The form that is particularly suitable for comprising the bonding film of the bonding film that contains resin combination layer (A layer) and supporter film (B layer) and the RCC type that forms resin combination layer (A layer) at Copper Foil is used.
Bonding film can be according to well known to a person skilled in the art method, for example prepare by following method, namely, the resinous varnish of hot curing resin composition of the present invention has been dissolved in preparation in organic solvent, at supporter film and this resinous varnish of Copper Foil coating, by heating or brush hot blast etc. and make the organic solvent drying, form the hot curing resin composition layer.
Supporter film (B layer) is the supporter during as the bonding film of preparation, and it can finally be peeled off or remove in the preparation of multilayer printed circuit board.The supporter film for example can be enumerated tinsels such as polyester, polycarbonate and release paper such as polyolefine such as polyethylene, polychlorostyrene ethene, polyethylene terephthalate (following abbreviate as sometimes " PET "), PEN or Copper Foil etc.Can also use heat stable resins such as polyimide, polymeric amide, polyamidoimide, liquid crystalline polymers.When using Copper Foil as the supporter film, can remove by carrying out etching with etching solutions such as iron trichloride, dichloride copper.Supporting film also can carry out the demoulding and handle except delustring (mat) processing, corona treatment, when considering separability, more preferably implements the demoulding and handles.The thickness of supporting film is not particularly limited, and is generally 10～150 μ m, preferably uses in the scope of 25～50 μ m.
For the situation of RCC type, Copper Foil uses as the part of the conductor layer of multilayer printed circuit board.In general, electrolytic copper foil, rolled copper foil can be enumerated, also extra thin copper foil can be used.Extra thin copper foil also can have carrier copper foil.The thickness of Copper Foil is not particularly limited, but in order to form the wiring of fine pitch, preferably uses extra thin copper foil.
Can enumerate for example aromatic hydrocarbons such as Trivalin SF class, toluene, dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone etc. such as acetate esters, cellosolve, diethylene glycol monobutyl ether such as ketones such as acetone, methyl ethyl ketone, pimelinketone, ethyl acetate, butylacetate, cellosolve acetate, propylene glycol methyl ether acetate, Trivalin SF acetic ester for the preparation of the organic solvent of varnish.Organic solvent can be used in combination more than 2 kinds.
Drying conditions is not particularly limited, but in order to keep the cementability of bonding film, no longer is important as long as hot curing resin composition just can solidify when drying.In addition, produce and expand owing to can cause solidifying the back when in the bonding film a large amount of organic solvent residual being arranged, therefore carry out drying so that the organic solvent in the hot curing resin composition contain proportional being generally below the 5 quality %, below the preferred 3 quality %.Concrete drying conditions is according to the solidified nature of hot curing resin composition or the organic solvent amount in the varnish and different, for example for the varnish of the organic solvent that contains 30～60 quality %, and usually can be 80～120 ℃ of dryings about 3～13 minutes.Those skilled in the art by simple experiment can set suitably, preferred drying conditions.
The thickness of resin combination layer (A layer) can be set in the scope of 5～500 μ m usually.The preferable range of A layer thickness is according to the purposes of bonding film and different, when being used for by lamination method (PVC Le De ア Star プ method) preparation multilayer printed circuit board, the thickness that forms the conductor layer of circuit is generally 5～70 μ m, and the A layer thickness that therefore is equivalent to interlayer insulating film is preferably the scope of 10～100 μ m.
The A layer also can be protected with protective membrane.By protecting with protective membrane, can prevent from adhering to dirt etc. or scar occurring at the resin combination laminar surface.Protective membrane can be peeled off when lamination.Protective membrane can use the material same with support membrane.The thickness of protective membrane is not particularly limited, and is preferably the scope of 1～40 μ m.
Bonding film of the present invention can suitably be laminated on the circuit substrate by vacuum lamination apparatus.Internal layer circuit substrate used herein mainly can be enumerated internal layer circuit substrates such as polyester substrate, polyimide substrate, polyamideimide-based plate, liquid crystalline polymers substrate.Bonding film of the present invention also can be used for the further multiple stratification of multilayer printed circuit board in addition.Consider that from the angle of the adaptation of insulation layer and circuit substrate the preferred circuit surface utilizes hydrogen peroxide/sulfuric acid, メ Star Network エ Star チ ボ Application De surface treatment agents such as (productions of メ Star Network (strain) society) to carry out roughening treatment in advance.
As commercially available vacuum lamination apparatus, can enumerate vacuum coater (バ キ ユ one system ア Star Block リ ケ one タ one), (strain) name mechanism of for example ニ チ go one モ one ト Application (strain) production and make vacuum pressure type laminating machine of producing, the dry-coated machine of roll-type that the テ of Hitachi Network ノ エ Application ジ ニ ア リ Application グ (strain) produces, vacuum lamination apparatus of the エ of Hitachi one ア イ one シ one (strain) production etc.
In lamination, when bonding film has protective membrane, after removing this protective membrane, on one side press sticking support on circuit substrate bonding film pressurization and heating on one side.As the condition of lamination, preferably as required bonding film and circuit substrate are preheated, press sticking temperature to be preferably 70～140 ℃, press sticking pressure to be preferably 1～11kgf/cm 2, under air is pressed to the decompression below the 20mmHg, carry out lamination.In addition, the method for lamination can be intermittent type, also can be for using the continous way of roller.
For the situation of the bonding film that contains resin combination layer (A layer) and supporter film (B layer), follow following operation.With bonding film lamination after on the circuit substrate, near the cool to room temperature and peel off the supporter film.Then, the hot curing resin composition that is laminated on the circuit substrate is heating and curing.The condition that is heating and curing is that 150～220 ℃, time are that 20～180 minutes scope is selected in temperature usually, is that 160～200 ℃, time are that 30～120 minutes scope is selected in temperature more preferably.And, when the supporter film carries out that the demoulding is handled or when having peel ply such as silicon, also can hot curing resin composition be heating and curing the back or be heating and curing and perforate after peel off the supporter film.
After the cured article that forms resin combination is insulation layer, also can carry out perforate with the method for awl, laser, plasma body or their combination etc. at circuit substrate as required, form perforation (PVC ア ホ one Le) or through hole.General especially use utilizes the perforate of laser such as carbon dioxide laser or YAG laser.
Then carry out the surface treatment of insulation layer.Surface treatment can be adopted the method for using in decontamination operation (テ ス ミ ア Block ロ セ ス), can carry out with the form of double as decontamination operation.The reagent that is used for the decontamination operation generally is oxygenant.Oxygenant can be enumerated for example permanganate (potassium permanganate, sodium permanganate etc.), dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid etc.The preferred use handled as the alkaline permanganic acid solution (for example aqueous sodium hydroxide solution of potassium permanganate, sodium permanganate) of following oxygenant, and described oxygenant is general oxygenant when utilizing lamination method to prepare the alligatoring of carrying out insulation layer in the multilayer printed circuit board preferably.With before the oxidizer treatment, also can utilize swelling agent to handle.In addition, after utilizing oxygenant to handle, utilize reductive agent to carry out neutralizing treatment usually.
In order to improve the stripping strength of the conductor layer that is formed by plating, above-mentioned decontamination operation has the alligatoring surface of insulating layer concurrently and concavo-convex purpose is set.
After carrying out surface treatment, form conductor layer by plating at surface of insulating layer.The formation of conductor layer can be used the method for electroless plating and electro deposition combination is implemented.In addition, conductor layer also can only form with electroless plating by forming the plating protective layer of anti-graphics.After forming conductor layer, handle by the annealing of under 150～200 ℃ temperature, carrying out 20～90 minutes (anneal), can further increase the stripping strength of conductor layer and make its stabilization.
As the method for conductor layer being carried out composition processing and formation circuit, can use and for example well known to a person skilled in the art metal covering etch, semi-additive process etc.When using the metal covering etch, the thickness of electroless plating copper layer is 0.1～3 μ m, preferred 0.3～2 μ m.Thereon behind the thickness formation electrolytic coating (panel coating) with 3～35 μ m, preferred 5～20 μ m; form etch protection layer, and carry out etching with etching solutions such as iron trichloride, dichloride copper, form conductor fig thus; by the release etch protective layer, can obtain circuit substrate then.In addition, when using semi-additive process, the thickness that makes electroless plating copper layer is 0.1～3 μ m, after preferred 0.3～2 μ m forms electroless plating copper layer like this, forms the figure protective layer, then peels off after electro-coppering, can obtain circuit substrate thus.
For the situation of the bonding film of the RCC type that forms resin combination layer (A layer) at Copper Foil, follow following operation.The bonding film of lamination on circuit substrate makes hot curing resin composition be heating and curing as described above.Then carry out perforate as described above, the surface treatment of boring a hole by soft etching.Then carry out electroless plating, use metal covering etch etc. can obtain circuit substrate as described above.As the Copper Foil that uses, use the electrolytic copper foil of 12 or 18 μ m kinds usually, can enumerate for example Mitsui Metal Co., Ltd.'s mining industry (strain) system " DFF ", " NS-VLP ", day ore deposit metal (strain) system " JTC " etc.In addition, according to the requirement of fine-line, also extra thin copper foil can be used, for example Mitsui Metal Co., Ltd.'s mining industry (strain) system " Micro Thin Ex ", Japanese electrolysis (strain) system " YSMAP " etc. can be enumerated.
Embodiment
Below, specify content of the present invention by embodiment, but present embodiment there is not any restriction to the present invention.
＜preparation example 1 〉
The preparation of＜polyimide resin (polyimide resin varnish A) 〉
In the flask that has whipping appts, thermometer and condenser, add 203.07g λ-butyrolactone, 304.60g ソ Le ベ Star ソ 150 as solvent, and adding isophorone diisocyanate 88.8g (0.4 mole), hydrogenated butadiene polymer glycol (hydroxyl value 48.5KOH-mg/g, molecular weight is 2313) 231.3g (0.1 mole) and polybutadiene diol (hydroxyl value 52.6KOH-mg/g, molecular weight is 2133) 213.3g (0.1 mole), 70 ℃ of reactions 4 hours.(hydroxyl equivalent is 229.4g/ep then to add the nonyl lacquer resins, average out to 4.27 officials can, the average computation molecular weight is the 979.5g/ mole) 195.9g (0.2 mole) and ethylene glycol bisthioglycolate dehydration trimellitate (エ チ レ Application グ リ コ one Le PVC ス ア Application ヒ De ロ ト リ メ テ one ト) 41.0g (0.1 mole), be warming up to 150 ℃ with 2 hours, and reacted 12 hours.
Reaction back forms transparent dark brown liquid, obtain non-volatile component and be 60% and viscosity be the polyimide resin solution of 15Pas (25 ℃).The solution coat of gained polyimide resin on the KBr plate, is made the solvent composition volatilization and obtains sample, measure its infrared absorption spectrum, the result can confirm the 2270cm as the characteristic absorbance of isocyanate group -1Completely dissolve is at 725cm -1, 1780cm -1And 1720cm -1There is the absorption of imide ring at the place.Can confirm at 1540cm in addition -1There is the absorption of amino-formate bond at the place.In addition, follow the carrying out of imidization and the amount of carbon dioxide that produces can be followed the trail of according to the variation of flask charge weight, this amount is 8.8g (0.2 mole).Functional group's equivalent of the acid anhydrides of ethylene glycol bisthioglycolate dehydration trimellitate is 0.2 mole, and the generation of carbonic acid gas also is 0.2 mole, and conclusion is that acid anhydrides is used to form imide fully, does not have carboxylic acid anhydride.
Therefore can obtain following conclusion, namely, in isocyanate group, there is 0.2 mole to be transformed to imide bond, remaining isocyanate group forms amino-formate bond with the hydroxyl of hydrogenated butadiene polymer two pure and mild polybutadiene diol and the phenol hydroxyl in the nonyl lacquer resins, obtain in resin, having the phenol hydroxyl of nonyl lacquer resins thus, and a part of phenol hydroxyl is by the imide-urethane resin of amino-formate bond modification.
＜preparation example 2 〉
The preparation of＜polyimide resin (polyimide resin varnish B) 〉
In the flask that has whipping appts, thermometer and condenser, add 292.09g ethyl Diethylene Glycol acetic ester, 292.09g ソ Le ベ Star ソ 150 as solvent, and adding isophorone diisocyanate 88.8g (0.4 mole) and polybutadiene diol (hydroxyl value 52.6KOH-mg/g, molecular weight is 2133) 426.6g (0.2 mole), 70 ℃ of reactions 4 hours.(hydroxyl equivalent is 229.4g/ep then to add the nonyl lacquer resins, average out to 4.27 officials can, the average computation molecular weight is the 979.5g/ mole) 195.9g (0.2 mole) and ethylene glycol bisthioglycolate dehydration trimellitate 41.0g (0.1 mole), be warming up to 150 ℃ with 2 hours, and reacted 12 hours.
Reaction back forms transparent dark brown liquid, obtain non-volatile component and be 56% and viscosity be the polyimide resin solution of 12Pas (25 ℃).The solution coat of gained polyimide resin on the KBr plate, is made the solvent composition volatilization and obtains sample, measure its infrared absorption spectrum, the result can confirm the 2270cm as the characteristic absorbance of isocyanate group -1Completely dissolve is at 725cm -1, 1780cm -1And 1720cm -1There is the absorption of imide ring at the place.Can confirm at 1540cm in addition -1There is the absorption of amino-formate bond at the place.In addition, follow the carrying out of imidization and the amount of carbon dioxide that produces can be followed the trail of according to the variation of flask charge weight, this amount is 8.8g (0.2 mole).Functional group's equivalent of the acid anhydrides of ethylene glycol bisthioglycolate dehydration trimellitate is 0.2 mole, and the generation of carbonic acid gas also is 0.2 mole, and conclusion is that acid anhydrides is used to form imide fully, does not have carboxylic acid anhydride.Therefore can obtain following conclusion, namely, in isocyanate group, there is 0.2 mole to be transformed to imide bond, remaining isocyanate group forms amino-formate bond with the hydroxyl of polybutadiene diol and the phenol hydroxyl in the nonyl lacquer resins, obtain in resin, having the phenol hydroxyl of lacquer resins thus, and a part of phenol hydroxyl is by the polyimide urethane resin of amino-formate bond modification.
＜reference example 1 〉
40 parts of the polyimide resin varnish A that obtains in the preparation example 1 of interpolation as composition (A), (aromatic hydrocarbons is mixed solvent: bright dipping petroleum chemistry (strain) system) mix varnish and (form minute 50% admittedly as the diethylene glycol monoethyl ether acetic ester (following note is made EDGAc) of the bisphenol-A phenolic varnish type Resins, epoxy of composition (B) and イ Block ゾ one Le 150, epoxy equivalent (weight) 210, ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " 157S70 ") 10.9 part, 0.5 part of imdazole derivatives (ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " P200H50 "), (specific surface area is 80m to preparing spherical SiO 2 2/ g) 10 parts of 6 parts and toluene, 5.5 parts of resin combinations that prepare the varnish shape of gamma-butyrolactone.
＜reference example 2 〉
40 parts of polyimide resin varnish A that obtain in the preparation example 1 of interpolation as composition (A), mix varnish as the EDGAc of the bisphenol-A phenolic varnish type Resins, epoxy of composition (B) and イ ズ ゾ-Le 150 and (form minute 50% admittedly, epoxy equivalent (weight) 210, ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " 157S70 ") 10.9 parts, 0.5 part of imdazole derivatives (ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " P200H50 "), (specific surface area is 6.2m to preparing spherical SiO 2 2/ g) 6 parts and 10 parts of resin combinations that prepare the varnish shape of toluene.
＜reference example 3 〉
40 parts of polyimide resin varnish B that obtain in the preparation example 2 of interpolation as composition (A), mix varnish as the EDGAc of the bisphenol-A phenolic varnish type Resins, epoxy of composition (B) and イ Block ゾ-Le 150 and (form minute 50% admittedly, epoxy equivalent (weight) 210, ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " 157S70 ") 10.9 parts, 0.5 part of imdazole derivatives (ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " P200H50 "), (specific surface area is 80m to preparing spherical SiO 2 2/ g) 6 parts and 10 parts of toluene, 5.5 parts of resin combinations that prepare the varnish shape of gamma-butyrolactone.
＜reference example 4 〉
40 parts of polyimide resin varnish B that obtain in the preparation example 2 of interpolation as composition (A), mix varnish as the EDGAc of the bisphenol-A phenolic varnish type Resins, epoxy of composition (B) and イ Block ゾ one Le 150 and (form minute 50% admittedly, epoxy equivalent (weight) 210, ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " 157S70 ") 10.9 parts, 0.5 part of imdazole derivatives (ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " P200H50 "), (specific surface area is 6.2m to preparing spherical SiO 2 2/ g) 6 parts and 10 parts of resin combinations that prepare the varnish shape of toluene.
＜embodiment 1 〉
40 parts of polyimide resin varnish A that obtain in the preparation example 1 of interpolation as composition (A), mix varnish as the EDGAc of the bisphenol-A phenolic varnish type Resins, epoxy of composition (B) and イ Block ゾ-Le 150 and (form minute 50% admittedly, epoxy equivalent (weight) 210, ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " 157S70 ") 10.9 parts, 0.5 part of imdazole derivatives (ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " P200H50 "), (specific surface area is 30m to preparing spherical SiO 2 2/ g) 6 parts and 10 parts of toluene, 2 parts of resin combinations that prepare the varnish shape of gamma-butyrolactone.
＜embodiment 2 〉
40 parts of polyimide resin varnish B that obtain in the preparation example 2 of interpolation as composition (A), mix varnish as the EDGAc of the bisphenol-A phenolic varnish type Resins, epoxy of composition (B) and イ Block ゾ one Le 150 and (form minute 50% admittedly, epoxy equivalent (weight) 210, ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " 157S70 ") 10.9 parts, 0.5 part of imdazole derivatives (ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " P200H50 "), (specific surface area is 30m to preparing spherical SiO 2 2/ g) 6 parts and 10 parts of toluene, 2 parts of resin combinations that prepare the varnish shape of gamma-butyrolactone.
＜embodiment 3 〉
40 parts of polyimide resin varnish A that obtain in the preparation example 1 of interpolation as composition (A), mix varnish as the EDGAc of the bisphenol-A phenolic varnish type Resins, epoxy of composition (B) and イ Block ゾ-Le 150 and (form minute 50% admittedly, epoxy equivalent (weight) 210, ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " 157S70 ") 10.9 parts, 0.5 part of imdazole derivatives (ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " P200H50 "), (specific surface area is 20m to preparing spherical SiO 2 2/ g) 6 parts and 10 parts of toluene, 4 parts of resin combinations that prepare the varnish shape of gamma-butyrolactone.
＜embodiment 4 〉
40 parts of polyimide resin varnish B that obtain in the preparation example 2 of interpolation as composition (A), mix varnish as the EDGAc of the bisphenol-A phenolic varnish type Resins, epoxy of composition (B) and イ Block ゾ one Le 150 and (form minute 50% admittedly, epoxy equivalent (weight) 210, ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " 157S70 ") 10.9 parts, 0.5 part of imdazole derivatives (ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " P200H50 "), (specific surface area is 20m to preparing spherical SiO 2 2/ g) 6 parts and 10 parts of toluene, 4 parts of resin combinations that prepare the varnish shape of gamma-butyrolactone.
＜embodiment 5 〉
40 parts of polyimide resin varnish A that obtain in the preparation example 1 of interpolation as composition (A), mix varnish as the EDGAc of the bisphenol-A phenolic varnish type Resins, epoxy of composition (B) and イ Block ゾ one Le 150 and (form minute 50% admittedly, epoxy equivalent (weight) 210, ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " 157S70 ") 10.9 parts, 0.5 part of imdazole derivatives (ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " P200H50 "), (specific surface area is 22m to ball-aluminium oxide 2/ g) 6 parts and 10 parts of resin combinations that prepare the varnish shape of toluene.
＜embodiment 6 〉
40 parts of polyimide resin varnish B that obtain in the preparation example 2 of interpolation as composition (A), mix varnish as the EDGAc of the bisphenol-A phenolic varnish type Resins, epoxy of composition (B) and イ Block ゾ one Le 150 and (form minute 50% admittedly, epoxy equivalent (weight) 210, ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " 157S70 ") 10.9 parts, 0.5 part of imdazole derivatives (ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " P200H50 "), (specific surface area is 22m to ball-aluminium oxide 2/ g) 6 parts and 10 parts of resin combinations that prepare the varnish shape of toluene.
＜dispersiveness 〉
For reference example 1～4, when room temperature left standstill about 12 hours, filling settlement, varnish separated with varnish, but in embodiment 1～6, filler can maintain homodisperse state.
＜embodiment 7 〉
For the varnish that obtains among the embodiment 1, (thickness is 38 μ m to handle polyethylene terephthalate in the demoulding, be designated hereinafter simply as PET) on utilize coating machine to be coated with this resin combination, making dried resin thickness is 60 ℃, form the resin combination layer in dry 12 minutes down at 80～120 ℃ (average 100 ℃), obtain bonding film.
＜embodiment 8 〉
For the varnish that obtains among the embodiment 2, form the resin combination layer at PET similarly to Example 7 and obtain bonding film.
＜embodiment 9 〉
For the varnish that obtains among the embodiment 3, form the resin combination layer at PET similarly to Example 7 and obtain bonding film.
＜embodiment 10 〉
For the varnish that obtains among the embodiment 4, form the resin combination layer at PET similarly to Example 7 and obtain bonding film.
＜embodiment 11 〉
For the varnish that obtains among the embodiment 5, form the resin combination layer at PET similarly to Example 7 and obtain bonding film.
＜embodiment 12 〉
For the varnish that obtains among the embodiment 6, form the resin combination layer at PET similarly to Example 7 and obtain bonding film.
To be heating and curing 90 minutes at 180 ℃ by the bonding film that embodiment 7～12 obtains.The characteristic of the cured article of each resin combination is shown in table 1.Tensile break strength is measured and is carried out according to JIS (JIS) K7127.In addition, dielectric characteristics is estimated with cavity method (ア ジ レ Application ト テ Network ノ ロ ジ one (strain) E8362B processed of society).Characteristic value is shown in table 1.
＜comparative example 1 〉
As a comparative example 1, the interlayer dielectic (aginomoto Off ア イ Application テ Network ノ (strain) ABF-GXcode13 processed of society) of Resins, epoxy system was heating and curing 90 minutes at 180 ℃, obtain cured article.With above-mentioned same, the characteristic value of cured article is shown in table 1.
＜table 1 〉
Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Comparative example 1
Young's modulus (MPa) 57 131 88 151 66 141 4000
Tensile strength (MPa) 13 13 15 20 16 16 93
Elongation at break (%) 105 65 73 53 76 45 5
Specific inductivity (1GHz) 2.42 2.48 2.54 2.75 2.83 2.84 3.35
Tangent of the dielectric loss angle (1GHz) 0.008 0.007 0.006 0.007 0.008 0.006 0.012
＜embodiment 13 〉
Closing force (1) with Copper Foil
Utilizing (strain) name mechanism to make made vacuum lamination apparatus is that 100 ℃, pressure are 7kgf/cm in temperature 2, air pressure is under the following condition of 5mmHg, and the bonding film that obtains among the embodiment 7 is carried out single sided lamination respectively on the S face of Copper Foil (day ore deposit metal (strain) JTC paper tinsel processed) and M face, prepares 3 layers of thing of Copper Foil/bonding film/PET respectively.Then the PET film is handled in the demoulding and peeled off, on the copper plating film laminated plate that メ Star Network エ Star チ ボ Application De CZ-8100 handled, carry out lamination equally.Under 120 ℃, be heating and curing 30 minutes then, and then under 180 ℃, be heating and curing 90 minutes.The substrate of use gained is measured the stripping strength at the interface of resin/Copper Foil, and peeling off of S face is 0.66kgf/cm as a result, and peeling off of M face is 1.22kgf/cm.Stripping strength is measured and is estimated according to JIS C 6481 in addition, and copper thickness is set at 18 μ m.
＜embodiment 14 〉
Closing force (2) with Copper Foil
Use the bonding film that obtains among the embodiment 8, measure the stripping strength at the interface of resin/Copper Foil similarly to Example 13, peeling off of S face is 0.73kgf/cm as a result, and peeling off of M face is 1.05kgf/cm.
＜embodiment 15 〉
Closing force (3) with Copper Foil
Use the bonding film that obtains among the embodiment 9, measure the stripping strength at the interface of resin/Copper Foil similarly to Example 13, peeling off of S face is 0.50kgf/cm as a result, and peeling off of M face is 1.04kgf/cm.
＜embodiment 16 〉
Closing force (4) with Copper Foil
Use the bonding film that obtains among the embodiment 10, measure the stripping strength at the interface of resin/Copper Foil similarly to Example 13, peeling off of S face is 0.67kgf/cm as a result, and peeling off of M face is 0.94kgf/cm.
＜embodiment 17 〉
Closing force (5) with Copper Foil
Use the bonding film that obtains among the embodiment 11, measure the stripping strength at the interface of resin/Copper Foil similarly to Example 13, peeling off of S face is 0.46kgf/cm as a result, and peeling off of M face is 1.13kgf/cm.
＜embodiment 18 〉
Closing force (6) with Copper Foil
Use the bonding film that obtains among the embodiment 12, measure the stripping strength at the interface of resin/Copper Foil similarly to Example 13, peeling off of S face is 0.44kgf/cm as a result, and peeling off of M face is 1.06kgf/cm.
＜comparative example 2 〉
The interlayer dielectic (aginomoto Off ア イ Application テ Network ノ (strain) ABF-GXcode13 processed of society) of the Resins, epoxy system of use, measure the stripping strength at the interface of resin/Copper Foil similarly to Example 13, peeling off of S face is 0.29kgf/cm as a result, and peeling off of M face is 1.44kgf/cm.
Embodiment 13～18, comparative example 2 the results are summarized in table 2.Even also can show good adaptation for the level and smooth like this surface of the S face of Copper Foil among the embodiment as can be known.
＜table 2 〉
Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Comparative example 2
S face (kgf/cm) 0.66 0.73 0.50 0.67 0.46 0.44 0.29
M face (kgf/cm) 1.22 1.05 1.04 0.94 1.13 1.06 1.44
＜embodiment 19 〉
Peel off (1) about coating
Utilizing (strain) name mechanism to make made vacuum lamination apparatus is that 100 ℃, pressure are 7kgf/cm in temperature 2, air pressure is under the following condition of 5mmHg, and the bonding film that obtains among the embodiment 8 is carried out two-sided lamination at the copper plating film laminated plate that メ Star Network エ Star チ ボ Application De CZ-8100 handled.Then the PET film is handled in the demoulding and peeled off, being heating and curing at 180 ℃ formed insulation layer in 30 minutes.The surface treatment program of the insulation layer of double as decontamination operation is used the following liquid medicine of ア ト テ Star Network ジ ヤ パ Application society system.Swelling agent " Swelling Dip Securiganth P ", oxygenant " Concentrate CompactCP " (permanganic acid alkaline solution), reductive agent " Reduction solution Securiganth P-500 ".
Under 80 ℃ temperature, carry out 5 minutes surface treatment with swelling agent solution, then under 80 ℃ temperature, carry out 5 minutes surface treatment with oxygenant, at last 40 ℃ of neutralizing treatment of carrying out 5 minutes with reductant solution.Then give the catalyzer of electroless plating copper layer at surface of insulating layer, then in electroless plating copper liquid, under 32 ℃ temperature dipping 30 minutes, form the electroless plating copper film of 1.5 μ m.It after 30 minutes, is carried out acid elution 150 ℃ of dryings, as positive pole, is 2.0A/dm in cathode current density with phosphorous copper coin 2Condition under carry out 12 minutes, form copper plating film.Then further 180 ℃ of anneal of carrying out 30 minutes.The stripping strength of gained conductor layer is 0.71kgf/cm.In addition, stripping strength is measured and is estimated according to JIS C6481, and the conductor thickness of coating is about 25 μ m.
＜comparative example 3 〉
The interlayer dielectic (aginomoto Off ア イ Application テ Network ノ (strain) ABF-GXcode13 processed of society) of the Resins, epoxy system of use forms insulation layer similarly to Example 19.Use the liquid medicine of ア ト テ Star Network ジ ヤ パ Application society system to carry out surface treatment equally.
The surface treatment that utilizes swelling agent solution to carry out under 60 ℃ temperature 5 minutes is then carried out 15 minutes surface treatment with oxygenant under 80 ℃ temperature, at last with reductant solution 40 ℃ of neutralizing treatment of carrying out 5 minutes.In addition, the stripping strength of gained conductor layer is 0.6kgf/cm.
＜preparation example 3 〉
The preparation of＜wire modified polyimide resin (wire modified polyimide resin varnish C) 〉
In reaction vessel, with G-3000 (2 functionality C-terminal polyhutadiene, number-average molecular weight=5047 (GPC method), hydroxyl equivalent=1798g/eq, Gu formation branch 100w%: Japanese Cao Da (strain) system) 50g, 23.5g イ Block ゾ one Le 150, dibutyl tin laurate 0.005g mix, and make its uniform dissolution.Be warming up to 50 ℃ after reaching uniform state, add Toluene-2,4-diisocyanate while further stir, (4.8g of isocyanate group equivalent=87.08g/eq.) carries out about 3 hours reaction to the 4-vulcabond.Then, after this reactant is cooled to room temperature, to wherein adding benzophenone tetracarboxylic dianhydride (anhydride equivalent=161.1g/eq.) 8.96g, triethylenediamine 0.07g, ethyl Diethylene Glycol acetic ester (ダ イ セ Le chemical industry (strain) society system) 40.4g, be warming up to 130 ℃ while stirring, carry out about 4 hours reaction.Confirm 2250cm by FT-IR -1The NCO peak disappear.When the terminal point of confirming that the NCO peak is considered as reacting when disappearing, reactant is cooled to room temperature after, filter with 100 purpose filter clothes, obtain wire modified polyimide resin (wire modified polyimide resin varnish C).
The proterties of wire modified polyimide resin varnish A: viscosity=7.5Pas (25 ℃, E type viscometer)
Acid number=16.9mgKOH/g
Gu form branch=50w%
＜reference example 5 〉
35 parts of polyimide resin varnish C that obtain in the preparation example 3 of interpolation as composition (A), mix varnish as the EDGAc of the bisphenol-A phenolic varnish type Resins, epoxy of composition (B) and イ Block ゾ one Le 150 and (form minute 50% admittedly, epoxy equivalent (weight) 210, ジ ヤ パ Application エ ボ キ シ レ ジ Application (strain) system " 157S70 ") 10.9 parts, 4.5 parts of lacquer resinss (big Japanese ink chemical industry (strain) system " TD2090-60M "), (specific surface area is 4.1m to preparing spherical SiO 2 2/ g) 6 parts and 10 parts of toluene, 2 parts of resin combinations that prepare the varnish shape of gamma-butyrolactone.
＜dispersiveness 〉
For comparative example 4, even varnish is left standstill about 12 hours in room temperature, filler also can be kept uniform dispersion state.
＜physics value 〉
For the varnish that obtains in the comparative example 4, form the resin combination layer at PET similarly to Example 7, obtain bonding film, be heating and curing 90 minutes at 180 ℃.The characteristic value of cured article is shown in table 3.In addition, use the bonding film that is obtained by comparative example 4, measure the stripping strength at the interface of resin/Copper Foil similarly to Example 13, peeling off of S face is 0.55kgf/cm as a result, and peeling off of M face is 0.67kgf/cm.
＜table 3 〉
Reference example 5
Young's modulus (MPa) 33
Tensile strength (MPa) 12
Elongation at break (%) 67
Specific inductivity (1GHz) 2.64
Tangent of the dielectric loss angle (1GHz) 0.013

Claims (11)

1. the resin composition for interlayer insulation of multilayer printed circuit board, it contains following composition (A), (B) and (C):
(A) have polybutadiene configuration, carboxylamine ester structure, imide structure at intramolecularly, and the polyimide resin that has the phenol structure in molecular end;
(B) Resins, epoxy;
(C) specific surface area is 18～50m 2The inorganic filler of/g is selected from more than one of silicon-dioxide and aluminum oxide,
Wherein further contain composition [D] has 2 above phenol hydroxyls in 1 molecule multifunctional phenolic compound, and with respect to the total 100 weight % of composition (A) polyimide resin, composition (B) Resins, epoxy and the multifunctional phenolic compound of composition (D), contain composition (A) 40～85 weight %, composition (B) 15～40 weight % and composition (D) 0～20 weight %.
2. the resin composition for interlayer insulation of multilayer printed circuit board, it contains following composition (A), (B) and (C):
(A) has the polyimide resin of phenol structure in molecular end, this resin is by making [a] have the polybutadiene polyol compound of 2 above alcohol hydroxyl groups in 1 molecule and the reaction of [b] diisocyanate cpd generating diisocyanate prepolymer, further has the multifunctional phenolic compound reaction of 2 above phenol hydroxyls with [c] tetraprotic acid dianhydride and [d] in 1 molecule and obtains;
(B) Resins, epoxy;
(C) specific surface area is 18～50m 2The inorganic filler of/g is selected from more than one of silicon-dioxide and aluminum oxide,
Wherein further contain composition [D] has 2 above phenol hydroxyls in 1 molecule multifunctional phenolic compound, and with respect to the total 100 weight % of composition (A) polyimide resin, composition (B) Resins, epoxy and the multifunctional phenolic compound of composition (D), contain composition (A) 40～85 weight %, composition (B) 15～40 weight % and composition (D) 0～20 weight %.
3. resin combination according to claim 1 and 2, wherein, the specific surface area of composition (C) inorganic filler is 18～40m 2/ g.
4. resin combination according to claim 1 and 2, wherein, the specific surface area of composition (C) inorganic filler is 18～35m 2/ g.
5. resin combination according to claim 1 and 2, wherein, the specific surface area of composition (C) inorganic filler is 20～30m 2/ g.
6. resin combination according to claim 1 and 2, wherein, inorganic filler is silicon-dioxide.
7. resin combination according to claim 2, wherein, [d] has 2 above phenol hydroxyls in 1 molecule multifunctional phenolic compound is phenolic novolac.
8. resin combination according to claim 1 and 2, wherein, the polybutadiene polyol compound is the hydrogenated butadiene polymer polyol compound.
9. resin combination according to claim 2, wherein, in the polyimide resin of composition (A), with the hydroxyl that has the polybutadiene polyol of 2 above alcohol hydroxyl groups with respect to reacted constituent [a] in 1 molecule, functional group's equivalence ratio of the isocyanate group of reacted constituent [b] diisocyanate cpd is that 1: 1.5～1: 2.5 ratio reacts.
10. be used to form the adhering film of the interlayer insulating film of multilayer printed circuit board, form layers on supporter forms with claim 1 or 2 described resin combinations for it.
11. multilayer printed circuit board, wherein right to use requires 1 or 2 described resin combinations to form interlayer insulating film.
CN2008800200655A 2007-06-14 2008-06-12 Resin composition for interlayer insulation of multilayer printed wiring board Active CN101679612B (en)

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