CN101909878A - Copper foil with resin and process for producing copper foil with resin - Google Patents
Copper foil with resin and process for producing copper foil with resin Download PDFInfo
- Publication number
- CN101909878A CN101909878A CN2008801233016A CN200880123301A CN101909878A CN 101909878 A CN101909878 A CN 101909878A CN 2008801233016 A CN2008801233016 A CN 2008801233016A CN 200880123301 A CN200880123301 A CN 200880123301A CN 101909878 A CN101909878 A CN 101909878A
- Authority
- CN
- China
- Prior art keywords
- copper foil
- resin
- tree fat
- curing
- semi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000011347 resin Substances 0.000 title claims abstract description 459
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- 239000011889 copper foil Substances 0.000 title claims abstract description 248
- 238000000034 method Methods 0.000 title claims abstract description 78
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- 125000003118 aryl group Chemical group 0.000 claims description 19
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- VMYXFDVIMUEKNP-UHFFFAOYSA-N trimethoxy-[5-(oxiran-2-yl)pentyl]silane Chemical compound CO[Si](OC)(OC)CCCCCC1CO1 VMYXFDVIMUEKNP-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
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Abstract
Disclosed is a copper foil with a resin that can realize an improvement in dimensional stability of a build-up printed wiring board and can realize the formation of a fine pitch circuit. Also disclosed is a process for producing the copper foil with a resin. The copper foil with a resin comprises a copper foil, and a cured resin layer and a semi-cured resin layer provided in that order on a surface of the copper foil. The surface roughness (Rzjis) of a side, of the copper foil, in contact with the cured resin layer is 0.5 mu m to 2.5 mu m. The cured resin layer comprises any resin component selected from polyimide and polyamide-imide resins having a coefficient of thermal expansion of 0 ppm/ DEG C to 25 ppm/ DEG C or composite resins of the polyimide resins and the polyamide-imide resins. The semi-cured resin layer is provided on the cured resin layer and has a coefficient of thermal expansion of 0 ppm/ DEG C to 50 ppm/ DEG C after curing.
Description
Technical field
The present invention relates to a kind of as the tape tree fat Copper Foil of printed wiring board material use and the preparation method of tape tree fat Copper Foil.
Background technology
Tape tree fat Copper Foil, be on as the Copper Foil of conductor laminated configuration as the resin bed of insulating barrier and form, and in the manufacturing field of the multilayer printed-wiring board that always is used for making with various purposes (below, abbreviate " lamination type printed wiring board " sometimes as) etc. by lamination method.For example, in the manufacturing of lamination type printed wiring board, the insulating barrier that the resin bed by tape tree fat Copper Foil that sticks on the internal layer core is formed, carry out perforate processing by Laser Processing etc. and form via, after the internal perisporium face of this via is implemented the interlayer conduction plating, the surface of outer copper foil is carried out the pattern etching and formed outer circuit.Then, further stacked tape tree fat Copper Foil on the surface of the outer circuit after the pattern etching and processing, and repeat same outer circuit and form operation, thereby produce the lamination type printed wiring board.
In recent years, in printed wiring circuit, advanced the miniaturization of circuit, the high-density installationization of electronic unit, require printed wiring board have the circuit of the high frequency characteristics considered etching factor, be used to improve the circuit position precision of packing density.Particularly, in repeating stacked lamination type printed wiring board, Copper Foil is carried out etching and the circuit that forms is trickle more, produce the problem of the positional precision of conductor circuit at interlayer.For example, the thermal history when owing to processing printed wiring plate when interlayer causes position deviation, piles up the stacked position generation deviation of via, can't obtain good interlayer conduction state.Consequently, even used tape tree fat Copper Foil,, also need to make the copper foil layer attenuation and require to be provided with resin bed with excellent size stability in order to ensure the good etching resistance energy as the material of lamination type printed wiring board.
In order to satisfy this requirement, for example, in patent documentation 1, a kind of inorganic filler that adds silica etc. in resin bed is disclosed, reducing thermal coefficient of expansion, thus the product that the dimensional stability of printed wiring slab products is improved.In addition, in this patent documentation 1, in order to reduce thermal coefficient of expansion, use BMI is that resin and cyano group ester are the high resins of glass transition temperature such as resin more.Yet, the resin material of the resin bed that is used to form tape tree fat Copper Foil shown in patent documentation 1, when inorganic filling material is disperseed to be mixed in the resin, promptly allow to reduce the thermal coefficient of expansion of resin bed, can make the circuit position of the interlayer of lamination type printed wiring board concern good, but the resin bed after solidifying has the tendency that becomes fragile, circuit that is formed by Copper Foil and the bonding stability reduction between the resin bed.Therefore; in tape tree fat Copper Foil; in order to improve the adherence of Copper Foil and resin bed; use forms fine metal particle or carries out forming the Copper Foil that the roughening of roughened surface etc. is handled by etching method pasting to adhere on the copper foil surface of side with resin bed, thereby performance is anchored (anchor) effect when pasting.
Patent documentation 1:JP spy opens the 2005-322682 communique
Patent documentation 2:JP spy opens flat 11-10794 communique
Summary of the invention
The problem that invention will solve
Yet, paste insulating barrier on the surface of the roughening Copper Foil that in patent documentation 1, uses, and copper foil layer is carried out under the situation of etching and processing, must guarantee to be used for the mistake etching period that rough form is removed in etching, therefore, exist the problem of the minuteness space circuit that is difficult to form the etching factor excellence.
On the other hand, only pay attention to the etching factor of circuit and when forming the minuteness space circuit, for example, disclosed as patent documentation 2, its be with provide peel strength that a kind of peel strength that has when using the roughening Copper Foil is equal to and the copper particle after the etch processes can not residue in copper clad laminate that circuit in the resin forms the property excellence with Copper Foil as purpose, and provide a kind of copper clad laminate Copper Foil that forms in that the adhesive linkage more than two-layer is set on the no roughening Copper Foil.Yet, from patent documentation 2 disclosed contents as can be known, be provided with the no roughening Copper Foil of two-layer above adhesive linkage, the bonding stability of shortcoming between its no roughening Copper Foil and the resin bed, and all characteristics such as its scolding tin hear resistance, resistance to sudden heating do not have the degree of circuit minuteness space desirable characteristics in recent years of can tackling, can't obtain and the equal hot expansibility of patent documentation 1 disclosed tape tree fat Copper Foil, can not improve the dimensional stability of lamination type printed wiring board.
In view of the above problems, wish the tape tree fat Copper Foil develop the dimensional stability that to improve the lamination type printed wiring board and can form the minuteness space circuit.
Solve the method for problem
The inventor etc. have adopted the manufacture method of following tape tree fat Copper Foil and tape tree fat Copper Foil through concentrated research.Tape tree fat Copper Foil of the present invention has the low resin bed of thermal coefficient of expansion, and the excellent in dimensional stability when being processed into printed wiring board.And, the tape tree fat Copper Foil of the present invention of the following stated, even use the no roughening Copper Foil of low roughness, the adherence between itself and the resin bed is also excellent, is suitable as high density printed wiring board material.Below, summary of the present invention is described.
Tape tree fat Copper Foil: tape tree fat Copper Foil of the present invention, it is the tape tree fat Copper Foil that on the surface of Copper Foil, forms curing resin layer and semi-solid preparation resin bed successively, it is characterized in that, with the surface roughness (Rzjis) of the Copper Foil of above-mentioned curing resin layer contact side be 0.5 μ m～2.5 μ m, above-mentioned curing resin layer is to be the polyimide resin of 0ppm/ ℃～25ppm/ ℃ by thermal coefficient of expansion, one of any resinous principle in polyamide-imide resin and their compound resin constitutes, and the thermal coefficient of expansion after having curing on the above-mentioned curing resin layer is the semi-solid preparation resin bed of 0ppm/ ℃～50ppm/ ℃.
In the tape tree fat Copper Foil of the present invention, more preferably the thermal coefficient of expansion after the curing of the resin bed integral body of curing resin layer that forms on the surface of above-mentioned Copper Foil and semi-solid preparation resin bed is below 40ppm/ ℃.
In the tape tree fat Copper Foil of the present invention, more preferably the glass transition temperature of above-mentioned curing resin layer is more than 300 ℃.
In the tape tree fat Copper Foil of the present invention, more preferably above-mentioned semi-solid preparation resin bed is that the employing maleimide is that resin forms.
In the tape tree fat Copper Foil of the present invention, more preferably above-mentioned maleimide is that resin is the aromatic series maleimide resin that has two above dimaleoyl iminos in the molecule.
In the tape tree fat Copper Foil of the present invention, more preferably above-mentioned maleimide is that resin is the polymerization addition product that the aromatic series maleimide resin that has two above dimaleoyl iminos in the molecule and aromatic polyamine are polymerized.
In the tape tree fat Copper Foil of the present invention, when more preferably above-mentioned semi-solid preparation resin bed being made as 100 weight portions, the maleimide that this semi-solid preparation resin bed contains 20 weight portions～70 weight portions is a resin.
In the tape tree fat Copper Foil of the present invention, more preferably the thickness of above-mentioned curing resin layer is 3 μ m～30 μ m.
In the tape tree fat Copper Foil of the present invention, the thickness of more preferably above-mentioned semi-solid preparation resin bed is 7 μ m～55 μ m.
In the tape tree fat Copper Foil of the present invention, the total gross thickness of more preferably above-mentioned curing resin layer and above-mentioned semi-solid preparation resin bed is 10 μ m～60 μ m.
In tape tree fat Copper Foil of the present invention, more preferably above-mentioned Copper Foil adopts no roughening Copper Foil.
The manufacture method of tape tree fat Copper Foil: the manufacture method of tape tree fat Copper Foil of the present invention is the manufacture method of above-mentioned tape tree fat Copper Foil, it is characterized in that, through following operation A and process B.
Operation A: be on the surface of Copper Foil of 0.5 μ m～2.5 μ m in surface roughness (Rzjis), using thermal coefficient of expansion is one of any resinous principle in polyimide resin, polyamide-imide resin and their compound resin of 0ppm/ ℃～25ppm/ ℃, forms curing resin layer;
Process B: by the thermal coefficient of expansion after on the above-mentioned curing resin layer curing being set is the semi-solid preparation resin bed of 0ppm/ ℃～50ppm/ ℃, obtains tape tree fat Copper Foil.
In the manufacture method of tape tree fat Copper Foil of the present invention, more preferably in above-mentioned operation A, be on the surface of Copper Foil of 0.5 μ m～2.5 μ m in surface roughness (Rzjis), using thermal coefficient of expansion is the polyimide resin of 0ppm/ ℃～25ppm/ ℃ when forming curing resin layer, adopts casting method or laminating.
In the manufacture method of tape tree fat Copper Foil of the present invention, more preferably in above-mentioned process B, with the maleimide that contains that is used to form this semi-solid preparation resin bed is the amount of the resin combination of resin when being made as 100 weight portions, and the maleimide that this resin combination contains 20 weight portions～70 weight portions is a resin.
In the manufacture method of tape tree fat Copper Foil of the present invention, more preferably between above-mentioned operation A and process B, be provided with the surface modification operation of the surface of curing resin layer being carried out plasma treatment or sided corona treatment.
The invention effect
Because the resin bed of tape tree fat Copper Foil of the present invention, therefore, be processed into the adhesion excellent in stability between the resin bed after Copper Foil (circuit) and the curing behind the printed wiring board with the adherence excellence between metal forming and resin bed.In addition, used the lamination type printed wiring board of tape tree fat Copper Foil of the present invention, because the thermal coefficient of expansion of resin bed is little after the curing of this tape tree fat Copper Foil, therefore, the thermal history in the time of can be to processing printed wiring plate keeps good dimensional stability.And, tape tree fat Copper Foil of the present invention, even roughening is not carried out on the surface of the resin bed side of Copper Foil to be handled, also can between Copper Foil and resin bed, obtain good adherence, be processed into after the printed wiring board, also can demonstrate good adhesion stability at the Copper Foil that constitutes tape tree fat Copper Foil and between the resin bed after solidifying.
In addition, because tape tree fat Copper Foil of the present invention constitutes resin bed by curing resin layer and semi-solid preparation resin bed, therefore, even the thickness that can't operate separately by Copper Foil, owing to there is hard curing resin layer, in Copper Foil, produce the damage of gauffer, bending etc. in the time of also can preventing to operate effectively, can make the operability excellence.And then, because tape tree fat Copper Foil of the present invention also can use no roughening Copper Foil, therefore, be suitable for forming the minuteness space circuit.And, because in the tape tree fat Copper Foil of the present invention, its resin bed has low thermal coefficient of expansion after curing, therefore, can improve the positional precision between the interlayer circuit of lamination type printed wiring board, easily realize the densification of circuit.
In addition, the manufacture method of tape tree fat Copper Foil of the present invention when laminated copper foil, curing resin layer, semi-solid preparation resin bed, need not special special installation, also need not new equipment investment, can produce excellent tape tree fat Copper Foil.
The specific embodiment
Below, the preferred implementation of the manufacture method of tape tree fat Copper Foil of the present invention and tape tree fat Copper Foil is described successively.
Tape tree fat Copper Foil: tape tree fat Copper Foil of the present invention is the tape tree fat Copper Foil that forms with the state that stacks gradually curing resin layer and semi-solid preparation resin bed on the surface of Copper Foil.
One of feature of tape tree fat Copper Foil of the present invention, be as Copper Foil use surface roughness (Rzjis) with the curing resin layer contact side be 0.5 μ m～2.5 μ m, have the Copper Foil of utmost point low roughness or do not have the roughening Copper Foil.And in the tape tree fat Copper Foil of the present invention, also can use the surface roughness with the curing resin layer contact side is the Copper Foil of 0.5 μ m～2.0 μ m, therefore, can satisfy the low profileization of desired Copper Foil in recent years.In the past, in order to improve the adherence between resin bed and the Copper Foil, roughening was implemented on the surface of Copper Foil handled.Yet tape tree fat Copper Foil of the present invention is handled even without Copper Foil is implemented roughening, also has good adherence between Copper Foil and the resin bed.That is, in tape tree fat Copper Foil of the present invention, the stacked curing resin layer that disposes on the surface of Copper Foil, even the surface of the Copper Foil of this curing resin layer side of laminated configuration is a low roughness, the adherence between itself and the curing resin layer is also excellent.Particularly, when using no roughening Copper Foil as the Copper Foil that constitutes tape tree fat Copper Foil of the present invention, the manufacturing cost that not only can cut down Copper Foil, and, also can realize the low profileization of Copper Foil.In addition, when forming conductor circuit, can carry out etching equably, and, there is no need to be provided with long mistake etching period, therefore, can easily form the minuteness space circuit of etching factor excellence.In addition, there is no particular limitation to the thickness of Copper Foil, but when using electrolytic copper foil, preferably its thickness is 7 μ m～18 μ m.And, when the Copper Foil below the use 5 μ m, the preferred band carrier copper foil that uses.
In this manual, " curing resin layer " is meant by the layer that constitutes by the resin that heats the degree that can not flow again.In other words, be meant by curing degree at least than semi-solid preparation resin (B stage resin) height, even and its be cured to and be subjected to making its resin bed of forming of resin of the heating of the liquidity degree that also can not flow again in fact again.
In addition, preferably this curing resin layer is to be that the resin of 0ppm/ ℃～25ppm/ ℃ constitutes by the thermal coefficient of expansion after solidifying.If the thermal coefficient of expansion of curing resin layer is above 25ppm/ ℃, when being used for laminat molding when processing belt resin Copper Foil, significant thermal expansion takes place in curing resin layer, reduce with the adherence on the interface of the thermal expansion Copper Foil littler than curing resin layer, can't prevent that the circuit that expansion contractive action that thermal history or thermal shock because of printed wiring board manufacturing process cause causes from peeling off, simultaneously, be difficult to obtain the dimensional accuracy of gained lamination type printed wiring board.On the other hand, the thermal coefficient of expansion of curing resin layer is low more, and the dimensional accuracy of the lamination type printed wiring board of use tape tree fat Copper Foil is good more, and therefore, it is 0ppm/ ℃ that the lower limit of thermal coefficient of expansion is set.In addition, the thermal coefficient of expansion of this curing resin layer, molecular-weight adjusting in the time of can being the selection, combination of sour composition, amine component or isocyanate prepolymer composition and addition reaction by the raw material of polyimide resin or polyamide-imide resin is adjusted, and it is adjusted to 0ppm/ ℃～25ppm/ ℃.In addition, more preferably above-mentioned thermal coefficient of expansion is below 20ppm/ ℃.
In addition, about resinous principle,, may be used in the tape tree fat Copper Foil of the present invention so long as have aforesaid thermal coefficient of expansion and in the Electrical and Electronic material applications, can bring into play the resinous principle of enough insulating properties.But in having the resin of aforesaid thermal coefficient of expansion, preferably use one of any resinous principle in polyimide resin, polyamide-imide resin and their compound resin.These resins have extremely excellent electric insulating energy, mechanical strength, flexibility, are suitable in the electronic material purposes.Because this curing resin layer plays a role as the supporting course of Copper Foil, therefore, the shortcoming operability even employed copper foil layer is thin, but, also can access good operability as tape tree fat Copper Foil.At this, in thermal coefficient of expansion is in above-mentioned scope, and when requiring to carry out the adjustment of suitable flowability, the maleimide that curing resin layer also can add aequum is resin, epoxy resin, polyethersulfone resin, cyano group ester resin etc.
Herein, polyimide resin is the resin that obtains by the following method.That is, make the material and 4 that has two carboxylic acid dianhydride in the pyromellitic dianhydride equimolecular, the polyamino compound that has two amino in 4 '-diaminodiphenyl-methane equimolecular carries out addition reaction, then, makes by heating that it dewaters, closed loop obtains.In addition, polyamide-imide resin is reacted by the isocyanate compound that makes the compound that has carboxyl and carboxylic acid anhydrides in the trimellitic anhydride equimolecular simultaneously and methylene diisocyanate etc. to obtain.In addition, the compound resin of polyimide resin and polyamide-imide resin, be meant that the part with the sour composition of polyamide-imide resin is replaced into the material that has two carboxylic acid dianhydride in the molecule, thereby make polyimide modified polyamide-imide resin, therefrom material of Xing Chenging etc.
And from improving the desired stable on heating viewpoints of various printed wiring boards such as scolding tin hear resistance, resistance to sudden heating, high temperature durability, preferably this curing resin layer use glass transition temperature is the curing resin layer more than 300 ℃.When the glass transition temperature of this curing resin layer is lower than 300 ℃, because the scolding tin that is applied in the manufacture process of the manufacture process of tape tree fat Copper Foil, lamination type printed wiring board refluxes under the temperature of the thermal shock that causes, the high temperature heating that pressurization processing causes etc., peeling off phenomenon in the interface between " Copper Foil or circuit " and " curing resin layer ", what delamination, circuit were peeled off is dangerous high, thereby not preferred.
The thickness of above-mentioned curing resin layer is 3 μ m～30 μ m preferably.When the thickness of curing resin layer during less than 3 μ m, by can not being improved the effect of dimensional stability in the multilayer printed-wiring board of lamination method manufacturing fully, thereby not preferred.On the other hand, when the thickness of curing resin layer surpasses 30 μ m, on Copper Foil, form in the operation of curing resin layer, when resin combination carries out drying after coating, because this heating, cause the distortion of so-called " curling " significantly to produce, become state in the clot of curing resin layer side, therefore, as the operability reduction of tape tree fat Copper Foil, can't use automatically and pile up (piling) device and carry out stacked automatically (lay-up), thus not preferred.And the thickness of curing resin layer is more preferably 5 μ m～30 μ m.In this manual, " thickness " is meant, the surface of supposing Copper Foil is plane completely, and applies the resin of ormal weight and the calculated thickness of the resin coating that obtains on this plane.
Use the curing resin layer of above-mentioned polyimide resin or polyamide-imide resin, even use no roughening Copper Foil, also has excellent adherence, and, compare with the resin combination of the epoxy resin of usually using as the resin bed of tape tree fat Copper Foil, can significantly reduce thermal coefficient of expansion.Yet, because this curing resin layer has high-fire resistance and can not flow again, therefore, want also to be in the solid state that is difficult to slit landfill resin between circuit by the slit landfill resin between the circuit of the internal layer circuit on internal layer core surface of the extrusion forming in the lamination method.Therefore, in the present invention, on this curing resin layer, further laminated configuration semi-solid preparation resin bed, with can be between the circuit of internal layer circuit slit landfill resin.
This semi-solid preparation resin bed is arranged on the resin bed on the curing resin layer, by taking place mobile by heating again and causing that the thermosetting resin of curing reaction forms.And, preferably 0ppm/ ℃ of the thermal coefficient of expansion after the curing of this semi-solid preparation resin bed～50ppm/ ℃.By making the thermal coefficient of expansion after the curing be adjusted into this scope, can suppress poor with the thermal coefficient of expansion of curing resin layer, can prevent the splitting that the difference of the contractive action of institute's received heat caused owing to the resin bed integral body after solidifying etc.In addition, the more preferably scope of thermal coefficient of expansion is 0ppm/ ℃～30ppm/ ℃ after the curing of semi-solid preparation resin bed.
And thermal coefficient of expansion is preferably below 40ppm/ ℃ after the curing of the resin bed integral body that is made of curing resin layer and semi-solid preparation resin bed.Be suppressed at below 40ppm/ ℃ by the thermal coefficient of expansion that will solidify back resin bed integral body, can improve the dimensional stability of printed wiring slab products.
It is that resin forms that above-mentioned semi-solid preparation resin bed preferably uses maleimide.Before curing, demonstrate high flowability though maleimide is a resin, have excellent hear resistance and low thermal coefficient of expansion after solidifying.And, comparing with epoxy resin, maleimide is that the thermal coefficient of expansion of resin is low.But, in case being resin, this maleimide has the characteristic of solidifying with regard to becoming hard and crisp, therefore low to the adhesion strength of metal formings such as Copper Foil, even use with no roughening Copper Foil combination, also can not get can practical adhesion strength.Therefore, be the semi-solid preparation resin bed that resin forms by maleimide, be the formation that can be used for the resin bed of tape tree fat Copper Foil after making up with above-mentioned curing resin layer.
At this said maleimide is resin, preferably uses the aromatic series maleimide resin that has two above dimaleoyl iminos in the molecule.And maleimide is that resin both can directly use above-mentioned aromatic series maleimide resin, also can use the aromatic series maleimide resin that has two above dimaleoyl iminos in the molecule and the aromatic polyamine polymerization addition product of polymerization in addition.At this moment, aromatic polyamine also works as curing agent for epoxy resin, and therefore, when also with maleimide resin and epoxy resin, the interpolation of aromatic polyamine can be worked as making both crosslinked means.About these, describe in detail in the manufacture method below.
In addition, in this semi-solid preparation resin bed, when formed semi-solid preparation resin bed was made as 100 weight portions, the maleimide that preferably contains 20 weight portions～70 weight portions was a resin.By being that the content of resin is adjusted in this scope with maleimide, effect that reduces thermal coefficient of expansion and the effect that suppresses the fragility of resin can get both.At this, when maleimide be the content of resin be lower than 20 weight portions the time, the effect that can not get making the thermal coefficient of expansion of the semi-solid preparation resin bed after the curing to reduce, thereby not preferred.On the other hand, when maleimide is the content of resin when surpassing 70 weight portions, the semi-solid preparation resin bed becomes crisp resin bed after solidifying, and is easy to generate crackle in this resin bed, reduces the reliability as the insulating barrier of printed wiring board, thereby not preferred.
In addition, at the thickness of this said semi-solid preparation resin bed 7 μ m～55 μ m preferably.When the thickness of this semi-solid preparation resin bed during,, also be difficult to slit between resin landfill circuit if want slit between the circuit of the internal layer circuit by resin landfill internal layer core surface less than 7 μ m.On the other hand, when the thickness of semi-solid preparation resin bed surpasses 55 μ m, pressurizeing man-hour by lamination method, it is big that the thickness deviation of the resin bed of the tape tree fat Copper Foil after the curing becomes, and can encourage the thickness deviation in the printed wiring board face, thereby not preferred.In addition, more preferably the thickness of semi-solid preparation resin bed is 15 μ m～55 μ m.
And then in tape tree fat Copper Foil of the present invention, the total gross thickness of preferred consolidation resin bed and semi-solid preparation resin bed is 10 μ m～60 μ m.When the total gross thickness of the resin bed of this tape tree fat Copper Foil during less than 10 μ m, the thickness thickening of above-mentioned curing resin layer, the thickness of semi-solid preparation resin bed is than the thin thickness of optimum range.Its result, it is difficult that the landfill of internal layer circuit becomes, and becomes to be not suitable for practical tape tree fat Copper Foil.On the other hand, via is by the via about the diameter 50 μ m of Laser Processing formation in recent years.Consider this point, when the total gross thickness of the curing resin layer of tape tree fat Copper Foil of the present invention and semi-solid preparation resin bed surpasses 60 μ m, be difficult to make hole shape reach good state, be difficult to make the internal perisporium face of via to reach level and smooth surface state by Laser Processing.Its result, existing problems during the interlayer conduction plating after forming via is handled, thereby not preferred.In addition, more preferably the total gross thickness of curing resin layer and semi-solid preparation resin bed is 20 μ m～60 μ m.
Tape tree fat Copper Foil of the present invention has the semi-solid preparation resin bed that can paste with the internal layer core, and then, also have curing resin layer, thus, can suppress thermal expansivity, be suitable for lamination method.So, when constituting the resin bed of tape tree fat Copper Foil by this curing resin layer and this semi-solid preparation resin bed, viewpoint from the resin composition, interface at this curing resin layer and semi-solid preparation resin bed, exist resin to form the layer that mixes mutually, can guarantee the adherence at two resin bed interfaces, can suppress because the change in size that suffered thermal history or thermal shock cause in the manufacturing procedure after stacked.
Tape tree fat Copper Foil of the present invention not only is applied in the purposes of printed wiring board, also can be used as the capacitor circuit formation material of curing resin layer as dielectric layer used.For example, tape tree fat copper foil layer of the present invention is stacked on the copper circuit pattern, and carries out hot pressing, be pressed into tape tree fat Copper Foil thus, so that the semi-solid preparation resin bed is between the copper circuit pattern, and, can make curing resin layer as dielectric layer by curing resin layer is contacted with the copper circuit pattern.
The manufacture method of tape tree fat Copper Foil: the tape tree fat Copper Foil of making the invention described above by following operation A and process B.Below, each operation is described.
Operation A: be on the surface of Copper Foil of 0.5 μ m～2.5 μ m in surface roughness (Rzjis), using thermal coefficient of expansion is one of any resinous principle in polyimide resin, polyamide-imide resin and their compound resin of 0ppm/ ℃～25ppm/ ℃, forms curing resin layer.At first, Copper Foil is described.In the notion of this said " Copper Foil ", comprise all Copper Foils of making by rolling process and electrolysis.But, when considering the cost of product, preferably use electrolytic copper foil.
In addition, preferably on this electrolytic copper foil, form antirust processing layer.Antirust processing layer forms in order to prevent from electrolytic copper foil surface oxide etch to take place, to allow to can not bring obstacle in the manufacture process of copper clad laminate and printed wiring board.The method of using in the antirust processing can adopt the organic rust preventing that uses BTA, imidazoles etc. or use any one method in zinc, chromate, kirsite etc. inorganic antirust.Can adopt the method for the spray coating, electrodeposition process etc. of electrolytic copper foil.Inorganic when antirust when adopting, can use by electrolysis to make antirust element separate out method on the surface of electrolytic copper foil, other so-called displacement deposition methods etc.For example, when carrying out the antirust processing of zinc, can adopt zinc pyrophosphate electroplating bath, zinc cyanide electroplating bath, zinc sulfate electroplating bath etc.For example, when being the zinc pyrophosphate electroplating bath, its condition can be enumerated: zinc concentration is that 5g/L～30g/L, potassium pyrophosphate concentration are that 50g/L～500g/L, liquid temperature are that 20 ℃～50 ℃, pH value are 9～12, current density is 0.3A/dm
2～10A/dm
2Deng.
In addition, do not limit the kind of antirust processing as described above, still, use under the situation of cathode copper of the present invention when not carrying out roughening to handle, in order to improve the wettability of resin molding and copper foil surface as much as possible, and in order to improve adherence, preferably adopt following antirust processing.That is, preferably use nickel-kirsite as antirust processing layer.Particularly, except unavoidable impurities, the nickel-kirsite that constitutes antirust processing layer preferably contains the nickel of 50wt%～99wt% and the composition of 50wt%～1wt% core.This is because by have nickel in antirust processing, can make the adhesive improvement tendency with respect to the formation resin of base material become remarkable.The antirust processing layer that is formed by this nickel-kirsite, when nickel content was lower than 50wt%, adhesive effect with various resin moldings can't be improved.In addition, when nickel content surpassed 99wt%, tendency residual after the etching was strong, thereby not preferred.According to the inventor's research, in tape tree fat Copper Foil of the present invention, when forming the antirust processing layer of nickel and zinc, preferably make the total adhesion amount of total of nickel and zinc be adjusted into 20mg/m
2～100mg/m
2Scope.Particularly, if form the antirust processing layer of this nickel-kirsite, in the time of on being bonded in the specific substrate that is difficult to keep adhesion strength, electrolytic copper foil can easily not peeled off from this bonding interface, makes its resistance to chemical reagents, moisture-proof or scolding tin excellent heat resistance.When the total adhesion amount of above-mentioned total is lower than 20mg/m
2The time, can't obtain the antirust processing layer of uniform thickness, the deviation of adhesion strength strengthens.On the other hand, if add up to total adhesion amount to surpass 100mg/m
2, when carrying out etching, the tendency of the etch residue that produces the nickel composition is arranged in order to form conductor circuit, thus not preferred.
And having confirmed that the nickel amount has for a long time improves adhesion strength, resistance to chemical reagents, moisture-proof, the stable on heating tendency of scolding tin, and when increasing the zinc amount, then has the resistance to chemical reagents of reduction, the stable on heating tendency of scolding tin.When forming the antirust processing layer of nickel-kirsite, confirmed total adhesion amount of nickel and zinc is adjusted into 20mg/m
2～100mg/m
2The time, the ratio of this nickel and zinc is adjusted into nickel: the scope of zinc=6: 4～8: 2 is suitable in practicality.If the ratio of nickel surpasses 80%, then when forming circuit, the tendency that produces etch residue is arranged, on the other hand, when the ratio of zinc surpasses 40%, have the resistance to chemical reagents of reduction, the stable on heating tendency of scolding tin.
In addition, also preferably constitute antirust processing layer with nickel-zinc alloy layer and chromate coating.By the existence of chromate coating, when improving corrosion resistance, also has the adhesive tendency that can improve with resin bed.The formation of the chromate coating of this moment can be adopted any one method in displacement method, the electrolysis according to conventional methods.
And, after nickel-kirsite plating processing or chromate processing, carry out silane coupler and handle.Silane coupler is handled, be meant that roughening processings, antirust processing etc. finish after, in order chemically to improve and the adherence of insulating barrier constituent material and the processing carried out.Saidly be used for silane coupler that silane coupler handles there is no particular limitation at this, can be according to the proterties of electroplate liquid that uses in employed insulating barrier constituent material, the printed wiring board manufacturing process etc., be that silane coupler, amino are that silane coupler, sulfydryl are at random to select silane coupler etc. and use from epoxy.
More particularly, with with glass cloth as the prepreg of printed wiring board-use on the same coupling agent of the coupling agent that uses be the center, can use vinyltrimethoxy silane, the ethenylphenyl trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, 4-glycidyl butyl trimethoxy silane, γ-An Jibingjisanyiyangjiguiwan, N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-3-(4-(the amino propoxyl group of 3-) butoxy) propyl group-3-TSL 8330, imidazoles silane, triazine silane, γ-Qiu Jibingjisanjiayangjiguiwan etc.
Below, the method that forms curing resin layer on the surface of Copper Foil is described.On the surface of Copper Foil, form the method for curing resin layer, thus can use separate out copper on the curing resin layer by no electrolysis and make by electrolysis its growth obtain the method for stacked state, at the surperficial laminated resin film of Copper Foil and pressurizeed and process all known technologies that coated with resins varnish on the method for pasting, the surface at Copper Foil and heat drying make the cladding process etc. of its curing.But, under the situation that forms polyimide resin layer or polyamide-imide resin layer, preferably use casting method or laminating.
When using casting method to form polyimide resin layer, surface-coated polyimides precursor varnish in metal forming, cause imidization reaction by heating, and make its curing and make polyimide resin, above-mentioned operation is repeated repeatedly to form polyimide resin layer.In addition, when using casting method to form the polyamide-imide resin layer, can be dissolved in the organic solvent of N-methyl pyrrolidone etc. by reaction product isocyanates such as the sour composition of trimellitic anhydride and methylene diisocyanates, obtain resin varnish, this resin varnish is coated on copper foil surface, heat and remove solvent, form the polyamide-imide resin layer thus.At this moment, different with the situation that forms above-mentioned polyimide resin layer, the generation of imide is finished, therefore, can not follow dehydration, ring-closure reaction.This casting method has the polyimide resin layer that can easily form desired thickness or the advantage of polyamide-imide resin layer.
When adopting laminating, can be the mode of passing through the stacked polyimide film of laminating, polyamidoimide film etc. behind the coating bonding agent.In addition, the band bond layer Copper Foil that also can adopt the applicant to propose in No. 3949676, Japan Patent is gone up by the stacked commercially available polyimide film of laminating at the bond layer (very thin primer resin layer) of this band bond layer Copper Foil etc.
Process B: in this operation, be the semi-solid preparation resin bed of 0ppm/ ℃～50ppm/ ℃, obtain tape tree fat Copper Foil by the thermal coefficient of expansion after on the above-mentioned curing resin layer curing being set.The semi-solid preparation resin bed is to use following resin combination to form, promptly, this resin combination is to be the amount of the resin combination of resin when being made as 100 weight portions with containing maleimide, and the maleimide that contains 20 weight portions～70 weight portions is the resin combination of resin.Maleimide in this resin combination is the content of resin, is that semi-solid preparation resin bed as tape tree fat Copper Foil demonstrates the scope of Ideal Characteristics and stipulates.Below, the resin combination that is used to form the semi-solid preparation resin bed is described.Resin combination as used herein, be with maleimide be resin, epoxy resin, linear polymer with crosslinkable functional group is the resin combination of neccessary composition.And, be resin as maleimide, also can use aromatic series maleimide resin and the aromatic polyamine polymerization addition product of polymerization in addition.In addition, as required, can also in the semi-solid preparation resin bed, add with maleimide be that resin has reactive cyano group ester resin or epoxy resin.
As being resin at this said maleimide, can use 4,4 '-diphenyl methane BMI, polyphenylene methane maleimide, meta-phenylene bismaleimide, bisphenol-A diphenyl ether BMI, 3,3 '-dimethyl-5,5 '-diethyl-4,4 '-diphenyl methane BMI, the 4-methyl isophthalic acid, 3-phenylene BMI, 4,4 '-diphenyl ether BMI, 4,4 '-diphenyl sulfone BMI, 1, two (the 3-maleimide phenoxy group) benzene of 3-, 1, two (4-maleimide phenoxy group) benzene of 3-etc.When maleimide is the content of resin during less than 20 weight portions, the effect of the thermal coefficient of expansion of the semi-solid preparation resin bed after solidifying that can't be reduced, thereby not preferred.On the other hand, when maleimide is the content of resin when surpassing 70 weight portions, the semi-solid preparation resin bed becomes crisp resin bed after solidifying, and occurs crackle in this resin bed easily, reduces the reliability as the insulating barrier of printed wiring board, thereby not preferred.
At this employed epoxy resin, be meant that so-called bis-phenol is an epoxy resin.And preferred the use is selected from a kind of in the group of being made up of bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A D type epoxy resin or mixes wherein two or more of use.At this, selecting bis-phenol for use is epoxy resin, be because: it is aqueous epoxy resin under 25 ℃, and when manufacturing has the tape tree fat Copper Foil of resin bed of semi-cured state, can access the curl effect of phenomenon of significant inhibition; And, can access resin molding after the curing and the good adherence between the Copper Foil, and obtain can be along the suitable solation amount (resin flow) of the shape of convex-concave surface.In addition, when liquid epoxy resin is high-purity, after passing through cool condition, turn back to the epoxy resin that looks like solid shape in appearance that normal temperature also keeps the crystallization state even also have.In this case, it also can turn back to aqueous and use, and therefore, it is included in the said herein liquid epoxy resin.In addition, why indicating 25 ℃ temperature, is near the clear and definite meaning room temperature.
In addition, when epoxide equivalent surpasses 200, become semi-solid shape or solid shape under 25 ℃, therefore, the preparation of resin combination is difficulty also, and the curling phenomenon when tape tree fat Copper Foil is made in inhibition does not have help yet, thereby not preferred.In addition, at this said epoxide equivalent, be meant the gram number (g/eq) of the resin of the epoxy radicals that contains 1 gram equivalent.In addition,, both can use independent a kind ofly, also can mix two or more uses when being above-mentioned bis-phenol when being epoxy resin.And, when mixing two or more use, its mixing ratio is not done special qualification.
When resin combination was made as 100 weight portions, this bis-phenol was that epoxy resin is the cooperation ratio use with 3 weight portions～20 weight portions.When this epoxy resin was lower than 3 weight portions, the resin bed after the curing became fragile, and is easy to generate crackle.On the other hand, when surpassing 20 weight portions, under 25 ℃, on resin surface, produce viscosity, thereby the operability shortcoming.
Linear polymer with crosslinkable functional group preferably has the functional group that hydroxyl, carboxyl etc. help the curing reaction of epoxy resin.In addition, this has the linear polymer of crosslinkable functional group, and preferably dissolving in boiling point is in the organic solvent of 50 ℃～200 ℃ of temperature.At this said instantiation, can enumerate polyethylene acetal resin, phenoxy resin, polyethersulfone resin, polyamide-imide resin etc. with linear polymer of functional group.When resin combination was made as 100 weight portions, this linear polymer with crosslinkable functional group was the cooperation ratio use with 3 weight portions～30 weight portions.When this epoxy resin was lower than 3 weight portions, resin flows strengthened.Consequently, common to phenomenon from the end generation tree cosmetics of the copper clad laminate of manufacturing, also can't improve the anti-hygroscopicity of the resin bed under the semi-cured state.On the other hand, even surpass 30 weight portions, resin flows is also little, and is easy to generate defective such as space in the insulating barrier of the copper clad laminate of manufacturing.
In addition, in making molecule, formation has the aromatic series maleimide resin of plural dimaleoyl imino and aromatic polyamine in addition during the polymerization addition product of polymerization, as aromatic polyamine, for example, the preferred m-phenylenediamine of using, P-pHENYLENE dI AMINE, 4,4 '-diamino-dicyclohexyl methane, 1, the 4-DACH, 2, the 6-diamino-pyridine, 4,4 '-diaminodiphenyl-methane, 2, two (4-aminophenyl) propane of 2-, 4,4 '-diamino-diphenyl ether, 4,4 '-diaminourea-3-methyldiphenyl base ether, 4,4 '-diamino-diphenyl thioether, 4,4 '-diaminobenzophenone, 4,4 '-diamino diphenyl sulfone, two (4-aminophenyl) aniline, m-xylene diamine, the paraxylene diamines, 1, two (4-amino-benzene oxygen) benzene of 3-, 3-methyl-4,4 '-diaminodiphenyl-methane, 3,3 '-diethyl-4,4 '-diaminodiphenyl-methane, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, 2,2 ', 5,5 '-tetrachloro-4,4 '-diaminodiphenyl-methane, 2, two (3-methyl-4-aminophenyl) propane of 2-, 2, two (3-ethyl-4-aminophenyl) propane of 2-, 2, two (2, the 3-two chloro-4-aminophenyls) propane of 2-, two (2,3-dimethyl-4-aminophenyl) diphenylphosphino ethane, ethylene diamin(e) and hexamethylene diamine etc.
In addition, in the time that epoxy curing agent must be added, can use the amine of dicyandiamide, imidazoles, aromatic amine etc.; The phenols of bisphenol-A, brominated bisphenol A etc.; The novolaks class of phenol novolac resin and cresols novolac resin etc.; The acid anhydrides of phthalic anhydride etc. etc.At this moment, with respect to epoxy resin, the addition of epoxy curing agent can naturally and understandably be derived from equivalent separately, therefore, its addition is not done special qualification.
By the resin combination that above-described resinous principle constitutes, preferably using boiling point is 50 ℃～200 ℃ organic solvent, is prepared into resin varnish.When boiling point is lower than 50 ℃,,, be difficult to obtain good semi-cured state when when the resin varnish state is adjusted to the semi-solid preparation resin because the gaseous volatilization that causes of heating is serious.On the other hand, when boiling point surpasses 200 ℃, easy residual solvent under semi-cured state.That is, common desired evaporation rate can not be satisfied, industrial productivity can not be satisfied.The instantiation of organic solvent described herein can be enumerated a kind of independent solvent that is selected from the group of being made up of methyl alcohol, ethanol, MEK, toluene, propylene glycol monomethyl ether, dimethyl formamide, dimethylacetylamide, cyclohexanone, ethylene glycol monoethyl ether etc. or two or more mixed solvents.
Above-mentioned resin combination is made resin varnish, and this resin varnish is coated on the curing resin layer of Copper Foil, make its drying, thereby form the semi-solid preparation resin bed.Painting method, drying means to this moment are not done special qualification.
And, preferably between operation A and process B, the surface modification operation of the curing resin layer that is undertaken by plasma treatment or sided corona treatment as the additional process setting.By this surface modification operation is set, the surface of curing resin layer is modified, and can improve the adherence with the semi-solid preparation resin.Promptly, because curing resin layer is formed by different resin combinations with the semi-solid preparation resin bed, and a resin bed is cured, therefore, reduce the adherence between both resin beds sometimes, even in this case, implement plasma treatment or sided corona treatment by surface to curing resin layer, also can improve the adherence between curing resin layer and the semi-solid preparation resin bed.
Plasma treatment described herein is meant that normally used making by applying the plasma air-flow that high voltage produces contacts the processing of carrying out with the surface of hard resin layer.In addition, sided corona treatment is meant that between electrode configuration has the Copper Foil of curing resin layer, then, applies high frequency, high voltage and carries out corona discharge, is cured the surface modification of resin bed thus.In addition, plasma treatment or sided corona treatment can be used all known method.
Below, specify the present invention by embodiment, but the present invention is not limited to following embodiment.
Embodiment 1
Be illustrated among the embodiment 1 on the surface of electrolytic copper foil and form polyimide resin layer, and to adopt maleimide in the formation of semi-solid preparation resin bed be the tape tree fat Copper Foil of resin as curing resin layer.
Electrolytic copper foil: use glassy surface, and thickness is the electrolytic copper foil of 12 μ m with surface roughness Rzjis=0.70.Working concentration is the dilution heat of sulfuric acid of 100g/L, under 30 ℃ of liquid temperature with this electrolytic copper foil dipping 30 seconds and clean.Then, as the antirust processing of glassy surface, carry out nickel-kirsite plating processing, chromate processing, silane coupler processing successively.Wherein, nickel-kirsite plating is to bathe (nickel 2.5g/L, zinc 0.5g/L, 40 ℃ of liquid temperature, current density 0.6A/dm at pyrophosphoric acid
2, 8 seconds) condition under carry out.In addition, electrolytic chromate is handled, and being to use concentration is the chromic acid of 1.0g/L, is 12 in the pH value, 30 ℃ of liquid temperature, current density 1.8A/dm
2, electrolysis time is to carry out under 8 seconds the condition.
In addition, silane coupler is handled, be to use ion exchange water as solvent and add the gamma-amino propyl trimethoxy silicane so that its concentration reaches the solution of 5.0g/L, this solution is blown on the surface of antirust processing layer by spray process, carry out adsorption treatment, thereby on antirust processing layer, form silane coupling agent layer.
After the silane coupler processing finishes, finally spent 4 seconds, promote the condensation reaction of silane coupler by making it dry in the stove, finish electrolytic copper foil, wherein, described stove is to adjust the environmental gas temperature by the heater heating, so that the paper tinsel temperature can reach 140 ℃ stove.The surface roughness of the glassy surface after this surface treatment is Rzjis=0.72 μ m.
The preparation of polyamide acid varnish: following, the polyamide acid varnish that uses when illustrating by casting method formation curing resin layer.With pyromellitic acid anhydride 1mol and 4,4 '-diamino-diphenyl ether 1mol is dissolved in the N-methyl pyrrolidone as solvent and mixes.The reaction temperature of this moment is 25 ℃, and the reaction time is 10 hours.Obtain the polyamide acid varnish that the resin solid component content is 20 quality %.
The formation of curing resin layer: then, use the polyamide acid varnish that obtains, form curing resin layer by casting method.By multicoating machine (M-400, ヒ ラ ノ テ Network シ one De society makes), polyamide acid varnish is coated on the glassy surface of above-mentioned electrolytic copper foil, in air drier, under 110 ℃ * 6 minutes condition, carry out drying.The resin thickness of dried resin bed is 35 μ m, and the dissolvent residual rate in this stage is 32wt% with respect to the resin bed total amount.This complex that is coated with the electrolytic copper foil of polyamide acid varnish is put into hot-air oven by nitrogen replacement, was warming up to 400 ℃ from room temperature with 15 minutes, then, 400 ℃ keep 8 minutes down after, cooled off.Thus, from the complex of the electrolytic copper foil that is coated with polyamide acid varnish, remove residual solvent,, obtain the copper-clad polyimide resin base material of the state of stacked curing resin layer on copper foil surface by the imide reaction of dehydration closed-loop polyamic acid.The dissolvent residual rate of the copper-clad polyimide resin base material that obtains by this final heat treatment is with respect to being 0.5wt% attached to the resin total amount on the electrolytic copper foil.
Then, the Copper Foil (copper-clad polyimide resin base material) that is laminated with curing resin layer is carried out sided corona treatment, thereby carry out the surface modification of this curing resin layer.Sided corona treatment is that electric power is that 210W, speed are that 2m/min, discharge capacity are 300Wmin/m in atmosphere
2, the irradiation distance that begins from electrode is to carry out under the condition of 1.5mm.
And in order to measure the thermal coefficient of expansion of curing resin layer, electrolytic copper foil is removed in the Copper Foil that is laminated with curing resin layer (the copper-clad polyimide resin base material after the sided corona treatment) etching after surface modification treatment.Consequently, the resin thickness of removing the curing resin layer (polyimide film) that obtains behind the electrolytic copper foil is 27 μ m, and thermal coefficient of expansion is 25ppm/ ℃.
The formation of semi-solid preparation resin bed:, on the curing resin layer of the copper-clad polyimide resin base material after the sided corona treatment, form the semi-solid preparation resin bed at this.At first, with N, N '-dimethylacetylamide dissolves the resin combination of the following stated as solvent, and preparation resin solid composition is the resin varnish of 30wt%.
[forming the resin combination of the semi-solid preparation resin bed of embodiment 1]
Maleimide resin: 4,4 '-diphenyl methane BMI (trade name: BMI-1000, big and change into industrial society and make)/30 weight portions
The aromatic polyamine resin: 1, two (4-amino-benzene oxygen) benzene of 3-(trade name: TPE-R, Wakayama refine industrial society make)/35 weight portions
Epoxy resin: bisphenol A type epoxy resin (trade name: エ ピ Network ロ Application 850S, big Japanese イ Application Network chemical industry society makes)/20 weight portions
Linear polymer with crosslinkable functional group: the polyethylene acetal resin (trade name: デ Application カ Block チ ラ one Le 5000A, electrochemical industry society makes)/15 weight portions
Above-mentioned resin varnish is coated on the polyimide resin face of the copper-clad polyimide resin base material after the sided corona treatment, at room temperature carries out 5 minutes air-dry, under 160 ℃ * 5 minutes condition, carry out heat drying, thus stacked formation semi-solid preparation resin bed.The resin thickness of the semi-solid preparation resin bed of this moment is 20 μ m.
And, for the thermal coefficient of expansion after the curing of measuring the semi-solid preparation resin bed, the above-mentioned resin varnish that will in the formation of semi-solid preparation resin bed, use, by method same as described above, be coated on the heat-resistant film of fluorine system, at room temperature carry out 5 minutes air-dry, under 160 ℃ * 5 minutes condition, carry out heat drying, then, carry out 200 ℃ * 2 hours curing heating, thereby obtain the test curing resin layer that thickness is 20 μ m.That is the situation after, this test semi-solid preparation resin bed of being equivalent to tape tree fat Copper Foil of the present invention with curing resin layer solidifies.This test is 45ppm/ ℃ with the thermal coefficient of expansion of curing resin layer.
The thickness of the resin bed integral body of the tape tree fat Copper Foil that obtains as mentioned above is 47 μ m.Then, remove Copper Foil, use this, carry out 200 ℃ * 2 hours curing heating, and measure the thermal coefficient of expansion that makes the resin bed integral body after this semi-solid preparation resin bed solidifies by the resin bed that curing resin layer and semi-solid preparation resin bed are formed from this tape tree fat Copper Foil etching.Consequently, thermal coefficient of expansion is 35ppm/ ℃.In addition, peel strength is 1.0kgf/cm.
Embodiment 2
The cured resin layer thickness of embodiment 2 is different with embodiment 1.That is, in the formation of the curing resin layer of embodiment 1, dried resin thickness was 35 μ m in 110 ℃ * 6 minutes, and is relative therewith, and in embodiment 2, dried resin thickness was adjusted into 8 μ m in 110 ℃ * 6 minutes.In addition, adopt the method making tape tree fat Copper Foil identical with embodiment 1.The curing resin layer of this embodiment 2 is 5 μ m through 400 ℃ * 8 minutes dried resin thicknesses, and the dissolvent residual rate is 0.1wt%.And the thermal coefficient of expansion of the resin bed integral body after the semi-solid preparation resin is solidified fully is 38ppm/ ℃, and the peel strength of Copper Foil is 0.95kgf/cm.
Embodiment 3
Embodiment 3 compares with embodiment 1, the formation difference of its curing resin layer.Promptly, in the formation of curing resin layer, use resin to change バ イ ロ マ Star Network ス HR16NN (trade name, Japan weaving society makes) into institute, 110 ℃ * 6 minutes dried cured resin layer thicknesses are adjusted into 28 μ m, and it is 380 ℃ that the maximum temperature of drying condition is afterwards set.In addition, adopt the method making tape tree fat Copper Foil identical with embodiment 1.At this moment, the thickness of 380 ℃ * 8 minutes dried curing resin layers is 24 μ m, and the dissolvent residual rate is 0.8wt%, and the thermal coefficient of expansion of curing resin layer is 23ppm/ ℃.And the thermal coefficient of expansion of the resin bed integral body of the tape tree fat Copper Foil after the semi-solid preparation resin is solidified fully is 34ppm/ ℃, and the peel strength of Copper Foil is 0.80kgf/cm.
Embodiment 4
Among the embodiment 4, the resin that uses in the formation with the semi-solid preparation resin bed is adjusted into the following composition, adopts the method manufacturing tape tree fat Copper Foil identical with embodiment 1.
[forming the resin combination of the semi-solid preparation resin bed of embodiment 4]
Maleimide resin: bisphenol-A diphenyl ether BMI (trade name: BMI-4000, big and change into industrial society and make)/25 weight portions
Epoxy resin: the cresols phenolic resin varnish type epoxy resin (trade name: エ Port ト one ト YDCN-703, Dongdu changes into society and makes)/25 weight portions
Linear polymer with crosslinkable functional group: the polyethylene acetal resin (trade name: デ Application カ Block チ ラ one Le 5000A, electrochemical industry society makes)/10 weight portions
Epoxy curing agent: cyanate ester resin (trade name: Primaset PT-30, Lonza Ltd. makes)/40 weight portions
As the above-mentioned resin combination of dissolution with solvents, preparation resin solid composition is the solution of 40wt% with dimethylacetylamide.Then, add imidazolium compounds (trade name: キ ユ ア ゾ one Le 2P4MHZ, four countries change into industrial society and make)/0.5 weight portion and zinc acetylacetonate (reagent, 0.01 weight portion), obtain resin varnish as curing catalysts.Adopt the method identical with embodiment 1, with this resin varnish applied, dry, curing, stacked formation semi-solid preparation resin bed.The resin thickness of the semi-solid preparation resin bed of this moment is 20 μ m.
Then, adopt the method identical, the thermal coefficient of expansion after the curing of mensuration semi-solid preparation resin bed with embodiment 1.Consequently, thermal coefficient of expansion is 48ppm/ ℃.And, adopting the method identical with embodiment 1, mensuration makes the thermal coefficient of expansion behind the resin bed integrally curing of the tape tree fat Copper Foil that obtains among the embodiment 4.Consequently, thermal coefficient of expansion is 38ppm/ ℃, and the peel strength of Copper Foil is 1.0kgf/cm.
Comparative example
Comparative example 1
In comparative example 1, be illustrated in the tape tree fat Copper Foil that only forms the semi-solid preparation resin bed identical on the identical electrolytic copper foil of the electrolytic copper foil that uses with embodiment 1 with embodiment 1.
The glassy surface side of the electrolytic copper foil identical with the electrolytic copper foil that uses among the embodiment 1, be coated in the resin combination varnish that the semi-solid preparation resin bed for preparing under the condition identical with embodiment 1 is used, at room temperature carry out 5 minutes air-dry, under 160 ℃ * 5 minutes condition, carry out heat drying, form the semi-solid preparation resin bed.The thickness of the semi-solid preparation resin bed of this moment is 20 μ m.
In addition, similarly to Example 1, the thermal coefficient of expansion after the curing of mensuration semi-solid preparation resin bed.Thickness after the curing of the semi-solid preparation resin bed of this moment is 20 μ m, and thermal coefficient of expansion is 45ppm/ ℃.And, adopt the method identical with embodiment 1, measure the peel strength that makes after the curing of semi-solid preparation resin bed.Consequently, peel strength is 0.3kgf/cm.In order to compare, these values are summarized in the table 1 with embodiment.
Comparative example 2
The composition of the semi-solid preparation resin bed of comparative example 2 is different with embodiment 1, and in addition, the formation of Copper Foil, curing resin layer is to make under the condition identical with embodiment 1.For fear of repeating record, omit explanation to the formation of Copper Foil, curing resin layer.
The semi-solid preparation resin bed that forms in the comparative example 2 is with N, and N '-dimethylacetylamide is as the following resin combination of dissolution with solvents, thereby preparation resin solid composition is the resin varnish of 30wt%.
[forming the resin combination of semi-solid preparation resin bed]
Heat resistant epoxide resin: naphthalene type heat resistant epoxide resin (trade name: HP-4700, big Japanese イ Application Network chemical industry society makes)/40 weight portions
Aromatic polyamine: 1, two (4-amino-benzene oxygen) benzene of 3-(trade name: TPE-R, Wakayama refine industrial society make)/25 weight portions
Epoxy resin: bisphenol A type epoxy resin (trade name: エ ピ Network ロ Application 850S, big Japanese イ Application Network chemical industry society makes)/20 weight portions
Linear polymer with crosslinkable functional group: the polyethylene acetal resin (trade name: デ Application カ Block チ ラ one Le 5000A, electrochemical industry society makes)/15 weight portions
In addition, on the surface of the polyimide resin layer of the copper-clad polyimide resin base material after the sided corona treatment of making under the condition identical with embodiment 1, apply above-mentioned resin varnish, at room temperature carry out 5 minutes air-dry, under 160 ℃ * 5 minutes condition, carry out heat drying, form the semi-solid preparation resin bed.The thickness of the semi-solid preparation resin bed of this moment is 20 μ m.
In addition, similarly to Example 1, the thermal coefficient of expansion after the curing of mensuration semi-solid preparation resin bed.Thickness after the curing of the semi-solid preparation resin bed of this moment is 20 μ m, and thermal coefficient of expansion is 70ppm/ ℃.The thickness of the resin bed integral body of the tape tree fat Copper Foil that obtains in comparative example 2 in addition, is 47 μ m.And, adopt the method identical with embodiment 1, measure the thermal coefficient of expansion and the peel strength that make the resin bed integral body that constitutes by curing resin layer and semi-solid preparation resin bed after the curing of semi-solid preparation resin bed.Consequently, thermal coefficient of expansion is 62ppm/ ℃, and peel strength is 1.0kgf/cm.In order to compare, these values are summarized in the table 1 with embodiment.
Table 1
[contrast of embodiment and comparative example]
About the tape tree fat Copper Foil that obtains in embodiment and the comparative example, the measurement result of its scolding tin hear resistance, peel strength, thermal coefficient of expansion is shown in table 1, and with reference to table 1, comparative example and comparative example.At first, all characteristics all show excellent especially numerical value among embodiment 1～embodiment 4.Relative therewith, comparative example 1 is the example that only forms the semi-solid preparation resin bed of embodiment 1, and its thermal coefficient of expansion, peel strength, scolding tin hear resistance all do not demonstrate and can fully satisfy practical numerical value.Hence one can see that, when only forming the semi-solid preparation resin bed on the surface of Copper Foil, can not be met the practical tape tree fat Copper Foil that requires.
Next, when comparing embodiment 1～embodiment 4 and comparative example 2, though their scolding tin hear resistance and peel strength are peer-levels, the thermal coefficient of expansion aspect, the thermal coefficient of expansion of embodiment 1～embodiment 4 is starkly lower than comparative example 2.Hence one can see that, and using maleimide in the formation of the semi-solid preparation resin bed that carries out behind the formation curing resin layer on the surface of Copper Foil is resin, the reduction of the thermal coefficient of expansion of resin bed after can realizing solidifying.
Next, the evaluation method of scolding tin hear resistance, peel strength, the assay method of thermal coefficient of expansion are described.
In order to estimate scolding tin hear resistance, peel strength, made printed wiring board.On two surfaces of the copper clad laminate of having implemented FR-4 grade internal layer circuit, thickness of slab 0.5mm that melanism is handled, that there are 12 μ m on the surface, by vacuum pressure device, at pressure 20kgf/cm
2, under 170 ℃ * 60 minutes the condition of temperature, the tape tree fat Copper Foil that obtains in pressurize stacked embodiment or the comparative example.Manufacturing has the multilayer printed-wiring board of 4 layers of copper layer.
Then, cut this multilayer printed-wiring board, obtain the heat-resisting test piece of scolding tin of 2.5cm * 2.5cm size, it is swum in 260 ℃ solder bath, be measured to the time that produces till the bubble.
In addition, peel strength is to carry out etching by the outer copper foil to above-mentioned multilayer printed-wiring board, and the peel strength mensuration that forms wide 10mm is used direct-wire circuit, and this direct-wire circuit to become 90 ° direction to peel off with respect to substrate, is measured peel strength thus.
And thermal coefficient of expansion is to measure by the following method: prepare the tape tree fat Copper Foil that obtains in two each embodiment and the comparative example respectively, and the mode that is in contact with one another between the resin face with this tape tree fat Copper Foil is stacked, is solidified by hot pressing.The condition of cure of this moment is that pressure is 20kgf/cm
2, 170 ℃ * 60 minutes.After the curing, remove Copper Foil by etching method, stacked once more above-mentioned tape tree fat Copper Foil, and Copper Foil is removed in etching.Repeat aforesaid operations, make the resin plate of the about 0.2mm of thickness.Then, according to JIS C 6481, measure the thermal coefficient of expansion of this resin plate.
Industrial applicibility
In the resin Copper Foil of the present invention, by consisting of resin bed by the two-layer of curing resin layer and semi-solid preparation resin bed, even the low profile copper foil that the copper foil surface of resin bed is low roughness is set, between resin bed and Copper Foil, also can obtain good adherence. In addition, resin Copper Foil of the present invention is compared with resin Copper Foil in the past, has the low resin bed of thermal coefficient of expansion, therefore, when in lamination method, using as the manufacturing raw material of multilayer printed-wiring board, therefore the high temperature thermal history that applies in the manufacturing process to this printed wiring board, the excellent in dimensional stability of thermal shock, can provide high-quality multilayer printed-wiring board. Consequently, minuteness space and the densification of lamination type printed wiring board circuit can be easily tackled, and the steady production of fine wiring printed wiring board can be realized. In addition, resin Copper Foil of the present invention can be used as the capacitor circuit formation material of curing resin layer as dielectric layer.
Claims (15)
1. tape tree fat Copper Foil, it is the tape tree fat Copper Foil that forms curing resin layer and semi-solid preparation resin bed on the surface of Copper Foil successively, it is characterized in that,
With the surface roughness of the Copper Foil of above-mentioned curing resin layer contact side be 0.5 μ m～2.5 μ m,
Above-mentioned curing resin layer is to be that one of any resinous principle in polyimide resin, polyamide-imide resin and their compound resin of 0ppm/ ℃～25ppm/ ℃ constitutes by thermal coefficient of expansion,
Thermal coefficient of expansion after having curing on the above-mentioned curing resin layer is the semi-solid preparation resin bed of 0ppm/ ℃～50ppm/ ℃.
2. tape tree fat Copper Foil according to claim 1, wherein, the thermal coefficient of expansion after the curing of the resin bed integral body of curing resin layer that forms on the surface of above-mentioned Copper Foil and semi-solid preparation resin bed is below 40ppm/ ℃.
3. tape tree fat Copper Foil according to claim 1, wherein, the glass transition temperature of above-mentioned curing resin layer is more than 300 ℃.
4. tape tree fat Copper Foil according to claim 1, wherein, above-mentioned semi-solid preparation resin bed is that the employing maleimide is that resin forms.
5. tape tree fat Copper Foil according to claim 4, wherein, above-mentioned maleimide is that resin is the aromatic series maleimide resin that has two above dimaleoyl iminos in the molecule.
6. tape tree fat Copper Foil according to claim 4, wherein, above-mentioned maleimide is that resin is the polymerization addition product that the aromatic series maleimide resin that has two above dimaleoyl iminos in the molecule and aromatic polyamine are polymerized.
7. tape tree fat Copper Foil according to claim 1, wherein, when above-mentioned semi-solid preparation resin bed was made as 100 weight portions, the maleimide that this semi-solid preparation resin bed contains 20 weight portions～70 weight portions was a resin.
8. tape tree fat Copper Foil according to claim 1, wherein, the thickness of above-mentioned curing resin layer is 3 μ m～30 μ m.
9. tape tree fat Copper Foil according to claim 1, wherein, the thickness of above-mentioned semi-solid preparation resin bed is 7 μ m～55 μ m.
10. tape tree fat Copper Foil according to claim 1, wherein, the total gross thickness of above-mentioned curing resin layer and above-mentioned semi-solid preparation resin bed is 10 μ m～60 μ m.
11. tape tree fat Copper Foil according to claim 1, wherein, above-mentioned Copper Foil adopts no roughening Copper Foil.
12. the manufacture method of a tape tree fat Copper Foil, it is the manufacture method of the described tape tree fat of claim 1 Copper Foil, it is characterized in that, and through following operation A and process B,
Operation A: be on the surface of Copper Foil of 0.5 μ m～2.5 μ m in surface roughness, using thermal coefficient of expansion is one of any resinous principle in polyimide resin, polyamide-imide resin and their compound resin of 0ppm/ ℃～25ppm/ ℃, forms curing resin layer;
Process B: by on above-mentioned curing resin layer, thermal coefficient of expansion after the curing is set is the semi-solid preparation resin bed of 0ppm/ ℃～50ppm/ ℃, obtain tape tree fat Copper Foil.
13. the manufacture method of tape tree fat Copper Foil according to claim 12, wherein, in above-mentioned operation A, when using thermal coefficient of expansion on the surface of Copper Foil that in surface roughness is 0.5 μ m～2.5 μ m is the polyimide resin of 0ppm/ ℃～25ppm/ ℃ when forming curing resin layer, adopts casting method or laminating.
14. the manufacture method of tape tree fat Copper Foil according to claim 12, wherein, in above-mentioned process B, with the maleimide that contains that is used to form this semi-solid preparation resin bed is the amount of the resin combination of resin when being made as 100 weight portions, and the maleimide that this resin combination contains 20 weight portions～70 weight portions is a resin.
15. the manufacture method of tape tree fat Copper Foil according to claim 12 wherein, is provided with the surface modification operation of the surface of curing resin layer being carried out plasma treatment or sided corona treatment between above-mentioned operation A and process B.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007338720 | 2007-12-28 | ||
| JP2007-338720 | 2007-12-28 | ||
| JP2008-325025 | 2008-12-22 | ||
| JP2008325025A JP5636159B2 (en) | 2007-12-28 | 2008-12-22 | Copper foil with resin and method for producing copper foil with resin |
| PCT/JP2008/073412 WO2009084533A1 (en) | 2007-12-28 | 2008-12-24 | Copper foil with resin and process for producing copper foil with resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101909878A true CN101909878A (en) | 2010-12-08 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008801233016A Pending CN101909878A (en) | 2007-12-28 | 2008-12-24 | Copper foil with resin and process for producing copper foil with resin |
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| Country | Link |
|---|---|
| JP (1) | JP5636159B2 (en) |
| KR (1) | KR101357230B1 (en) |
| CN (1) | CN101909878A (en) |
| MY (1) | MY159854A (en) |
| TW (1) | TWI461287B (en) |
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| CN103786402A (en) * | 2014-01-27 | 2014-05-14 | 中原工学院 | Method for preparing huge two-sided flexible copper foil by sprinkling complex solution with atomizing powder sprinkling device |
| CN109476923A (en) * | 2016-07-19 | 2019-03-15 | 日立化成株式会社 | Resin combination, plywood and multilayer printed circuit board |
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| JP5580135B2 (en) * | 2010-08-03 | 2014-08-27 | 三井金属鉱業株式会社 | Printed wiring board manufacturing method and printed wiring board |
| US9138964B2 (en) | 2010-11-22 | 2015-09-22 | Mitsui Mining & Smelting Co., Ltd | Surface-treated copper foil |
| JP2013123907A (en) * | 2011-12-16 | 2013-06-24 | Panasonic Corp | Metal clad laminated plate and printed wiring board |
| JP6375952B2 (en) * | 2013-01-07 | 2018-08-22 | 株式会社ニコン | Composition, laminate, method for producing laminate, transistor and method for producing transistor |
| KR101851882B1 (en) | 2013-07-23 | 2018-04-24 | 제이엑스금속주식회사 | Treated surface copper foil, copper foil with carrier, substrate, resin substrate, printed circuit board, copper clad laminate, and printed circuit board manufacturing method |
| TWI645755B (en) | 2013-07-24 | 2018-12-21 | Ｊｘ日鑛日石金屬股份有限公司 | Surface-treated copper foil, copper foil with carrier, substrate, resin substrate, printed wiring board, copper-clad laminate, and printed wiring board manufacturing method |
| JP6403503B2 (en) * | 2013-09-30 | 2018-10-10 | 新日鉄住金化学株式会社 | Copper-clad laminate, printed wiring board and method of using the same |
| KR101582398B1 (en) * | 2014-01-06 | 2016-01-05 | 주식회사 두산 | Resin double layer coated copper multilayered printed circuit board and method of manufacturing the same |
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| KR101852671B1 (en) | 2015-01-21 | 2018-06-04 | 제이엑스금속주식회사 | Copper foil with carrier, laminate, printed circuit board and method of manufacturing printed circuit board |
| KR101942621B1 (en) | 2015-02-06 | 2019-01-25 | 제이엑스금속주식회사 | Copper foil with carrier, laminate, printed circuit board, electronic device and method of manufacturing printed circuit board |
| JP2017193778A (en) | 2016-04-15 | 2017-10-26 | Ｊｘ金属株式会社 | Copper foil, copper foil for high frequency circuit, copper foil with carrier, copper foil with carrier for high frequency circuit, laminate, method for manufacturing printed wiring board and method for producing electronic apparatus |
| CN113584537B (en) * | 2021-08-03 | 2023-01-06 | 东强（连州）铜箔有限公司 | Ultra-thin copper foil with resin layer and extremely low roughness and manufacturing method thereof |
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- 2008-12-22 JP JP2008325025A patent/JP5636159B2/en active Active
- 2008-12-23 TW TW097150190A patent/TWI461287B/en active
- 2008-12-24 KR KR1020107014604A patent/KR101357230B1/en active IP Right Grant
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- 2008-12-24 MY MYPI2010002988A patent/MY159854A/en unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103786402A (en) * | 2014-01-27 | 2014-05-14 | 中原工学院 | Method for preparing huge two-sided flexible copper foil by sprinkling complex solution with atomizing powder sprinkling device |
| CN109476923A (en) * | 2016-07-19 | 2019-03-15 | 日立化成株式会社 | Resin combination, plywood and multilayer printed circuit board |
| CN109476923B (en) * | 2016-07-19 | 2022-04-05 | 昭和电工材料株式会社 | Resin composition, laminate, and multilayer printed wiring board |
| CN114479459A (en) * | 2016-07-19 | 2022-05-13 | 昭和电工材料株式会社 | Resin composition, laminate, and multilayer printed wiring board |
| US11377546B2 (en) | 2016-07-19 | 2022-07-05 | Showa Denko Materials Co., Ltd. | Resin composition, laminate sheet, and multilayer printed wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5636159B2 (en) | 2014-12-03 |
| MY159854A (en) | 2017-02-15 |
| TWI461287B (en) | 2014-11-21 |
| JP2009173017A (en) | 2009-08-06 |
| KR20100100930A (en) | 2010-09-15 |
| KR101357230B1 (en) | 2014-02-03 |
| TW200944370A (en) | 2009-11-01 |
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Application publication date: 20101208 |