CN101890829B - Treated copper foil and preparation method thereof - Google Patents
Treated copper foil and preparation method thereof Download PDFInfo
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- CN101890829B CN101890829B CN 201010217376 CN201010217376A CN101890829B CN 101890829 B CN101890829 B CN 101890829B CN 201010217376 CN201010217376 CN 201010217376 CN 201010217376 A CN201010217376 A CN 201010217376A CN 101890829 B CN101890829 B CN 101890829B
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- copper foil
- silane
- laminated plate
- chromium oxide
- oxide layer
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Abstract
The invention relates to a treated copper foil, comprising a copper foil and a trivalent chromium oxide layer, wherein a zinc oxide layer is adhered to at least one bottom surface of the copper foil and has thickness shown in the specification; and the trivalent chromium oxide layer is adhered to the zinc oxide layer. In a specific embodiment, the copper foil is provided with a layer of organic silane coupling agent adhered to the trivalent chromium oxide layer. The invention also relates to a method for applying the zinc oxide layer and the trivalent chromium oxide layer on the copper foil. The invention also relates to a laminated material formed by a dielectric matrix and the copper foil adhered to the matrix. In a specific embodiment, the dielectric matrix is formed by epoxy resins made of curing agents different from amine curing agents.
Description
The application divides an application, and the applying date of its female case is that September 16, application number in 1999 are 99817006.2, and name is called " treated copper foil and its preparation method ".
Technical field
The present invention relates to the preparation method of a kind of treated copper foil (treated copper foil) and a kind of treated copper foil.Treated copper foil has a zinc oxide thin layer to be attached on its basal surface at least simultaneously, adheres to again one deck trivalent chromium oxide on zinc oxide film.Treated copper foil is used for making laminated material and printed circuit board (PCB).
Background technology
Copper Foil is for the production of printed circuit board (PCB), although it is fabulous electronic conductor, uses this Copper Foil that some problems are also arranged.Copper is easy to oxidized and corrosion.In the production of printed circuit board (PCB), generally Copper Foil need to be bonded on the dielectric matrix so that Copper Foil has size and structural stability.When making sheet or roll extrusion, Copper Foil generally is inadequate to the bonding force of this matrix.Copper can accelerate or the decomposition of catalysis dielectric matrix also is known.Owing to these reasons, the sale of Copper Foil normally adds one or more layers protective layer in its surface.
The existing method that adds protective layer at Copper Foil generally comprises following step order: the first, and at copper foil surface deposition pomegranate shape or dendroid copper layer, the dendroid layer can be added on the matsurface or glassy surface of Copper Foil, or is added in simultaneously on the two sides of Copper Foil.Add the dendroid layer and be in order to increase the mechanical connection between dielectric matrix and the copper foil surface, to increase the bonding strength of Copper Foil: the second, on the dendroid layer of Copper Foil, deposit again one deck barrier layer (generally forming with brass).Add the barrier layer and be in order to stop the thermal degradation at metal-resin interface, thereby kept the bonding force of Copper Foil to resin; The 3rd, add stabilized zone (generally being formed by zinc or chromium) on the two sides of Copper Foil.Stabilized zone helps anti-oxidant, anti-storage and moisture resistance.
Above-mentioned method has many shortcomings.Dendroid copper layer has increased copper thickness and the required etching period of etching copper foil circuit.The dendroid layer has reduced the Copper Foil quality because having increased the recessed number in hole, and has also reduced process linear speeds.The barrier layer requires to use the bath that contains cyanide of causticity, and the processing of its discarded object is difficulty and expensive.Apply the barrier layer and also require to use the soluble anode that can make Copper Foil debase and the anode that is easy to polarize.When applying stabilized zone, in bath, can form undesirable precipitation.The invention provides the Copper Foil that does not need the desired pomegranate shape of prior art Copper Foil or dendroid copper layer or barrier layer, overcome above problems, but still had initial bonding strength and the heat resistanceheat resistant degradation property that matches in excellence or beauty with the prior art Copper Foil.
Dielectric matrix (sometimes being referred to as prepreg) epoxy resin commonly used used on the market prepares.The many prepregs based on epoxy resin that provide now are to use to make such as the amine hardener of dicyanodiamine.Yet there are many problems all relevant with this amine hardener of use, comprise environment, safety and processing.Recently introduced again the new prepreg based on epoxy resin on the market, its preparation does not need this amine hardener.These new epoxy prepregs are referred to as " non-dicyan (non-dicy) " prepreg sometimes.These non-dicyan prepregs are favourable, but the typical initial bonding strength that uses a problem of this prepreg to relate between Copper Foil and the prepreg is generally lower, in some instances when using conventional epoxy prepreg low about 10%.The invention provides the treated copper foil that can use and still have with non-dicyan prepreg desired peel strength, also overcome this problem.
Summary of the invention
The present invention relates to treated copper foil, this Copper Foil comprises: a Copper Foil, adhere to one deck zinc oxide on the basal surface of at least one side of this Copper Foil, and the thickness of this zinc oxide film is about
One deck trivalent chromium oxide layer is attached on the said zinc oxide film.In one embodiment, Copper Foil has one deck organo silane coupling agent to be attached on the trivalent chromium oxide layer.The present invention also relates to apply at said Copper Foil the method for zinc oxide film and trivalent chromium oxide layer.The present invention also relates to by dielectric matrix and be attached to the laminated material that the above-mentioned Copper Foil on the matrix forms.In a specific embodiments, the epoxy resin that dielectric matrix is made by the curing agent that is different from amine hardener forms, and namely dielectric matrix is a non-dicyan prepreg.
The specific embodiment
The used Copper Foil of the present invention is by a kind of the making in two kinds of technology.Ripe forging or rolling Copper Foil are that the thickness of using method such as rolling mechanically to reduce copper or copper alloy bar or (ingot) is produced.The Copper Foil of electrodeposition process production is that copper ion is deposited on the cathode drum of a rotation, and then from negative electrode the copper strips that deposits is stripped down.The Copper Foil of electro-deposition is useful especially in the present invention.
The typical nominal thickness of Copper Foil is about the 0.0002-0.02 inch.Copper Foil represents with weight that sometimes the weight of Copper Foil of the present invention or thickness generally are about 1/8-14 ounce/foot
2, the weight that useful especially Copper Foil has is 1/2,1 or 2 ounce/foot
2
Electro-deposition copper foil has smooth or glossiness one side (drum surface) and coarse or lacklustre one side (copper deposition growing face).Zinc oxide and trivalent chromium oxide can be applied on any one side of Copper Foil, are to be applied to simultaneously on two faces in some examples.
The one or both sides that apply the Copper Foil of zinc oxide film and trivalent chromium oxide layer can have " standard light cleanliness surface ", " best bright finish surface " or " catch light cleanliness surface "." standard light cleanliness surface " word refers to the R of copper foil surface
TmBe about the 7-10 micron; " best bright finish surface " word refers to the R of copper foil surface
TmBe about 4-7 micron or less; " catch light cleanliness surface " word refers to the R of copper foil surface
TmBe about 4 microns or less.R
TmBe the maximum peak measured of five continuous samplings-paddy mean value, available Surftronic profilometer (market sale, Rank Taylor Hobson, Ltd., Leicester, England) is measured.
The thickness of zinc oxide film is about
Be about in one embodiment
Be about in one embodiment
Be about in one embodiment
Be about in one embodiment
Be about in one embodiment
The thickness of zinc oxide film is crucial for reaching peel strength performance of the presently claimed invention.Zinc oxide film is to impose on the one or both sides of Copper Foil with the metallic zinc layer, and then carries out oxidation with the following method of being discussed.Before the oxidation, the thickness of metallic zinc layer is about
Be about in one embodiment
Be about in one embodiment
Be about in one embodiment
Be about in one embodiment
Be about in one embodiment
The metallic zinc layer is to impose on the basal surface of one or both sides of Copper Foil.Before applying the metallic zinc layer, the surface of Copper Foil is undressed." unprocessed " word refers to this fact of processing (such as imposing dendroid copper layer, barrier layer, stabilized zone etc.) that is to make with extra care or improve the Copper Foil performance that the basal surface of Copper Foil is not looked over so as to check.Yet the basal surface that should be noted in the discussion above that Copper Foil may have one deck natural non-dendroid attached to it or the cupric oxide of non-pomegranate shape.
In one embodiment, metallic zinc imposes on copper foil surface with vapour deposition process.Any phase deposition technique of gas known in the art all is operable, comprises physical vapour deposition (PVD) (PVD) technology and chemical vapour deposition (CVD) (CVD) technology.Physical vapour deposition (PVD) comprises thermal evaporation, electron beam deposition, induces and/or resistance deposition, ion plating, cathode vacuum spraying plating, plasma-activated evaporation, reactive evaporation and activation response evaporation.Physical vapour deposition (PVD) is also referred to as vacuum metal film plating and evaporation coating in the literature.In thermal evaporation deposition process, be to impose on metallic zinc on the Copper Foil in high vacuum (for example 10
-2-Yue 10
-6Torr (torr)) heating in, metallic zinc is then evaporated or is distilled and transfer to copper foil surface.In the vacuum evaporating method, the high energy inertia ion pair target that plasma discharge produces impacts, and metallic zinc is launched by exchange of kinetic energy.Physical vapour deposition (PVD) mainly comprises transfer and the formation of zinc layer on Copper Foil of metallic zinc, is to use the single one physical method.Contrast with chemical vapour deposition (CVD), in chemical vapour deposition (CVD), the transfer of metallic zinc is to work with the chemical reaction that the concentration gradient between temperature or matrix and the surrounding atmosphere is induced.The principle of the vapour deposition of various metals and step are described in that the people such as C.F.Powell compiles
Vapor Deposition(vapour deposition process) John Wiley ﹠amp; Sons, Inc., New York, 1966, at this as a reference.
Chemical vapour deposition (CVD) generally is accompanied by decomposition or the reaction of the gasification of zinc halide and the steam above copper foil surface, to produce the non-volatile metallic zinc as coating at copper foil surface.The chemical reaction of vapour deposition can be with heat deposition or hot tearing, hydrogen reduction, with the metal vapors reduction, transport reaction etc. with Copper Foil reaction, chemistry carries out.These methods are specified in that the people such as C.F.Powell compiles
Vapor Deposition, chapter 9, John Wiley ﹠amp; Sons, Inc., New York, 1966.This chapter narration CVD method, at this as a reference.
The metallic zinc layer also can come coating with electroplating technology known in the art.Zinc ion source in the dielectric solution can be any zinc salt, and its example comprises ZnSO
4, ZnCO
3Deng.In one embodiment, the release of the electrolyte hydrogen inhibitor that contains effective dose hydrogen when suppressing to electroplate.The hydrogen inhibitor can be following any ion: P
+ 3, W
+ 6, As
+ 3, As
+ 5, Pb
+ 2, Pb
+ 4, Hg
+ 1, Hg
+ 2, Cd
+ 2Or quaternary ammonium ion.P
+ 3, W
+ 6And As
+ 5Special useful, P
+ 3Useful especially.The ion gun of these ions comprises H
3PO
3, Na
2WO
4, HAsO
3, Pb (SO
4)
2, Hg
2SO
4, HgSO
4, CdSO
4Deng.Quaternary ammonium ion can represent it by following formula:
R in the formula
1, R
2, R
3And R
4Respectively the do for oneself alkyl of about 16 carbon atoms of 1-is the alkyl of about 8 carbon atoms of 1-in a specific embodiments, is the alkyl of about 4 carbon atoms in another embodiment.These ion guns comprise TBAH.
Zinc ion concentration in the electrolyte is generally in about 0.1-2 grams per liter scope; About 0.2-2 grams per liter in one embodiment; About 0.3-0.7 grams per liter in one embodiment; About 0.5 grams per liter in one embodiment.The ion concentration of hydrogen inhibitor generally can reach about 1 grams per liter scope; About 0.01-0.8 grams per liter in one embodiment; About 0.05-0.5 grams per liter in one embodiment; About 0.4 grams per liter in one embodiment.Electrolyte can comprise other habitual additive, such as Na
2SO
4, NaCl, NaOH, K
4P
2O
7Deng, its concentration can reach about 100 grams per liter scopes; About 5-100 grams per liter in one embodiment; About 5-50 grams per liter in one embodiment; About 10-30 grams per liter in one embodiment; About 10-20 grams per liter in one embodiment.The pH of electrolyte is generally in about 4-5.5 scope; About 4.5-5.5 in one embodiment; About 4.5-5 in one embodiment.Current density is generally at about 5-50 ampere/foot
2Scope; About 15-30 ampere/foot in one embodiment
2About 15-25 ampere/foot in one embodiment
2The temperature of electrolyte is generally in about 20-50 ℃ scope; About 30-45 ℃ in one embodiment; About 35-40 ℃ in one embodiment.Used electroplating time is generally in about 1-30 scope second; About 2-25 second in one embodiment; About 2-10 second in one embodiment; About 2-6 second in one embodiment; About 2-4 second in one embodiment.
The oxidation of metallic zinc layer is to apply in its surface one deck sexavalence chromium oxide with known electroplating technology.In this process, sexavalence chromium oxide is transformed into or is reduced into trivalent chromium oxide.The thickness of the trivalent chromium oxide layer that obtains is about
Be about in one embodiment
Be about in one embodiment
Sexavalence chromium oxide source can be chromium trioxide (CrO
3), such as chromyl amine (CrO
2(NH
2)
2) or chromyl chloride (CrO
2Cl
2) and so on chromyl (CrO
2 ++) compound, such as Na
2Cr
2O
4Or K
2Cr
2O
4And so on chromic acid (CrO
4 =) compound or such as Na
2Cr
2O
7Or K
2Cr
2O
7And so on dichromic acid (Cr
2O
7 =) compound.The concentration of sexavalence chromium oxide compounds is generally in about 1-5 grams per liter scope in the electrolyte; About 2-4 grams per liter in one embodiment; About 3 grams per liters in one embodiment.Electrolyte can comprise other habitual additive, such as Na
2SO
4, its concentration can reach about 15 grams per liter scopes; About 1-15 grams per liter in one embodiment.PH used in the electrolyte is generally at about 1.5-9; About 2-6 in one embodiment; About 4.5-5.5 in one embodiment.Current density is generally at about 2-20 ampere/foot
2Scope; About 10-20 ampere/foot in one embodiment
2The temperature of electrolyte is generally in about 20-50 ℃ scope; About 35-40 ℃ in one embodiment.Used electroplating time is generally in about 2-15 second; About 5-12 second in one embodiment; About 10 seconds in one embodiment.
On the trivalent chromium oxide layer, can apply one deck silane coupler.Silane coupler can represent it by following formula:
R
4-nSiX
n
R is the alkyl that sense replaces in the formula, and the sense substituent on the alkyl that said sense replaces is amino, hydroxyl, halogen, mercapto, alkoxyl, acyl group or epoxy radicals; X is a hydrolysising group, such as alkoxyl (such as methoxyl group, ethyoxyl etc.) or halogen (for example chlorine); N is 1,2 or 3, preferred 3.Silane coupler with the following formula representative comprises halogenated silanes, aminoalkoxy silane, aminophenyl silane, phenyl silane, heterocycle silane, N-heterocycle silane, acrylic silane, mercaptan silane and their both or the mixture more than the two.
Useful silane coupler comprises aminopropyl trimethoxysilane, tetramethoxy-silicane, tetraethoxysilane, two (2-ethoxy)-3-aminopropyl triethoxysilanes, 3-(N-styryl methyl-2-aminoethyl is amino) propyl trimethoxy silicane, 3-glycidol oxygen propyl trimethoxy silicane, N-methyl aminopropyl trimethoxysilane, 2-(2-aminoethyl-3-aminopropyl) trimethoxy silane, N-phenylamino propyl trimethoxy silicane, r-chloropropyl trimethoxyl silane and their both or the two above mixture.
A kind of useful silane coupled agent composition is the mixture of 3-glycidol oxygen propyl trimethoxy silicane and tetramethoxy-silicane or tetraethoxysilane.The weight ratio of the former with the latter can be about 1: about 10: 1 scopes of 10-; Be about in one embodiment 1: about 5: 1 of 5-; Be about in one embodiment 4: 1.
A kind of useful silane coupled agent composition is N-methyl aminopropyl trimethoxysilane and r-chloropropyl trimethoxyl silane mixture.The weight ratio of the former with the latter can be about 1: about 10: 1 scopes of 10-; Be about in one embodiment 1: about 5: 1 of 5-; Be about in one embodiment 1: 1.
A kind of useful silane coupled agent composition is the mixture of 3-(N-styryl methyl-2-aminoethyl is amino) propyl trimethoxy silicane and N-methyl aminopropyl trimethoxysilane.The weight ratio of the former with the latter can be about 1: about 10: 1 scopes of 10-; Be about in one embodiment 1: about 5: 1 of 5-; Be about in one embodiment 1: 1.
A kind of useful silane coupled agent composition is the mixture of 3-glycidol oxygen propyl trimethoxy silicane and N-methyl aminopropyl trimethoxysilane.The weight ratio of the former with the latter can be about 1: about 10: 1 scopes of 10-; Be about in one embodiment 1: about 5: 1 of 5-; Be about in one embodiment 1: 3.
Be coated in the trivalent chromium oxide surface with silane coupler and can adopt the pure silane coupling agent.But, preferably be used in general the surface of the silane coupler coating trivalent chromium oxide in the suitable medium.More particularly, the silane coupler that imposes on the trivalent chromium oxide surface can be the form of the solution in the mixture of water, water and ethanol or suitable organic solvent, or the aqueous emulsion form of the aqueous emulsion of silane coupler or the solution of silane coupler in the organic solvent that is fit to.Operable conventional organic solvent comprise alcohol for example, ether, ketone and they and aliphatic hydrocarbon or aromatic hydrocarbon mixture or with the mixture of acid amides such as DMF.Useful organic solvent comprises those wettabilities and the good solvent of drying property, comprises for example water, ethanol, isopropyl alcohol and MEK.The aqueous emulsion of silane coupler can form according to a conventional method, uses conventional dispersant and surfactant, comprises non-ionic surface active agent.The concentration of the silane coupler in these solution or emulsion can be up to the silane coupler of 100wt%; Can reach about 50wt% in one embodiment; Can reach about 20wt% in one embodiment; In one embodiment in about 0.1-5wt% scope; About 0.3-1wt% in one embodiment.Method with the silane coupler coating can repeat, and can carry out repeatedly when needing.Known coating method coating silane coupler be can use, inverse roller coating, blade coating, dip-coating, spraying comprised.
It is to carry out under about 15-45 ℃ temperature that silane coupler is imposed on the trivalent zinc oxide surface, is about in one embodiment 20-30 ℃.After silane coupler is imposed on the trivalent chromium oxide surface, silane coupler can be heated to temperature and be about 60-170 ℃, be about in one embodiment 90-150 ℃, the time generally was about 0.1 second-5 minutes, be about in one embodiment 0.2-2 minute, to increase the drying on surface.The thickness of silane coupler dry film generally is about the 0.002-0.1 micron, is about in one embodiment the 0.005-0.02 micron.
Copper Foil of the present invention can be bonded on the dielectric matrix, so that the Copper Foil with size and structural stability to be provided.As noted before, dielectric matrix is sometimes referred to as prepreg.Useful dielectric matrix can be partly solidified the woven glass reinforced material of resin-dipping, normally used is epoxy resin (for example two senses, four senses and multi-functional epoxy compound).Other useful resin comprises with the amino resins of formaldehyde and urea reaction or formaldehyde and melamine generation, polyester, phenolic resin, polysiloxanes, polyamide, polyimides, diallyl phthalate, phenyl silane, polybenzimidazoles, diphenyl ether, polytetrafluoroethylene (PTFE), cyanate etc.
In one embodiment, the used resin of preparation prepreg is epoxy resin, and it uses with curing agent, and used curing agent is non-amine hardener, and namely these epoxy resin do not have amine hardener.The amine hardener of avoiding using comprises polyamines, polyether diamine and other aliphatic polyamine such as dicyanodiamine, polymethylene diamines, alicyclic ring polyamines and the aromatic polyamine such as phenylenediamine, toluenediamine and diphenylamines methane such as Meng diamines.These resins are sometimes referred to as " non-dicyan " resin.The prepreg made from these resins is sometimes referred to as non-dicyan prepreg.
Useful epoxy resin comprises thermosetting resin, is made by epoxy monomer or oxidation performed polymer and non-amine hardener.Curing agent is the multifunctional reagent of coreaction with reactive hydrogen atom.The epoxy resin that can be used for preparing prepreg comprises monofunctional epoxy resin, two sense epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, face can epoxy resin and admixture, mixture and their product.In general, these epoxy resin free list chloropharins with single-, two-and trihydroxy benzene phenolic compounds, multinuclear polyhydroxy benzenes phenolic compounds and/or aliphatic polyol react to prepare.Two-and the example of trihydroxy benzene phenolic compounds comprise resorcinol, phloroglucin; Multinuclear polyhydroxy benzenes phenolic compounds comprises two (p-hydroxybenzene) methane and 4,4 '-dihydroxybiphenyl; The example of aliphatic polyol comprises BDO and glycerine.Epoxy resin also can prepare in acid solution with phenol (such as phenol, cresols, resorcinol or bisphenol-A) and formaldehyde.
The amount of the curing agent in epoxy resin forms is the effective dose of cured epoxy compound, generally is the about 0.75-1.25 equivalent of the every equivalent epoxide of stoichiometric amount.Percentage meter by weight, the amount of curing agent generally is about 10-70wt%; Be about in one embodiment 15-50wt%; Be about in one embodiment 15-40wt%, based on the total weight of epoxide and curing agent.
In one embodiment, curing agent is one to contain the compound of C, H and O atom, sometimes also contains the halogen atom such as bromine atoms.Effective curing agent of these epoxy resin comprises: for example mercaptan and the phenolic compound of acid (particularly organic carboxyl acid and carboxylate), acid anhydrides (particularly organic acid anhydride), alkoxide, phenates, polymerization.Phenols curing agent comprises phenol type phenolic resins, cresols type phenolic resins and other many hydroxyls phenolic compounds.
Phenol-ing fixed agent also comprises polyhydric phenols, such as resorcinol, catechol, quinhydrones, p-tert-butyl catechol, saligenin, bisphenol-A, bis-phenol, trihydroxy methyl allyloxy phenol, trihydroxy diphenyl dimethyl ethane, 4,4 '-dihydroxybiphenyl, dihydroxydiphenylsulisomer and phenol resin.
Acid as curing agent comprises inorganic acid such as the acid of ore deposit and the organic acid such as polybasic carboxylic acid, such as adipic acid, phthalic acid, glutaric acid, malonic acid, butanedioic acid, maleic acid, fumaric acid, oxalic acid, citraconic acid, itaconic acid acid, trimellitic acid, 1,2,4,5-, four benzoic acids, pentamethylene tetracarboxylic acid, dimeric dibasic acid and polyacrylic acid.
Anhydride curing agent comprises phthalic anhydride, succinyl oxide, itaconic anhydride, citraconic anhydride, the alkene acid anhydrides, dodecenylsuccinic anhydride, the tricarballylic acid acid anhydride, maleic anhydride, linoleic maleic anhydride adduct, maleic anhydride and styrol copolymer, the maleic anhydride adduct of conjugated diolefin polymer, the maleic anhydride adduct of acetylene series conjugated diene random copolymer, the maleic anhydride adduct of natural fat, the maleic anhydride adduct of methyl cyclopentadiene, methyl-2-replaces the cyclobutenyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, 1,2,4,5-four benzoic anhydrides, the pentamethylene tetracarboxylic acid anhydride, the benzophenone tetracarboxylic anhydride, 1,2-ethylene glycol, two trimellitates, trimellitic anhydride, dodecyl succinic anhydride and dichlorosuccinic acid acid anhydride.
In one embodiment, curing agent is a phenol degree of functionality greater than about 1.75 phenol type compound.These compounds comprise phenol type phenolic resins, are to react preparation by the dihydroxy phenol such as resorcinol or bisphenol-A and formaldehyde in acid solution.A kind of useful phenol resin curing agent is bisphenol-A and the curing agent of formaldehyde in acid solution.A kind of useful phenol type phenolic resin curative is that weight is the about 60-500 of each phenolic group, is about 60-300 in one embodiment, and average per molecule more than 2 phenolic hydroxyl groups, be the bisphenol-A type phenolic resins of about 5 phenolic hydroxyl groups of 3-in one embodiment.These phenolic resin curatives are with trade mark
Provided by Shell company, for example
DX-175.
In a specific embodiments, the curing agent of epoxy resin is a bisphenol-A formaldehyde phenolic resin, is provided by Georgia Pacific Resins company, and trade mark is BRWE 5300.This curing agent is produced with acid catalyst (normally oxalic acid), it is characterized in that its melt viscosity under about 125 ℃ is about the 800-1600 centipoise, and hydroxyl equivalent weight is that 120, Mettler softening point is about 80-105 ℃.
In a specific embodiments, curing agent is the mixture of a phenol resin curing agent and bromination phenol-ing fixed agent.The bromination phenol-ing fixed agent can be any monomer or polymerizable compound with the one or more bromine atoms at least one free phenolic hydroxyl group and the aromatic rings.The example of the bromination phenol-ing fixed agent that is fit to comprises brominated bisphenol-A phenolic resins, brominated phenols type phenolic resins, bromination polyoxy phenylene, brominated bisphenol-A and brominated bisphenol-A carbonate.The consumption of brominated bisphenol-A-as can reach about 40wt%, common about 10-30wt% is based on the total weight of epoxide and curing agent.
In order to promote the quick and/or low-temperature setting of epoxy resin ingredient, can alternatively be used curing accelerator.In that many suitable known accelerators are arranged in the art, such as ureas, imidazoles, phosphene, zincate and boron trifluoride.In one embodiment, accelerator is an imidazoles, such as 1-methylimidazole, 2-ethyl imidazol(e), glyoxal ethyline, 2-methyl-4-ethyl imidazol(e) or isopropylimdazole.The amount of accelerator is effectively to increase the solidification rate that forms and/or the amount that reduces solidification temperature in the composition, is generally 0.1-7wt%, is about in one embodiment 0.05-3wt%, calculates based on the weight that epoxy resin forms.
Epoxy resin be according to epoxy prepreg application process parameter designing within certain specification.The representative formula of epoxy resin is liquid, and imposes at epoxy resin under the temperature of time course required on the matrix and can not solidify.Epoxy resin generally has enough low-viscosities to make it that the saturated of good " soakage " or plate be arranged and need not executing material point working pressure carrying roller and using a large amount of volatile organic solvents.Yet once being applied on the matrix, epoxy resin generally has enough viscositys, is can not drip from the combination of epoxy resin/plate in the past arriving the thermal treatment zone therefore.
In one embodiment, the viscosity of epoxy resin is at about 0.5-10 pool scope, preferably about 0.5-6 pool.In one embodiment, epoxy resin is the mixture of bromination diglycidyl ether, phenol type phenolic resin curative and glyoxal ethyline accelerator of the bisphenol-A of the about 310-350 of diglycidyl ether, WPE with bisphenol-A of the about 175-190 of WPE and the about 30-50% of bromination content.
In one embodiment, epoxy resin comprises a water-containing organic solvent or diluent, and its amount can effectively reduce the viscosity of system so that processing.Example moisture or polar organic solvent comprises ketone, pure and mild glycol ethers.General its boiling point of useful solvent is lower than about 160 ℃, comprises the solvent mixture of ketone such as acetone, MEK and methyl iso-butyl ketone (MIBK) and these ketone and alkylene glycol ether such as propylene glycol monomethyl ether.Quantity of solvent in the composition can have larger variation, is decided by the amount of other component and the purposes of composition.But the solvent in dicyandiamide solution generally will consist of about 6-40wt% of epoxy resin gross weight.
Useful epoxy resin comprises epoxy phenolics, such as DEN 439 and DEN 438, is provided by Dow Chemical company.The feature of DEN 439 is that epoxy functionalities is 3.8, and epoxide equivalent weight is 191-210, and the Mettler softening point is about 48-58 ℃.The feature of DEN 438 is that epoxy functionalities is 3.6, and epoxide equivalent weight is 176-181, and the viscosity under about 52 ℃ is about 20,000-50,000 centipoise.Another operable epoxy phenolics is DEN 485, also is that Dow Chemical company produces.The epoxy functionalities of DEN 485 is 5.5, and epoxide equivalent weight is 165-195, and softening point is about 66-80 ℃.
Other epoxy resin comprises epoxy cresol novolac resin, is produced by Ciba Chemical company, and such as ECN 1235, its epoxy functionalities is 2.7, and epoxide equivalent weight is 200-227, and fusing point is about 34-42 ℃; ECN1273, its epoxy functionalities is 4.8, and epoxide equivalent weight is 217-233, and fusing point is about 68-78 ℃; ECN 1280, and its epoxy functionalities is 5.0, and epoxide equivalent weight is 213-233, and fusing point is about 78-85 ℃; ECN 1299, and its epoxy functionalities is 5.4, and epoxide equivalent weight is 217-244, and fusing point is about 85-100 ℃.
The epoxy resin that is fit to also comprises four trifunctional phenols, such as MTO 163, is provided by Ciba Chemical company, and its epoxy functionalities is 4, and epoxide equivalent weight is about 179-200, and fusing point is about 55-95 ℃; And
1031, provided by Shell company,, its epoxy functionalities is 3.5, and epoxide equivalent weight is about 200-240, is a hard resin, and the dynamic viscosity under about 25 ℃ is about Z2-Z7 (the 80wt% solution in MEK).
Other epoxy resin that is fit to comprises the epoxy phenolics of modification, such as the EPI-REZ SU resin of Shell company, such as EPI-REZ SU-2.5, its epoxy functionalities is 2.5, epoxide equivalent weight is 180-200, and the melt viscosity under about 25 ℃ is about the 2500-4500 centistoke; EPI-REZSU-3.0, its epoxy functionalities is 3.0, epoxide equivalent weight is 187-211, melt viscosity under about 25 ℃ is about 20,000-50,000 centistoke and EPI-REZ SU-8, its epoxy functionalities is 8.0, and epoxide equivalent weight is 195-230, and fusing point is about 77-82 ℃.
Two useful sense epoxy resin are bisphenol-A diglycidyl ether epoxy resin
826, provided by Shell company.The feature of this resin is that epoxy functionalities is 2, and epoxide equivalent weight is 178-186, and the viscosity under about 25 ℃ is about the 6500-9500 centipoise.
826 branch comprises the Araldite GY 6008 that CibaChemical company provides, the EPOTUF 37-139 that the DER 333 of Dow Chemical company and Reichold company provide.
Other bisphenol-A diglycidyl ether epoxy resin that is fit to comprises the following resin that Shell company produces:
828, its epoxide equivalent weight is 185-195, and the viscosity under about 25 ℃ is about 11,000-15,000 centipoise;
830, its epoxide equivalent weight is 190-198, and the viscosity under about 25 ℃ is about 17,700-22,500 centipoises;
1123, bisphenol-A bromination diglycidyl ether, its molecular weight be about 800 and
834, its epoxide equivalent weight is 230-280, under about 25 ℃ the Gardner-Hall moral viscosity is O-V (with the 70wt% measured in solution in the DEGMBE).
The bisphenol-f diglycidyl ether epoxy resin that is fit to comprises what Shell company produced
DPL8, its epoxide equivalent weight is 166-177, the viscosity under about 25 ℃ is about 3,000-45,000 centipoise; And the bisphenol-f diglycidyl ether epoxy resin of Ciba Chemical company production, such as Araldite GY 281, its epoxide equivalent weight is 158-175, and the viscosity under about 25 ℃ is about 5,000-7,000 centipoise, and Araldite GY 308, its epoxide equivalent weight is 173-182, the viscosity under about 25 ℃ is about 6,500-8,000 centipoise.
Operable other epoxy resin comprises ring grease epoxy resin, such as 3,4-7-oxa-bicyclo[4.1.0 acid 3,4-epoxycyclohexyl methyl esters (RRL 4221 of Union Carbide company), its epoxide equivalent weight is 131-143, and the viscosity under about 25 ℃ is about the 350-450 centipoise; 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3,4-epoxy radicals) cyclohexane trimethylene-formal (ERL 4234 of Union Carbide company), its epoxide equivalent weight is 133-154, the viscosity under about 38 ℃ is about 7,000-17,000 centipoise; Adipic acid 3,4-epoxy-6-methylcyclohexyl methyl esters (ERL 4289 of Union Carbide company), its epoxide equivalent weight is 205-216, the viscosity under about 25 ℃ is about 500-1,000 centipoise.Any epoxy resin or epoxy resin composition that other production firm produces also are operable.
The instantiation of the non-dicyan epoxy prepreg (producing with non-amine hardener) of supply of commodities comprises " Driclad " product that " ATS " that trade mark that GE company provides provides for " TS ", Polyclad company and IBM Corporation provide.
When the preparation laminated plate, it is useful that the reel prepreg of sliver form and Copper Foil are provided.In one embodiment, long Copper Foil and prepreg are produced lamination with continuity method.Under the condition of compressed stack, continuous Copper Foil to be contacted to form laminated construction with continuous prepreg in the method.Then lamination is being cut into the rectangular slab placement or is piling up.
In one embodiment, be that long Copper Foil and prepreg are cut into first rectangle, and then carry out lamination.In the method, rectangular copper foil and rectangle prepreg are placed or are piled up.
Each accumulation body is comprised of a preimpregnation flitch and the copper sheet on its two sides.The laminated plate that accumulation body can be between two plates of laminating machine prepares the sandwich style of prepreg between two copper foils with laminating temperature and the pressure of routine.
Prepreg is comprised of the fiberglass reinforcement of braiding, and with partly solidified second resin dipping.After imposing heat and pressing, Copper Foil is pressed to prepreg tightly, and the temperature that prepreg is accepted has activated resin, and it is solidified, and namely resin is crosslinked, thus Copper Foil is bonded on the prepreg dielectric matrix tightly.In general, the running of lamination comprises the temperature range of the pressure limit of about 250-750psi, about 175-235 ℃ and about 40 minutes-2 hours lamination cycle cycle.Then with the finished product laminate for the preparation of printed circuit (PCB).
In one embodiment, be that laminated plate is led pattern with copper etching null method formation electric lead or electricity, as the subprogram of the circuit board for preparing multilayer.Then second prepreg is attached on the etched pattern.The technology of preparation multilayer circuit board is being known in the art.Equally, the etching null method is also known, and the example is at U.S.5, and is open in 017,271, provides reference at this.
Existing many production methods can prepare printed circuit from laminated plate, and printed circuit board (PCB) also has many possible final application in addition, comprises radio, TV, computer etc.These production methods and final use are known in the art.
The embodiment that the below provides is for the present invention is described.Except as otherwise noted, the umber in embodiment below and entire description and claims and percentage number average refer to weight, and all temperature refer to all degree centigrade that all pressure all refers to atmospheric pressure.
Embodiment 1
Superficial velocity with rotation is that the cylinder negative electrode of 150 feet per minute clocks is 1 ounce/foot with weight
2The asperities of Copper Foil sample of electro-deposition on plating layer of metal zinc, its condition is as follows:
ZnSO
4: Zn
++Ion 0.5 grams per liter
H
3PO
3: P
+++Ion 0.4 grams per liter
Na
2SO
4: 15 grams per liters
Body lotion pH:5.0
Current density: 25 peaces/foot
2
Electroplating time: 20 seconds
Bathe temperature: 37.8 ℃ (100 °F)
The thickness of metallic zinc layer is
With metallic zinc layer and CrO
3Oxidation, CrO are carried out in solution (3.0 grams per liter) contact
3Solution transfers to 5.0 with NaOH with pH, and current density is 18 peaces/foot
2, the time is 10 seconds.The thickness of the trivalent chromium oxide layer that obtains is
Then with sample drying, and sample is immersed in the epoxy silane aqueous solution of 0.5wt% with coating one deck silane coupler.With sample drying.Dry silane coating thickness is about
The treated copper foil that obtains is layered on the non-dicyan prepreg.Prepreg is Polyclad ATS, is a Polyclad company product, is the prepreg made from tetrafunctional epoxy resin and a non-amine hardener through evaluation.Sample carries out initial bonding strength and HCl-etch test.9 pounds/inch of initial bonding strengths, HCl-etch are 13.3%.(the HCl-etch is that sample is immersed in the loss of the percentage peel strength after 1 hour among the 18%HCl)
Embodiment 2
The rotor negative electrode that with superficial velocity is 40 feet per minute clocks is 1 ounce/foot with weight
2The asperities of Copper Foil sample of electro-deposition on plating layer of metal zinc, its condition is as follows:
ZnSO
4: Zn
++Ion 0.62 grams per liter
H
3PO
3: P+++ ion 0.45 grams per liter
Na
2SO
4: 18 grams per liters
Body lotion pH:4.7
Current density: 17.5 peaces/foot
2
Electroplating time: 2.7 seconds
Bathe temperature: 37.8 ℃ (100 °F)
The thickness of metallic zinc layer is
With metallic zinc layer and CrO
3Oxidation, CrO are carried out in solution (3.0 grams per liter) contact
3Solution transfers to 5.1 with NaOH with pH, and current density is 12 peaces/foot
2, the time is 10 seconds.The thickness of the trivalent chromium oxide layer that obtains is
Then with sample drying, and sample is immersed in the epoxy silane aqueous solution of 0.5wt% with coating one deck silane coupler.With sample drying.Dry silane coating thickness is about
The treated copper foil that obtains is layered on the non-dicyan prepreg.Prepreg is Polyclad ATS, is a Polyclad company product, is the prepreg made from tetrafunctional epoxy resin and a non-amine hardener through evaluation.Sample carries out initial bonding strength and HC l-etch test.8.1 pounds/inch of initial bonding strengths, HCl-etch are 17.1%.
The present invention is illustrated with its best specific embodiments, but needs to understand, and after reading specification, various variant forms of the present invention all are apparent for the technology skilful person of the art.Therefore, clearly, disclosed hereinly this invention is intended to cover such variant form, because they are within the scope of appending claims.
Claims (15)
1. laminated plate, this laminated plate comprise dielectric matrix and are attached to treated copper foil on this matrix, the epoxy resin of said dielectric matrix for making with the curing agent that is different from amine hardener,
Described treated copper foil has matsurface and shiny surface:
The matsurface of this Copper Foil has zinc oxide film attached thereto, and described zinc oxide film forms with sexavalence chromium oxide oxidized metal zinc layer, and the thickness of said zinc oxide film is
With
One deck trivalent chromium oxide layer is attached on the said zinc oxide film, and the thickness of said trivalent chromium oxide layer is
Said trivalent chromium oxide layer forms with sexavalence chromium oxide,
Wherein the matsurface of this Copper Foil is undressed before applying the metallic zinc layer.
2. laminated plate claimed in claim 1, wherein said trivalent chromium oxide layer is to use CrO
3, chromyl compound, chromic acid compound or dichromic acid compound form.
3. laminated plate claimed in claim 1 wherein has one deck silane coupler to be attached on the said trivalent chromium oxide layer.
4. laminated plate claimed in claim 3, wherein said silane coupler represents it with following formula:
R
4-nSiX
n
R is the alkyl that sense replaces in the formula, and the sense substituent on the alkyl that said sense replaces is amino, hydroxyl, halogen, mercapto, alkoxyl, acyl group or epoxy radicals; X is hydrolyzable groups; N is 1,2 or 3.
5. laminated plate claimed in claim 3, wherein said silane coupler is two or more mixture of halogenated silanes, aminoalkoxy silane, phenyl silane, heterocycle silane, acrylic silane, mercaptan silane and they.
6. laminated plate claimed in claim 5, wherein said phenyl silane is aminophenyl silane.
7. laminated plate claimed in claim 5, wherein said heterocycle silane is N-heterocycle silane.
8. laminated plate claimed in claim 3, wherein said silane coupler is selected from two or more mixture of aminopropyl trimethoxysilane, tetramethoxy-silicane, tetraethoxysilane, two (2-ethoxy)-3-aminopropyl triethoxysilane, 3-glycidol oxygen propyl trimethoxy silicane, r-chloropropyl trimethoxyl silane and they.
9. laminated plate claimed in claim 8, wherein said aminopropyl trimethoxysilane is selected from 3-(N-styryl methyl-2-aminoethyl is amino) propyl trimethoxy silicane, N-methyl aminopropyl trimethoxysilane, 2-(2-aminoethyl-3-aminopropyl) trimethoxy silane, N-phenylamino propyl trimethoxy silicane and their mixture.
10. each described laminated plate of claim 1-9, wherein said Copper Foil is electro-deposition copper foil.
11. each described laminated plate of claim 1-9, wherein said Copper Foil is the wrought copper Copper Foil.
12. each described laminated plate of claim 1-9, wherein the said shiny surface of said Copper Foil has standard light cleanliness surface.
13. each described laminated plate of claim 1-9, wherein the said shiny surface of said Copper Foil has the best bright finish surface.
14. each described laminated plate of claim 1-9, wherein the said shiny surface of said Copper Foil has catch light cleanliness surface.
15. laminated plate claimed in claim 1, wherein said curing agent is acid, acid anhydrides, alkoxide, phenates, polymerization mercaptan or phenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010217376 CN101890829B (en) | 1999-09-16 | 1999-09-16 | Treated copper foil and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010217376 CN101890829B (en) | 1999-09-16 | 1999-09-16 | Treated copper foil and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99817006A Division CN1384782A (en) | 1998-09-10 | 1999-09-16 | Treated copper foil and process for making treated copper foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101890829A CN101890829A (en) | 2010-11-24 |
| CN101890829B true CN101890829B (en) | 2013-03-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010217376 Expired - Lifetime CN101890829B (en) | 1999-09-16 | 1999-09-16 | Treated copper foil and preparation method thereof |
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|---|---|---|---|---|
| JP6134485B2 (en) * | 2012-07-25 | 2017-05-24 | Ｊｘ金属株式会社 | Metal material having surface for bonding with liquid crystal polymer, metal-liquid crystal polymer composite, method for producing the same, and electronic component |
| CN117070945B (en) * | 2023-10-16 | 2024-02-06 | 瑞浦兰钧能源股份有限公司 | Copper foil and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0557073A1 (en) * | 1992-02-19 | 1993-08-25 | Nikko Gould Foil Co., Ltd. | Copper foil for printed circuits and process for producing the same |
| CN1111685A (en) * | 1994-02-24 | 1995-11-15 | 日本电解株式会社 | Non-cyanide copper-zinc electroplating bath, method of surface treatment of copper foil for printed wiring board using the same and copper foil for printed wiring board |
| US5622782A (en) * | 1993-04-27 | 1997-04-22 | Gould Inc. | Foil with adhesion promoting layer derived from silane mixture |
| US5709957A (en) * | 1994-04-22 | 1998-01-20 | Gould Electronics Inc. | Metallic body with vapor-deposited treatment layer(s) and adhesion-promoting layer |
-
1999
- 1999-09-16 CN CN 201010217376 patent/CN101890829B/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0557073A1 (en) * | 1992-02-19 | 1993-08-25 | Nikko Gould Foil Co., Ltd. | Copper foil for printed circuits and process for producing the same |
| US5622782A (en) * | 1993-04-27 | 1997-04-22 | Gould Inc. | Foil with adhesion promoting layer derived from silane mixture |
| CN1111685A (en) * | 1994-02-24 | 1995-11-15 | 日本电解株式会社 | Non-cyanide copper-zinc electroplating bath, method of surface treatment of copper foil for printed wiring board using the same and copper foil for printed wiring board |
| US5709957A (en) * | 1994-04-22 | 1998-01-20 | Gould Electronics Inc. | Metallic body with vapor-deposited treatment layer(s) and adhesion-promoting layer |
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| Publication number | Publication date |
|---|---|
| CN101890829A (en) | 2010-11-24 |
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