TW406137B - A method of treating copper or nickel foil - Google Patents

Abstract

In one embodiment, the present invention relates to a method of treating metal foil including sequentially contacting the metal foil with a first solution containing either a metal foil oxidizer and less than about 5 g/l of a hydroxide compound or water and at least about 7 ppm dissolved oxygen, contacting the metal foil with a chromium containing electrolytic bath and electrolyzing the bath, wherein the bath contains about 0.1 to about 5 g/l of a chromium compound, and contacting the metal foil with a second solution containing from about 0.1 to about 10% v/v of a silane compound, with the proviso that the metal foil is not contacted with a reducing agent after contact with the first solution.

Description

^-^ '部 屮 " 梂 " Bureau only -1 eliminates the combination of bamboo "-印 ^ A7 __— B7 ___ V. Description of the invention (丨)-TECHNICAL FIELD The present invention relates to a method for processing metal foil, to Added to polymer-based

I plate adhesion. In particular, the present invention relates to a method for treating a metal foil ', which comprises contacting the metal foil with an oxidizing solution, electrolyzing it in a bath containing chromium compound 05, and then contacting it with a silane solution. BACKGROUND OF THE INVENTION Metal foils, such as copper foils, are often laminated onto a dielectric substrate. The resulting laminates undergo numerous processing techniques, as well as unavoidable wear and tear. In this regard, there is a need to propose a laminate having high peel strength. High peel strength allows the laminate to maintain structural integrity during processing (exposure to chemicals and various etchant, such as hydrochloric acid), and general abrasion and tear (heat decay, physical agitation, etc.) β metal The foil is typically treated to increase surface roughness and thereby increase the peel strength of the resulting laminate. However, metal sinks with increasing degrees of surface roughness are prone to "treatment transfer", which is a poor migration phenomenon of metal substances from metal foils to dielectric substrates. Handling transfer decreases the peel strength and degrades the insulating properties of the dielectric substrate. Treatment transfer can also cause unsightly yellow contamination after the metal foil is etched. Therefore, there is a need to propose a metal foil that not only exhibits high peel strength when combined into a laminate, but also does not affect the insulating properties of the dielectric substrate. ------- 3____ This paper is used in the paper scale "« 家 标 今 （） Ｍ 蚬 格 （210x297 公 茇） (Please read the weeping on the back before filling in this KK) Λ. Order A7 B7 5 2. Description of the invention (乂) 406 · ^? · When the metal foil is treated to increase the surface roughness, it is typically an electrolytic method such as electrodepositing a nodular or tree-like copper or

I zinc layer to increase its surface roughness. This method is not only time consuming, but also expensive 'because it requires a huge amount of electricity to apply the nodular copper or zinc layer. Therefore, there is a need to increase the efficiency and cost-effectiveness of processing metal foil. The invention is described in an embodiment, "The present invention relates to a method for treating metal foil." The method includes sequentially contacting the metal fan with a first solution, which contains a metal hafnium oxidant and less than about 5 g / l of Hydroxide, or water containing at least about 7 ppm of dissolved oxygen: contacting the metal foil with a chromium-containing electrolytic bath and electrolyzing the bath, wherein the bath contains about 0.1 to about 5 grams / liter of chromium compound; and The metal foil is brought into contact with a second solution containing about 0.1 to about 10% vol / vol silane compound; however, the limitation is that the gold tin foil does not contact the reducing agent after contacting the first solution. In another embodiment, the present invention relates to a method for treating a metal foil, which includes sequentially contacting the metal foil with a first solution containing a metal foil oxidant and less than 5 g / L of hydroxide. Contacting the metal foil with a chromium-containing electrolytic bath and electrolyzing the bath, wherein the bath contains about 0.1 to about 5 g / liter of chromium compound: and contacting the metal foil with a second solution containing about 0.1 to About 10% vol / vol silane compound: but the limitation is that after the metal foil contacts the first solution, it does not contact the reducing agent. (Please read the notes on the back before filling this page)

T this paper ruler Xiaochuan middle-threshold prisoner; (H · (rNS) M specifications (2 丨 OX2W male f > A7 B7 pair >: 〃 · 部 屮 榡 钧 钧 钧 0 '消 -7 0-7') * '; Private 5. Description of the invention (' In another embodiment, the present invention relates to a method for treating metal foil ', which includes sequentially immersing the metal foil in a first solution, which contains I from about 20 to about About 180 g / L of alkali or alkaline earth metal chlorite or hypochlorite and less than about 3 g / L of alkali or alkaline earth metal hydroxide; after washing the metal foil, if necessary, The metal foil contacts a chromium-containing electrolytic bath and electrolyzes the bath, wherein the bath contains about 1 to about 3 g / liter of a chromium compound, and the metal foil is immersed in a second solution containing about 0.1 to about About 5% vol / vol silane compound: but its limitation is that the metal foil does not contact the reducing agent after being immersed in the first solution. In yet another embodiment, the present invention relates to an improved copper foil and dielectric properties. A method for adhesion between substrates, which includes sequentially: contacting the copper foil with a first solution containing 20 to about 180 g / L of Alkali metal chlorite or hypochlorite, and less than about 5 g / l of alkali metal hydroxide: contact the metal foil with a chromium-containing electrolytic bath and electrolyze the solution, wherein the bath contains About 1 to about 3 g./liter of chromium compound: and contacting the copper foil with a second solution containing about 0.1 to about 5% vol / vol silane compound: but the limitation is that the copper foil is in contact with After a solution, there is no contact with the reducing agent. In another embodiment, the present invention relates to a method for treating metal foil, which includes sequentially: contacting the metal foil with a metal foil oxidant solution, which contains water and at least about 7 ppm of dissolved oxygen: contact the metal foil with a chromium-containing electrolytic bath and electrolyze the bath 'where the bath contains about 0.1 to about 5 grams / I: -------- ^ -----— .η,%--{Please read the precautions on the back and fill in 1ΪΤ page) Wood paper thick scale iSj Chuan threshold g family standard pawn ((, NS) Λ4 grid (210X297 cm) ^ Ο 6 i. δ 7 B7 V. Description of the invention (f) * liter of chromium compound: and bringing the metal foil into contact with a silane solution containing about 0.1 to about 10% vol / vol silicon Compound 1. In another embodiment, the present invention relates to a method for treating a metal foil, comprising: sequentially immersing the metal foil in a metal foil oxidant solution containing deionized water and at least about 7.5 ppm dissolved oxygen: Wash the metal foil as needed: contact the metal foil with a chromium-containing electrolytic bath and electrolyze the bath, where the bath contains about 1 to about 3 g / liter of chromium compound, and dip the metal foil in a solution containing about About 5% by volume / volume of a silane compound in a silane solution. In yet another embodiment, the present invention relates to a method for improving adhesion between a copper foil and a dielectric substrate, which includes sequentially: making the copper The foil contacts a metal foil oxidant solution, which includes water and about 8 ppm to about 20 ppm of dissolved oxygen, thereby forming an oxide layer on the copper foil: contacting the metal foil with a chromium-containing electrolytic bath and electrolyzing the bath, A chromium-containing layer is formed on the oxide layer, wherein the bath contains about 1 to about 3 grams / liter of chromium compound: and the copper foil is contacted with a silane solution, which contains about 0.1 to about 5% volume / volume. Silane compounds Alkoxy-containing silicon layer is formed a layer: copper foil, but with the restriction that after contacting the first solution, the reducing agent is not in contact. As a result of the present invention, it is possible to provide a metal foil that partially exhibits high peel strength because it maintains structural integrity during processing. The hair — 11 ^ ------ installation ----- · order -7. '---(Read the notes on the back first and then fill out this page) Standard 彳 ((NS) Λ4 specification (210X 297 public-) --446x37 _-____ 5. Explanation of the invention (γ) ·, Ming also proposed that the metal foil 'shows little or no when combined into the laminate Handle the transfer phenomenon. 1 Description of the invention The conductive metal foil used in the present invention is preferably conductive copper, and copper cleaning and copper-based alloys are particularly preferred. Other examples include metal, nickel, tin, silver, gold, and others. And other alloys. Metal foils are prepared using one of two techniques. Wrought or rolled metal foils are obtained by mechanically reducing the thickness of copper bars or copper alloy bars or ingots by, for example, rolling. Electrodeposition < Bai Bao 'ία: is made by electrolytically depositing metal ions, such as copper ions, on a rotating cathode cylinder' and then peeling the deposition strip from the cathode. Electrolytic copper foil is a special Preferred. The metal foil typically has a nominal thickness from about 0.0002 inches to about 0.02 inches. The thickness of the metal box is Expressed in weight, the foil of the present invention typically has a weight or thickness of about 1/8 to about 14 ounces per square foot. Particularly useful metal foils are those having a weight of 1/2, 1 or 2 ounces per square foot. And especially copper foil with 1/2, 1 or 2 ounces per square foot. Electrodeposited metal foil has a smooth or shiny (cylindrical) surface, and a rough or dull (before the metal deposition layer grows) Metal foil (electrodepositor or forge) f One or both sides that can be treated according to the present invention may be the rough or matte side, shiny side, or both sides. These sides may be, standard "Contour surface", "Low-profile surface" or "Very low-profile surface," .3 A particularly preferred embodiment includes the use of foils having a matte surface and a standard contour surface., The standard contour sheet is scaled in the middle. K «Housemark Xi-J ---------- Λ ----- Ίΐτ -——: ---- ^-. _--First (please read the precautions before filling in两 本 二) 5. Description of the Invention (t) The term "face" is used herein to refer to a foil surface having an Rtm 値 of about 7 microns to about 12 microns. "Low-profile surface" means Run 値 foil surface with about 7 microns or less. "Very low profile surface" refers to foil surface with Run 値 of about 4 microns or less. Rm is the largest peak measured from every five consecutive samples The average radon of radon is measured vertically from to valley, and can be measured with a Surtronic 3 profilonieter sold by Rank Taylor Hobson, Ltd., Leicester. England. In one embodiment, the It may be characterized as not containing any additional zinc-containing metal layers. That layer includes a zinc layer and a zinc-containing metal alloy layer. In some cases, zinc can adversely interfere with metal foil oxidants, resulting in treated metal foils with undesirable properties. In one embodiment, the metal foil of the present invention may be characterized in that there is no additional surface roughening treatment on the surface of the substrate on one or both sides of the surface treated by the method of the present invention. The term "base surface" on one side of the foil refers to the original foil surface, which has not been treated with any post-treatment of the type discussed below to refine or increase the properties of the foil and / or increase the surface roughness. The term "additional surface roughening treatment" refers to any purpose of increasing the roughness of the foil surface, but not the surface of the foil \ according to the method of the present invention. In one embodiment, the additional surface roughening treatment can increase Rtni 値 by 3 micrometers or more: and in another embodiment, the additional surface roughening treatment can increase Rtm 値 by 10 micrometers or more . ________8__ This paper has a thick scale around the KS furniture in the state ((, NS) Λ4 size (210x29? Mm) I .---------- 4 ----- ΊΪΤ -—— :: --- -^..---(Please read the notes on the back before continuing to write K) __406137 B7__ V. Description of the invention (y) · In one embodiment, a metal treatment with surface roughness will be added, such as copper Treatment is excluded from the method of the present invention. Metal treatment includes substrates on the foil; copper or zinc electrolytically deposited in a nodular or dendritic form on the surface, and copper oxide grown in a nodular or dendritic form. Metal foil with a naturally occurring rather rough surface (sawtooth shape) on the matte surface of the substrate surface is not excluded from the scope of the present invention. In one embodiment, forging is imparted during rolling. The mechanical roughness of the metal foil, or the way to increase its roughness beyond the roughness of a standard contoured surface by subsequent abrasion, is considered an additional surface roughening treatment, and is therefore excluded from its scope according to the present invention. In addition, in one embodiment, the electrodeposited metal foil is given a rough thickness in the electrodeposition. Treatment that makes its roughness exceed that of a standard contour surface, it is also considered as an additional surface roughening treatment. In one embodiment, any roughness is given to the base portion of the metal foil, so that the foil has Increasing the roughness beyond the surface of a standard contour is regarded as an additional surface roughening treatment. In one embodiment, any roughness is given to the base portion of the metal foil, so that the foil has a roughness A treatment that is increased beyond that of a low-profile surface is regarded as an additional surface roughening treatment. In one embodiment, any roughness of the base portion of the metal foil is imparted to increase the roughness of the foil to Treatments exceeding those of very low-profile surfaces are considered as additional surface roughening treatments. In one embodiment, the base surface of one or both sides of the metal foil is untreated before being treated by the present invention The word "untreated" I, --------------'-(Please read the precautions and fill in this page.) This paper is WK! 家 标 in Sichuan rNS > Λ4 specification (2 丨 0X 297 males) A7 B 7 Five 'description of the invention (also). In this context refers to the surface of the substrate of the metal foil, which has not been subsequently treated for the purpose of refining or enhancing the properties of the foil and / or increasing the surface roughness. In an embodiment' The untreated plutonium has naturally occurring non-dendritic or non-nodular copper oxide, or another metal or metal alloy layer adsorbed on the surface of its substrate. These naturally-occurring non-dendritic layers are not another In one embodiment, the substrate surface on one or both sides of the foil is subjected to one or more of refined or reinforced coriander, or stomach, before receiving the treatment of the invention, but not to increase surface roughness The surface treatment layer has been treated for the purpose of the degree. $ Any foil surface that has been treated by the method of the present invention can be treated with one or more of them as needed. These surface treatments are all in the art. For example, the surface treatment includes adding a metal layer that does not increase the surface roughness before the method of the present invention is performed, wherein the metal is 絪, tin, chain, inscription, copper alloy. Copper-tin alloy 'and a mixture of two or more of them. This type of metal layer is sometimes referred to as a barrier layer. These metal layers preferably have a thickness in the range of about 0.01 to about i micrometers, and more preferably about 0.05 to about 0.1 micrometers. Such surface treatments also include the application of a metal layer that does not increase surface roughness before the practice of the present invention, wherein the metal is tin, nickel, molybdenum, molybdenum, or a mixture of two or more of them. Sometimes this type of metal layer _ _ 10__ This paper scale uses the Chinese Fujian family standard 埤 ((, NS) Λ4 present grid (2 丨 0 乂 297 fundraising) one '" ~~~~ 1 -— ^ 11 — I— In n II— I IJI • One. (Please read the following :; x meanings, then fill in the page on this page j. V. Description of the invention (Α7 Β7 are called stabilization layers). These stabilization The layer can be applied to the substrate surface of the foil, or they can be applied to the barrier layer I which has been added beforehand. Such stabilizers preferably have a thickness of about 0.005 to about 0.05 microns, and more preferably about 0.01 Thickness in the range of about 0.02 microns. In one embodiment, one or both sides of the foil are first treated with at least one barrier layer. In another embodiment, one or both sides of the foil are first treated with at least one stabilizer layer Treated. In yet another embodiment, before carrying out the method of the present invention, one or both sides of the foil are treated with at least one barrier layer, and then at least one of the treated sides is treated with at least one stabilization layer. Treated. The metal foil according to the present invention may be a single-layer metal foil, such as a copper foil, an aluminum foil Or a nickel foil, or a metal alloy foil. The metal foil according to the invention may be a foil containing multiple layers of metal or metal alloy, such as foils made of multiple layers of copper and brass. For any given contained metal foil The number of layers is not particularly limited. The method of the present invention includes performing at least three steps in sequence. First, the metal foil is contacted with a metal foil oxidant solution. The metal foil is subsequently contacted with a chromium-containing electrolytic bath and electrolyzed. After that, The metal foil is brought into contact with a silane solution. The term "sequentially" means that the three steps are performed in the listed order = that is, the contact with the chromium-containing electrolytic bath must be performed while the metal foil is in contact with the metal foil oxidant solution. Then, and before contacting the silane solution. However, the three steps do not necessarily have to be performed immediately after each other, because 11 I 7 ^ -1 I---.........-^^- —II 1 ——J--JI < '--(Read the precautions on the back before filling in this page) This paper is suitable for middle school prisoners in Sichuan «Housemark 綷 ((' NS) Λ4 size (210X 297 male f) ) 4 A7 _ B7 V. Description of the invention π) Additional steps may be implemented. For example, after the metal foil is contacted with the metal foil oxidant solution, but before the metal foil is contacted with the chromium-containing electrolytic bath, a washing step may be performed. Therefore, the term "sequentially" means What are the two necessary steps of the method of the present invention, rather than any additional steps in various embodiments of the method of the present invention = In one embodiment, the method of the present invention includes contacting a metal tank with an acidic solution. The acidic solution has A pH value below about 5, and preferably below about 3, and more preferably below about 2. The acidic solution contains an acid and a solvent, such as water, polar organic liquids, such as alcohols and glycols, and mixtures thereof I .---------- .. * 4 ----- ilix • -,. (Please read the precautions on the back before making this page.) Contacting metal foil with an acidic solution is used to remove surface oxides from the metal foil and to clean the surface of the metal foil. In addition, contact with an acidic solution facilitates subsequent processing steps. Metal foil is contacted with an acidic solution by any conventional means, including but not limited to impregnation, spraying, wiping, immersion and the like. In the preferred embodiment, the gold foil is immersed in an acidic solution. In another embodiment, the temperature of the acidic solution is from about 20 ° C to about 60 ° C, and more preferably about 30 ° C to about °. 40. The acidic solution contains at least one acid and a suitable solvent, which is typically water. However, other organic liquids can also be used, or water and polar organic liquids. Specification of Λ4 (2 丨 297 public dream) Α7 Β7 4061 ^ V. Combination of invention description (\ 丨) *. Both inorganic and organic acids can be used, but inorganic acids are preferred. Inorganic acids can be used in acidic liquid Specific examples include halogen acids such as

I I .----------- A ------- Order ', I. (Please read the precautions before completing this page) Hydrofluoric acid, hydrochloric acid, Hydrobromic acid and hydroiodic acid, sulfuric acid, sulfurous acid, nitric acid, perchloric acid, boric acid and phosphoric acids such as phosphorous acid and phosphoric acid, and combinations thereof. Nitric acid and sulfuric acid are the preferred inorganic acids. Examples of organic acids include carboxylic acids and polycarboxylic acids such as formic acid, acetic acid, propionic acid, citric acid, oxalic acid, and the like: organic phosphoric acids such as dimethylphosphoric acid and dimethylphosphonic acid: or sulfonic acids such as methanesulfonic acid, ethane Sulfonic acid, 1-pentanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, and the like, and mixtures thereof. In a preferred embodiment, after the metal foil is contacted with the acidic solution, the metal foil is optionally washed with a neutral solution, and in most cases it is washed with water, preferably deionized water. . The rinsing solution preferably does not contain a high degree of dissolved oxygen (especially in the embodiment where an oxidizing solution containing water and dissolved oxygen is used. In addition to neutralizing or washing the solution, the surface of the metal foil is neutralized. In addition, it is also used to remove excess acid from the surface of the metal foil. 4 '·' ^ · Ministry of Justice, only T &C; " Bamboo " Ink This metal foil is related to metal foil Contact with an oxidant solution, which contains a metal foil oxidant and a hydroxide, or water containing an amount of dissolved oxygen sufficient to oxidize the surface of the metal foil. The metal foil is contacted with the solution by any conventional means, including immersion, Spray cloth, wipe, dip and the like, but it is better to immerse the metal foil in this solution. No current is required to be applied. In one embodiment, the metal foil contains metal foil oxidant and hydrogen · _____ 13____ + Paper Size Shizhou KS House Standard (C, NS) Μ 蚬 格 (2 丨 OX 297 mm) 铒 " .Ministry of Central Standards and Technology Bureau β-τ Consumer Bamboo Seal, 5i A7-V. Invention Explanation (丨 Xi) Oxide metal foil oxidant solution contact. Implemented here The temperature of the solution is about 10 ° c to about 90 ° c, and more preferably about 40 ° c to about 80 ° c1. In one embodiment, the metal foil is placed in the metal foil oxidant solution It is about 2 to about 20 seconds, and more preferably about 5 to about 10 seconds. A metal foil oxidant is a chemical that can oxidize the surface of a metal foil. Metal foil oxidants include ammonium, alkali metal, and alkaline earth metal oxidants. " The term "ammonium" is used to include both ammonium ions (NH /) and organic ammonium ions, such as tetramethylammonium, tetraethylammonium, tetrapropylammonium, and tetrabutylammonium ions. Alkali metals include lithium, sodium, potassium, and rivet, of which Preferred are sodium and potassium. Alkaline earth metals include beryllium, magnesium, calcium, and total barium, of which magnesium and calcium are preferred. Examples of metal foil oxidants include ammonium, alkali and alkaline earth metal chlorites, hypochlorites. Salt, nitrate, nitrite, percarbonate, perborate, perchlorate, periodate and persulfate. Specific examples include ammonium nitrate, ammonium perchlorate, ammonium persulfate, tetramethyl nitrate Ammonium, tetraethylammonium sulfate, sodium chlorite, sodium hypochlorite, sodium nitrate, sodium nitrite, perboron Sodium, sodium percarbonate, sodium perchlorate, sodium periodate, sodium persulfate, potassium nitrate, potassium nitrite, potassium perborate, potassium perchlorate, potassium periodate, potassium persulfate, thallium nitrate, perchloric acid Fine, magnesium nitrate, magnesium perchlorate, calcium hypochlorite, calcium nitrate, calcium perchlorate, nitrate saw, and perchloric acid bonds. Preferred metal foil oxidants include sodium hypochlorite, sodium chlorite, and sodium persulfate. The content of the metal foil oxidant in the solution is about 20 to about 180 g / L, and preferably about 30 to about 170 g / L, and more preferably about 50 to about I · *: ···· Γ ^ —--fn--I —il (_ 士 I--II · i—- ~ 一 ^.-≪-(Please read the notes on the back before writing this page) Chinese KK family block net (rNS) Λ4 specifications (2IOX2V7 mm) A7 B7 V. Description of the invention (160 g / l. ! Hydroxide is any compound that provides hydroxide ions in solution. Examples of hydroxides include hydroxides of ammonium, alkali metals and alkaline earth metals. Pending examples of hydroxides include ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide. The hydroxide content in the solution is less than about 5 g / l, preferably less than about 3 g / l, more preferably less than about 2 g / l, and more preferably less than about 1.5 G / l. In this embodiment, the metal foil oxidant solution contains a suitable solvent such as water, a polar organic liquid such as an alcohol and a glycol, and / or a mixture thereof. Preferred is an aqueous solution. The metal foil oxidant solution may contain various additives. In one embodiment, the ratio of the metal foil oxidizing agent to the hydroxide expressed in grams per liter is at least about 20: 1. In another embodiment, the ratio of the metal foil oxidant to the hydroxide is at least about 30: 1. In a preferred embodiment, the ratio of the metal foil oxidant to the hydroxide is at least about 50: 1. In a preferred embodiment, the metal foil oxidant to hydroxide ratio is at least about 60: 1. This ratio is required for a proper reaction between the oxidizing solution and the metal foil. In this embodiment, the thickness of the oxide layer is about 50 to about 250 A. ____ \ 5______ This paper is happy to play with KH3 family logo (rNS) in Tongchuan according to the specifications (2 丨 0X 297 male ") --J-- -— J— I--n III n I nn TI nnn IIV-Λ.-----(Please read the precautions on the back before filling in this education) 5. Description of the invention (〖+), but less than Approximately 250 A. In another embodiment, the thickness of the oxide layer obtained on the metal foil is about 75 to about 200 A, but less than about 200 A. In another embodiment 1, the thickness of the obtained oxide layer on the metal foil is about 100 to about 175 A, but less than about 175 A. A solution containing a metal foil oxidant results in the formation of an oxide layer on the metal foil. As a result of the relatively low amount of hydroxide contained in the solution, the quality of the oxide layer is improved. This result is partly due to the formation of a needle-like black oxide layer. As a result, the laminate containing the metal foil treated according to the present invention can obtain increased peel strength without the need to electrolytically treat the metal foil. In another embodiment, the metal foil oxidant solution contains water and contains a sufficient amount of dissolved oxygen to oxidize the surface of the metal foil. In this embodiment, the temperature of the metal foil oxidant solution is about 2 ° C to about 50 ° C. In another embodiment, the temperature of the metal foil oxidant solution is about 4CTC to about 4CTC. In yet another embodiment, the temperature of the metal foil oxidant solution is about 15 ° C to about 30t. In one embodiment, 'the metal foil is in contact with the metal foil oxidant solution for about i to about 100 seconds. In another embodiment, the metal foil is contacted with the metal foil oxidant solution for about 2 to about 50 seconds. In yet another embodiment, the metal foil is contacted with the metal foil oxidant solution for about 5 to about 25 seconds. In a preferred embodiment, 'the water is deionized water, but it is also possible to use a paper-like degree iii, and close $ 财 (rNsTu ^ (210X 297 ^ 7 —, —-------- .. * Clothing — .--(Please read the notes on the back first, and then write two more) Order A7 B7__ V. Description of the Invention ((<) 'Tap water. The water of the metal foil oxidant solution contains at least about 7 ppm of dissolved oxygen. In a preferred embodiment, the water of the metal foil oxidant solution contains about

I 7.5 ppm dissolved oxygen. In one embodiment, the water contains about 8 ppm to about 20 ppm of dissolved oxygen. In another embodiment, the water contains about 9 ppm to about 15 ppm of dissolved oxygen. Water containing a specified degree of dissolved oxygen can be obtained by obtaining a relatively high degree of dissolved oxygen, or by aerating with pure oxygen or an oxygen-containing gas until the desired degree of dissolved oxygen has been reached. Oxygen-containing gases include air and oxygen and one or more emotional and non-reactive gases, such as a mixture of hydrogen, nitrogen, helium, neon, argon, krypton, and xenon. During the implementation of the method of the present invention, the metal foil oxidant solution may be exposed to air periodically or continuously to maintain a desirable minimum level or range of dissolved oxygen. The degree of dissolved oxygen in the metal foil oxidant solution can be measured periodically or continuously by any means known to measure the dissolved oxygen content. For example, one device is available from the Yellow Springs Instrument Company under the trade name YSI Model 57 Series Dissolved Oxygen Meter. A pharmaceutical method based on the Winkler method can also be used. Dissolved oxygen reagent group, using burette titration method, digital titrator method, or titration method, dissolved oxygen agent AccuVac® needle tube, and Pocket ColorimeterTM to measure dissolved oxygen are available from Hach Company. In this embodiment, the metal foil oxidant solution is free of metals as required: that is, the metal foil oxidant solution is characterized by not containing additional metals or metal compounds. Trace metals or metal compounds in tap water and deionized water can be tolerated. In another embodiment, the metal foil oxidant is soluble -------- 17 wood paper scale thorns in the house standard ^ (CNS) AAim (210 X 297¾ ^-one {read the precautions on the back first (Fill in this page) Order V. Description of the invention (4) ~ The solution does not contain organic solvents; that is, the metal foil oxidant solution is characterized by the absence of additional organic solvents. In yet another embodiment, in tap water or to

I-ion water may contain small amounts (less than about 2% by weight or less than about 1% by weight.) Of organic solvents. The oxide layer 1 formed by the contact of the metal film with the metal foil oxidant solution is very thin. In another embodiment, the thickness of the oxide layer is about 1 to about 25 A 'but less than about 25 A. In another embodiment, the thickness of the oxide layer obtained on the metal foil is about 2 to about 20 A, but less than about 20 A. In another embodiment, the thickness of the obtained oxide layer on the metal foil is about 3 to about 15 A, but less than about 15 A. A metal foil oxidant solution containing water and at least 7 ppm dissolved oxygen results in a relatively thin oxide layer on the metal foil. As a result of the solution containing a certain amount of dissolved oxygen, the quality of the oxide layer is increased. This is partly because the metal foil oxidant solution is not an aggressive oxidant, but can inhibit the formation of a needle-like black oxide layer. As a result, in the laminate including the metal foil treated according to the present invention and not subjected to electrolytic treatment, an increased peel strength can be obtained. In most cases, especially when an oxidizing solution containing an oxidizing agent and a hydroxide of a metal foil is used, after the metal foil has contacted the oxidizing solution, the metal foil is no longer in contact with the reducing agent. Reducing agents can adversely affect the metal foils that have been exposed to oxidizing solutions, especially metal foil oxidizers (please read the precautions on the back before filling this page)-± 4. K house standard 彳 ((, NS > Λ4 specification (210X 297 牦)) __AQ6l3 ^ V. Description of the invention (q) B7 has a surface. As a result of not contacting the reducing agent, it contains the metal foil treated according to the present invention. Increased peel strength is obtained in the laminate. Reducing agent I includes formaldehyde, hypophosphite, osmium, and amine borane. Reducing agents also include cyclogenic gases, such as from lower carbon number alcohols, aldehydes, and low carbon number carboxylic acids And its esters, ammonia, osmium, nitrogen-containing low-carbon amines, metal hydrides, and boron compounds derived from catalytic pyrolysis. Catalytic pyrolysis includes the production of hydrogen or carbon monoxide gas. In a preferred embodiment, the metal After the foil has come into contact with the oxidation solution of the metal foil, the metal foil is rinsed with a neutral solution if necessary, and in most cases water and specific deionized water are used. Neutralizing or rinsing solutions are used Remove from the surface of the metal foil Remaining oxidants and / or hydroxide ions. After the metal foil has been in contact with the metal foil oxidation solution and rinsed as necessary, the metal foil is placed in a chromium-containing electrolytic bath. The chromium-containing electrolytic bath contains An aqueous solution of a chromium compound and an optional performance-enhancing additive. An electric current is applied to the bath to cause a cathodic chrome layer to be electrolytically deposited on the metal foil. The chromium compound can be any metal foil capable of being deposited on the metal foil. A thin cathode chrome yellow or chromium layer compound is deposited. Examples of chromium compounds include chromium oxides such as chromium trioxide, chromic anhydride, chromic acid, hexavalent chromium compounds: dichromates such as potassium dichromate and heavy Sodium chromate: and chromates, such as potassium chromate, sodium chromate, and magnesium chromate. The content of the chromium compound in the chromium-containing electrolytic bath is about 0.1 to about 5 g / l, and preferably about 1 Up to about 3 g / l. _____19 This paper is from Du Hongzhou, Fujian and Fujian (('NS) Λ4 is now standard (2ΚΪΧ297)) --------- .. * 衣-(碕 read first Note on the back again, 4 this page j

The Ministry of Social Depression 屮 ^ UT Consumer Assets Co., Ltd. V A7__4 __ 5. Description of the Invention (0)-The performance-enhancing additives used as needed include zinc compounds, such as zinc salts (eg, zinc acetate, zinc chloride) , Zinc cyanide, zinc nitrate, and zinc sulfate), and phosphorus-containing compounds such as phosphoric acid, phosphorous acid, polyphosphoric acid, pyrophosphate, phosphate, pyrophosphate, and polyphosphate. In one embodiment, the temperature of the chromium-containing electrolytic bath in the electrodeposition step is about 15 ° c to about 30 ° c, and preferably about 20 ° c. To about 25 ° c. The pH of the chromium-containing electrolytic bath is determined by the nature of the particular chromium compound used in the particular embodiment and is therefore not critical. In one embodiment, the current density applied to the chromium-containing electrolytic bath is from about 10 to about 40 ASF. In another embodiment, the current density is about 15 to about 35 ASF, and more preferably about 20 to about 30 ASF. The metal foil is placed in the chromium-containing electrolytic bath for a time sufficient to form a relatively thin but uniform cathode chrome yellow layer on the surface of the metal foil treated with the metal foil oxidant. In one embodiment, the metal foil is placed in a chromium-containing electrolytic bath for about 2 to about 20 seconds, and more preferably about 5 to about 10 seconds. In one embodiment, the thickness of the obtained cathode chrome yellow layer is about 25 to about 125 A. In a preferred embodiment, the thickness of the obtained cathode chromium layer is about 50 to about 100 A. The thickness of the cathode chrome yellow layer is substantially uniform over the entire surface of the metal foil and follows any height on the surface of the metal foil. In a preferred embodiment, after the metal foil has come into contact with the chromium-containing electrolytic bath solution, the metal foil is washed with a neutral solution as needed ', and in most cases • _20_ This paper's inversion is applicable in "« Family standard (rNS) Λ4 is now (2 丨 O x 297 cm) (Please read the precautions on the back before filling in this page},-° Jing " 'Ministry of the Ministry? Hand " Bureau only -7 elimination 贽Printed by Hezhusha A7 B7 V. Description of the invention (p · Medium water and special deionized water. The neutralizing or washing solution is used to remove any remaining bath liquid on the surface of the metal foil Solution., 1 After the metal foil has been contacted with the metal foil oxidation solution and the chromium-containing electrolytic bath, the metal foil is contacted with a solution containing a silane compound in a suitable solution. The content of the silane compound in the solution is about 0_1 To about 10 ° / .vol / vol, preferably about 0.2 to about 5 ° / .vol / vol, and more preferably about 0.3 to about 3% vol / vol. The preferred silane compound is a silane coupling agent The preferred silane coupling agents are amine-silane compounds, epoxy-silane compounds, and alkoxy In one embodiment, the silane compound can be expressed by the following formula:-G4 I R1-Si-Ge I G5-η where G1, G2, G3, G4, G5 and G6 are independent Ground is halogen, hydrocarbyloxy, or hydroxyl: R1 is hydrocarbyl or nitrogen-containing hydrocarbyl: and η is 0 or i. In one embodiment, G1, G2, G3, G4, G5, and G6 are each independently chlorine, Alkoxy, alkoxyalkoxy, or alkoxyalkoxyalkoxy, and R1 is an alkylene or aromatic hydrocarbon group having up to about 10 carbon atoms, or a single group having up to about 10 carbon atoms Amine- or polyamino-substituted alkylene or aromatic hydrocarbon groups. In one embodiment, G1, G2, G3, and G6 are each an alkoxy group with up to 10 carbon atoms. (Please read the notes on the back first (Refill this page)

A * π G2 G'—Si-G3 The scale of this paper is suitable for "Prisoner's House Mark (('NS) Λ4) (210 × 297 mm) 5. Description of the Invention (〆 >). , Alkoxyalkoxy or alkoxyalkoxyalkoxy, and η is 0 ° | Examples of these silane compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra-n-butane Oxysilane, tetra (2-ethoxyethoxy) silane, osmium (2-ethylbutoxy) silane, tetra (2-ethylhexyloxy) silane, tetra (methoxyethoxyethoxy) ) Silane, tetra (2-methoxyethoxy) silane, tetra (1-methoxy-2-propoxy) silane, bis- [3- (triethoxysilyl) propyl] amine , Bis- [3- (trimethoxysilyl) propyl] ethylenediamine, 1,2-bis (trimethoxysilyl) ethane, bis (trimethoxysilylethyl) benzene, 1.6 -Bis (trimethoxysilyl) hexane, 1,2-bis (trichlorosilyl) ethane, 1.6-bis (trichlorosilyl) hexane, and 1,8-bis- (trichlorosilyl) ) Octane. In another embodiment, the silane compound may be a compound represented by the formula: R4 I R2 — S i ——R5 I R3 where R2, R3, R4, and R5 are independently hydrogen, halogen, alkoxy, hydroxyl, and organic functional groups, and these organic functional groups are on another substrate (such as prepreg) (prepreg)) Reactive or affinity. Organic functional group ________ 22_ ^^ 1 In i HI. Ruler--I i -i-In m * In--eJtiw {Please read the back Note for refilling this page) This paper 仄 X 度 谪 州 屮 1¾¾1 house standard (('NS) Λ4 specification (210X · 297 male f > 4061 ^ S V. Description of the invention (> /) ~ For example Including amine-containing, amine-containing, hydroxyl-, alkoxy-, hydrocarbon-containing ethyl, aromatic, heterocyclic, propyl-containing, epoxy-containing, hydrogen-containing sulfur A carboxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and a propylene methoxy group. In one embodiment, R3 ′ R4 and R5 are each chlorine, methoxy or ethoxy ′ and R2 is an organic functional group. In one embodiment, R4 and R5 are each chlorine, methoxy or ethoxy, and R2 and R3 are organic functional groups. Examples of such silane compounds include tetramethoxysilane: Tetraethoxysilane: diamine silicon Alkane; N- (2 · aminoethylamino) -3-aminopropyltrimethoxysilane: 3- (N · styrylmethyl-2-aminoethylamino) -propyltrimethoxy Silane: 3-aminopropyltriethoxysilane: bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane; / 3- (3,4-epoxycyclohexyl)- Ethyltrimethoxysilane: 3-glycidoxypropyltrimethoxysilane: 3-methacryloxypropyltrimethoxysilane; 3-chloropropyltrimethoxysilane: vinyltrichloro Silane: vinyltriethoxysilane; vinyl-tris (2-methoxyethoxy) silane; aminopropyltrimethoxysilane; N-methylaminopropyltrimethoxysilane: N-phenyl Aminopropyltrimethoxysilane, 3-Ethoxypropyltrimethoxysilane: N- (3-propenyloxy-2-hydroxypropylaminopropyltriethoxysilane: 3-propene Methoxypropyltrimethoxysilane: allyltriethoxysilane: allyltrimethoxysilane: 4-aminobutyltriethoxysilane: (aminoethylaminemethyl) phenethyl Trimethoxysilane: N- (2-aminoethyl-3-aminopropyl) trimethoxysilane: N- (2-amine Ethylethyl-3-aminopropyl) tri (2-ethylhexyloxy) silane; 6- (aminohexylaminopropyl) trimethoxysilane: aminophenyltrimethoxysilane: 3- (1-Aminopropoxy) -3,3-dimethyl-I-propylene _________23__ This paper size K1¾ house in Luzhou. (('NS) Λ4 size (210x297 public dream) (read first) Note on the back of the achievement, please fill out this page again} 妓 ️ # 部 屮 央 标 标 局 wt, consumption cooperation rights printed VJ A 74061¾ «_B7__ V. Description of the Invention (V >)-Trimethoxysilane: 3-amino group Propyltri (methoxyethoxyethoxy) silane: 3-aminopropyldiethoxylate: ω-aminoundecyldimethoxydioxane: 3-P-N- Benzylamine ethylaminopropyl) trimethoxysilane: bis- (2-merylethyl) -3-aminopropyltriethoxysilane: 8-bromooctyltrimethoxysilane: bromophenyl Trimethoxysilane: 3-bromopropyltrimethoxysilane: 2-chloroethyltriethoxysilane: p- (chloromethyl) phenyltrimethoxysilane: chloromethyltriethoxysilane: chlorine Phenyltriethoxysilane: 3-chloropropyltriethoxysilane: 3-chloropropyltrimethoxysilane : 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane: 3- (cyanoethoxy) -3,3-dimethyl-1-propenyltrimethoxysilane: 2-cyano Ethylethyltriethoxysilane: 2-cyanoethyltrimethoxysilane: (cyanomethylphenethyl) trimethoxysilane: 3-cyanopropyltriethoxysilane; 3-cyclopentyl Diallyltriethoxysilane; (N, N-diethyl-3-aminopropyl) trimethoxysilane; diethylphosphate ethyltriethoxysilane; (N, N- Dimethyl-3-aminopropyl) trimethoxysilane: 2- (diphenylphosphino) ethyltriethoxysilane: 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane: 3-iodopropyltrimethoxysilane: 3-isocyanatopropyltriethoxysilane: 3-hydrothiopropyltriethoxysilane: 3-hydrothiopropyltrimethoxy Silane: methacryloxypropenyl trimethoxysilane: 3-methacryloxypropyltrimethoxysilane; 3-methacryloxypropyltri (methoxyethoxy) silane : 3-methoxypropyltrimethoxysilane; N.methylaminopropyltrimethoxysilane: 0-4-methylcoumarin -N- [3- (triethoxysilyl) propyl] carbamate; 7-oct-1-enyltrimethoxysilane: N-phenethyl-N'-triethoxy Silylpropylurea: N-phenylaminopropyltrimethoxysilane; 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane ______24_ This paper is suitable for Sichuan Valve S house standard 肀 ((, is) 8 4 specifications (21〇-, 297 公 #) (Please read the note f on the back before filling tt? Page) ^ installed.

1T A7 B7 V. Description of the invention (8)-: 3-thiocyanopropyltriethoxysilane; triethoxysilylpropyl) ethynylglycinamine: N- (triethoxy Silylpropyl) dimethylaminonaphthalenesulfonamide; N- [3- (triethoxysilyl) propyl] -2,4-dinitroaniline: triethoxysilylpropylethyl Aminocarbamate: N- [3- (triethoxysilyl) -propyl] -4,5-dihydroimidazole; N-triethoxysilylpropyl-o-ylaminomethyl Ester: 3- (triethoxysilylpropyl) -p-nitrobenzamide; N- [3 · (triethoxysilyl) propyl] phthalamide; N- (tri Ethoxysilylpropyl) urea: 1-trimethoxysilyl-2- (p-, m-chloromethyl) phenylethane; 2- (trimethoxysilyl) ethylbenzylidene Nitrogen: / 3-trimethoxysilylethyl-2-pyridine: trimethoxysilyl octyltrimethylammonium: trimethoxysilylpropyl cinnamate: N- (3-trimethoxy chloride Silylpropyl) _N-methyl N, N-diallylammonium; trimethoxysilylpropyldiethylene triamine: N [(3-trimethoxysilyl) propyl 1 ethylene Diamine triethyl Acid trisodium salt: trimethoxysilylpropylisosulfide chloride: N- (3-trimethoxysilylpropyl) pyrrole: N · trimethoxysilylpropyltri-n-butylammonium bromide : N-trimethoxysilyl chloride-N, N, N-trimethylammonium chloride; vinyltriethoxysilane: vinyltriisopropoxysilane: vinyltrimethoxysilane: vinyltri- Tertiary butoxysilane: vinyltris (2-methoxyethoxy) silane; vinyltriisopropenylsilane; vinyltri (thirdbutoxy) silane: 2-ethoxyl Ethyltrichlorosilane: 3-propenyloxypropyltrichlorosilane: allyltrichlorosilane: 8-bromooctyltrichlorosilane: bromophenyltrichlorosilane: 3-bromopropyltrichlorosilane: 2- (methoxycarboxy) ethyltrichlorosilane: 1-chloroethyltrichlorosilane: 2-chloroethyltrichlorosilane; p- (chloromethyl) phenyltrichlorosilane: chloromethyltrichlorosilane ： Chlorophenyltrichlorosilane: 3-chloropropyltrichlorosilane: ____25_ Ruler * Claws 屮 家家 标 冷 (rNsTAWJL 格 (210X297 公 势 1 ~ ') (Please read the precautions on the back before filling this page } Order Α7 Β7 V. Invention (Battle) · 2- (4-Chlorosulfonylphenyl) ethyltrichlorosilane; (3-cyanobutyl) trichlorosilane: 3-cyanopropyltrichlorosilane: (dichloromethyl) Trichlorosilane, · (dichlorophenyl) | Trichlorosilane: 6-hexyl-1-enyltrichlorosilane: 3-methacryloxypropyltrichlorosilane: 3- (4-methoxy Phenyl) propyltrichlorosilane: 7-oct-1-enyltrichlorosilane: 3- (N-peptidylimino) propyltrichlorosilane: p-trichlorosilyl-2- (p, m · Chloromethylphenyl) ethane: 4- [2- (trichlorosilyl) ethyl] cyclohexene: 2- [2- (trichlorosilyl) ethyl] pyridine: 4- [2- ( Trichlorosilyl) ethyl] Pyridine: 3- (trichlorosilyl) propylchloroformate: and vinyltrichlorosilane. Mixtures of two or more of the silane compounds listed above may also be used. For example, in one embodiment, the silane compound is N- (2-aminoethyl-3-aminopropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane or 3-propylene oxide. Combination of oxypropyltrimethoxysilane and tetraethoxysilane or tetramethoxysand. The silane solution may be in the form of a dispersion or solution in water, a water / alcohol mixture, or a suitable organic solvent, or in the form of an aqueous emulsion of a silane mixture, or in the form of an aqueous emulsion of a solution of a silane compound in a suitable organic solvent. Conventional organic solvents can be used. They include alcohols, ethers, ketones, and mixtures of them with aliphatic or aromatic hydrocarbons or waves and the like with amidines such as N, N-dimethylformamide. Useful solvents are those with good wetting and drying properties, and include, for example, water, ethanol, isopropanol, and methyl ethyl ketone. Aqueous emulsions of silane compounds can be formed in a conventional manner using conventional dispersants and surfactants, including non-ionic dispersants. The metal foil and the silane solution __. 26 (Please read the precautions on the back before filling this page) -2¾ Γ This paper is according to the standard 迖; 丨 1 Chinese domestic standard 彳 (rNS > Λ4 now (210X 297) ()). "Ministry of China's decision standard ^ only -1 eliminate ^; Zhu Zhu" seal * ': ^ 406137 __ 5. Description of the invention (> <) * The contact steps can be repeated as necessary However, a single step usually yields useful results, and therefore the use of a single step is usually the better one. The contacting is done by known coating methods, including reverse roller coating, Squeegee coating 'dip coating' for immersion, brushing and spraying. The silane solution is typically at a temperature of about 5 ° C to about 45 ° C, and more preferably about 2 ° C to about 30 ° T. After the treated metal foil is brought into contact with the silane solution, the metal sink can be heated to about 60 ° F. (31 °? 170 t :, more preferably about 90 ° C to 150 ° C. The temperature is ~ about 3 to 5 minutes. 'Better' is about 0.2 to about 2 minutes to enhance surface drying. The dry film thickness of the silane compound on the metal foil is better. It is about 0 002 to about 0_1 micrometers, more preferably about 0.005 to about 0.02 micrometers. In one embodiment, 'the electrolysis step is not performed after the metal box has been treated according to the present invention. In another embodiment' Except for the electrolysis step that includes a chromium-containing electrolytic bath, no other electrolysis steps are performed. There is no additional electrolysis step that simplifies the production method of the metal fan 'and simplifies the processing and manufacture of the laminates used for printed circuit boards. The metal box can be bonded to the substrate to provide size and structural stability. The metal box treated in the present invention can enhance the bonding or peel strength between the processed metal foil and the substrate. These processed metals The advantage of the foil is that this kind of Fan can avoid the additional copper surface roughening treatment, or other electrolytic treatment, and still can show the dielectric base _ __27__ ^ paper size command used in Chinese «家 标 岭 ( < 'NS) A4% grid (2 ^ 0 ^ 297 public dance)' ---

mV., one m · one (Please read the notes on the back before filling in ft? This page J __406137 _ ^ __ V. Description of invention (> G) Effective bonding or peel strength of the board. Their foils can have a standard profile surface , Low-profile surface and even very low-profile surface, and still provide desirable peel strength. When using the foil of the present invention, any of its matte side or shiny side can be effectively bonded to the dielectric substrate Available substrates can be made by impregnating glass fiber fabric reinforced materials with impregnated resins, usually epoxy resins (such as difunctional, tetrafunctional, and multifunctional epoxy resins). Other available resins Including amine-based resins made from the reaction of formaldehyde with urea or the reaction of formaldehyde with melamine, polyester, phenolic resin, silicone, polyamine, polyimide, diallyl phthalate, phenylsilane , Polybenzimidazole, diphenyl ether, polytetrafluoroethylene, cyanate, and the like. These dielectric substrates are sometimes called prepregs. In the preparation of laminates: it is useful to use prepregs With metal foil to take the length of a roll Metal foils (webs) are provided. In one embodiment, 'these long metal foils and prepregs are laminated together in a continuous manner. In this procedure, the process of attaching an adhesion promotion layer is provided. Process the continuous sheet of metal foil and contact the prepreg material continuously under the conditions of lamination to form a laminated structure. Then cut this laminated structure into rectangular pieces, and then stack or assemble the rectangular pieces into an assembly stack. For example, these metal foils and prepregs are cut into rectangular pieces first, and then stacked. In this procedure, the metal foil rectangular pieces and prepreg rectangular pieces are stacked or assembled to form an assembly stack. __________— J8_____ Wood Paper Chinese SK family logo 4 *. (('NS) M is now grid (2 丨 OX 297 public) (Please read the precautions on the back before reading this page), ν9% Good ^ Ministry of Bank of China, only -T . ^ ilv ^ e.TI ^ pt 406181 ^ __ 5. Description of the invention (> p · Each assembly can include a prepreg sheet, and a treated metal foil on any side of it, and in each In the case, the treated metal foil

The surface of I (or one of the two surfaces) is arranged close to the prepreg β, and then the assembly can be subjected to a conventional lamination temperature and pressure between the laminated plates to prepare a prepreg clip Laminate between treated metal foils. The prepreg may be composed of a woven glass-reinforced fabric impregnated with a partially hardened two-stage resin. By applying heat and pressure, the copper foil is tightly pressed against the prepreg, and the temperature to which the assembly is subjected activates the resin to promote its hardening, that is, the crosslinking of the resin, so that the foil is tightly bonded to the pre-preg. Immersion dielectric substrate. In summary, the lamination operation includes a pressure in the range of about 250 to about 750 psi, a temperature in the range of about 175 ° C to 235 ° C, and a lamination cycle of about 40 minutes to about 2 hours. The finished laminate can then be used to make printed circuit boards (PCBs). In one embodiment, a subtractive copper etching process is performed on the laminate to form conductive lines or patterns as part of a process for manufacturing a circuit board. Then, using the technique discussed above, a second treatment is performed on the etched pattern, and a second piece of prepreg is adhered to the etched pattern: the second-treated metal foil face is configured to two etched The pattern is adhered to the second prepreg. Those who are familiar with the technology of manufacturing multilayer circuit boards are similarly familiar with the method of subtractive engraving. An example is disclosed in the U.S. Patent No. __M_, Heychang; < 1 KPjJ Family Standard ((, NS) Λ4 specifications (210X297 public power): --- rL ------ lt ------ order -----; --φ --- Γ J •--』 --(诮 Please read the notes on the back before filling in the ftT page) ___ ΛΠ (ν; λ7 Β7__ V. Inventive note (Μ) '5,017,271, which is incorporated herein by reference, there are many manufacturing methods available from Laminates are used to prepare PCBs. In addition, there are many possible end-use applications for PCBs, including radios, televisions, computers, etc. These methods and end-uses are known in the art. An advantage obtained by the present invention is: according to the present invention The obtained treated metal foil exhibits high peeling strength when combined into a laminate. This is because the method of the present invention allows the treated metal foil to maintain structural integrity during processing of the treated metal foil. Another advantage is that the treated metal foil, when combined into a laminate, exhibits a very good Little or no treatment transfer phenomenon. Another advantage is that the treated metal foil has increased resistance to, for example, hydrochloric acid that may come into contact with the treated metal foil. Without being intended to be so limited, the following examples It is used to clarify the various and novel parts of the present invention. Unless stated otherwise, in the following examples and throughout the specification and patent application, all parts and percentages are calculated by weight, and all temperature units are degrees Celsius And all pressures are atmospheric pressure. Example 1 A copper foil was immersed in a solution containing 150 g / L of sodium chlorite 'and 2 g / L of sodium hydroxide for about 15 seconds at about 80 ° C. Copper The foil was washed in deionized water. An aqueous electrolytic bath containing 2 g / l of chromium trioxide was prepared. _________30_ This paper is a scale suitable for the Sichuan family standard ((.NS > Λ'ί 忧 枋 (2 丨 OX297)) ) ^^^ 1 mn ^ — nn I ·.. 11¾ ^ n In ^^^ 1 I--^^^ 1 V4J-n One----(Please read the notes on the back before filling this page) 406 丄 37 B7___ 5. Description of the invention (> /) · Place the copper foil in the bath And a current density of 25 ASF was applied for 15 seconds. The copper foil was washed again in deionized water. The copper foil was then immersed in a solution containing volume / volume diamine silane and 0.5% volume / volume epoxy. An aqueous solution of silane was allowed to dry. Example 2 A copper foil was immersed in a solution containing about 140 g / L of sodium chlorite and 3 g / L of sodium hydroxide for 5 seconds at about 70 ° C. The copper foil was washed in deionized water. An aqueous electrolytic bath containing 1 g / L of chromium trioxide was prepared. The copper foil was placed in the bath, and a current density of 20 ASF was applied for 18 seconds. The copper foil was washed again in deionized water. The copper foil was then immersed in an aqueous solution containing 1% v / v diaminosilane and allowed to dry. Example 3 A copper foil was immersed in a solution of about 60 ° C, containing 120 g / L of potassium chlorite, and 1-5 g./L of potassium hydroxide for 8 seconds. Wash the copper foil in deionized water. An aqueous electrolytic bath containing 3 g / L of chromium trioxide was prepared. The copper foil was placed in the bath, and a current density of 15 ASF was applied for 20 seconds. The copper foil was washed again in deionized water. The copper foil was then immersed in an aqueous solution containing 0.5¾ vol / vol epoxy epoxy alkane and allowed to dry. Example 4 The copper foil was immersed at about 50 ° C., Containing 100 g / liter of sodium chlorite, and _______31_ This paper music scale cap 1¾ 彳: ㈣ ((, 1 ^ 丁 / \ 4 size (210 / ^ 97 public dream) one " --II ------- A ------- order ---------- Mi, 丨------(诮 Please read the notes on the back before filling out this page) The Department of Du Bi's ten times quasi-station only-χ 消 贽 合 竹 · 社Yinfan 406137 B7 V. Description of the invention (々〇) 10 seconds in a 1 g / L sodium hydroxide solution. Wash the copper foil in deionized water. Prepare 4 g / L chromium trioxide. Aqueous electrolytic bath β The copper foil was placed in the bath, and a current density of 15 ASF was applied for 20 seconds. The copper foil was then washed in deionized water. The copper foil was then immersed in a solution containing 3% by volume / Volume of an aqueous solution of diaminosilane and allowed to dry. Example 5 A copper foil having a brass stabilization layer was immersed at about 70 ° C., Containing 0 g / L of sodium chlorite, and 2 g / L. Liter of sodium hydroxide solution for 15 seconds. Rinse in deionized water. Prepare an aqueous electrolytic bath containing 0.5 g / L chromium trioxide. Place the multilayer metal foil in this bath and apply a current density of 35 ASF for 20 seconds. The multilayer metal foil After washing in deionized water, the multilayer metal foil was immersed in an aqueous solution containing 2% vol / vol of 3-glycidoxytrimethoxysilane and allowed to dry. Example 6 A nickel foil was immersed in About 803C, 15 seconds in a solution containing 150 g / L of sodium chlorite, and 2 g / L of sodium hydroxide. Wash the nickel foil in deionized water. Prepare 3 g / L of chromium trioxide. Aqueous electrolytic bath. The nickel foil was placed in the bath, and a current density of 25 ASF was applied for 15 seconds. The nickel foil was washed again in deionized water. The nickel foil was then immersed in a solution containing 1% by volume / Volume N · [3- (triethoxysilylpropyl] -4,5-dihydroimidazole and volume / volume tetraethoxysilane in an aqueous solution and allowed to dry ___ · _32 wood paper scale 蝻State KK Family Mark (rNS) Λ4 Specification (210X297 male) ----------- *-"-(Please read the notes on the back before filling This K)

* 1T ": · '^. The Ministry of Samples and Tenths of the Precise Bureau only worked in Hezhu. She printed *' '' 406137 5. Description of the Invention (々I). I Example 7 The copper foil was immersed in a solution containing oxygen at 8.8 ppm dissolved oxygen in deionized water at about 20 ° C for 5 seconds. Rinse the copper foil in deionized water. An oxide layer with a thickness of about ΠA was detected on the foil. An aqueous electrolytic bath containing 2 g / L of chromium trioxide was prepared. The copper foil was placed in the bath, and a current density of 15 ASF was applied for 5 seconds. The copper foil was washed again in deionized water. The copper foil was then immersed in an aqueous solution containing 1% v / v diamine silane and 0.5% v / v epoxysilane and allowed to dry. Example 8 A copper box was immersed in a solution containing about 205C of oxygen in deionized water and containing 8.8 ppm dissolved oxygen for 10 seconds. Rinse the copper box in deionized water. An oxide layer with a thickness of about 9A was detected on the foil. An aqueous electrolytic bath containing 1 g / L of chromium trioxide was prepared. The copper foil was placed in the bath, and a current density of 20 ASF was applied for 18 seconds. The copper foil was washed again in deionized water. The copper foil was then immersed in an aqueous solution containing 1% v / v diaminosilane and allowed to dry. Example 9 A copper fan was immersed in a solution containing about 7.5 ppm dissolved oxygen in deionized water at about 25 ° C for 5 seconds. Place the copper foil in deionized water ___33 Wood Paper Music Scale Linzhou Zhongjia Standard Mark (('NS) Λ4 Specification (2ίΟχ297 公 漦) ----------- Λ ------ -Order 1 (Please read the notes on the back before filling in this page) 406: 37 b7 V. Description of the invention (Washing. An oxide layer with a thickness of about 16A was detected on the foil. The preparation contains 3 g / L Aqueous electrolytic bath of chromium trioxide. The copper foil is placed in the bath

I and apply a current density of 15 ASF for 10 seconds. The copper foil was washed again in deionized water. The copper foil was then immersed in an aqueous solution containing 0.5% v / v epoxysilane and allowed to dry. Example 10 A copper foil was immersed at about 15 ° C. For 10 seconds in a solution containing 7.4 ppm dissolved oxygen when oxygen was passed through deionized water. Rinse the copper box in deionized water. An oxide layer with a thickness of about 5 A was detected on the foil. An aqueous electrolytic bath containing 3 g / L of chromium trioxide was prepared. The copper foil was placed in the bath, and a current density of 15 ASF was applied for 10 seconds. The copper foil was washed again in deionized water. The copper foil was then immersed in an aqueous solution containing 0.5% v / v epoxysilane and allowed to dry. Example 11 A copper foil was immersed at about 15 ° C for 15 seconds in a solution containing 7.4 ppm dissolved oxygen when oxygen was passed through deionized water. Wash the copper fan in deionized water. An oxide layer with a thickness of about 8A was detected on the foil. An aqueous electrolytic bath containing 3 g / L of chromium trioxide was prepared. The copper foil was placed in the bath, and a current density of 15 ASF was applied for 10 seconds. The copper foil was washed again in deionized water. The copper foil was then dipped in containing 0.5α '. The volume / volume of the epoxysilane is in an aqueous solution and allowed to dry. _____34_ This paper is scaled with Gyuan S House Standard ((’NS) Λ4 is present (210X 297 public dream) (Please read the precautions on the back before filling this page)

I

IT A7 A7 Okay, Huanbu decided to quasi fishing -T; (, ifr ^ '0 · Seal $ 4fHjl37-V. Description of the invention U3) · Example 12 The copper foil was immersed at about 18 ° C, containing Pass oxygen in deionized water to the solution containing 10PPm dissolved oxygen for 5 seconds. Rinse the copper foil in deionized water. An oxide layer with a thickness of about 9A was detected on the foil. An aqueous electrolytic bath containing 4 g / L of chromium trioxide was prepared. The copper foil was placed in the bath, and a current density of 15 ASF was applied for 5 seconds. The copper foil was washed again in deionized water. The copper foil was then immersed in an aqueous solution containing 3% v / v diamine silane and allowed to dry. Example 13 A copper foil having a brass stabilization layer was immersed in a solution containing about 10 sec. Of a solution containing 10 ppm of oxygen dissolved in oxygen in deionized water. The multilayer metal foil was washed in deionized water. An oxide layer with a thickness of about 6A was detected on the foil. An aqueous electrolytic bath containing 0.5 g / L of chromium trioxide was prepared. The multilayer metal foil was placed in the bath, and a current density of 25 ASF was applied for 3 seconds. The multilayer metal foil was washed again in deionized water. The multilayer metal foil was then immersed in an aqueous solution containing 2% vol / vol of 3-glycidoxytrimethoxysilane and allowed to dry. Example 14 A nickel foil was immersed in a solution containing oxygen permeated in deionized water and containing 10 ppm dissolved oxygen for 15 seconds. Rinse the nickel foil in deionized water. An oxide layer with a thickness of about 7A was detected on the foil. An aqueous electrolytic bath containing 3 g / L of chromium trioxide was prepared. Put the nickel foil in the bath (please read the precautions on the back first and then make this page), order-line ____15___ A7 __406137 5. In the description of the invention (that is, f), and apply a current density of 15 ASF for 10 seconds Zhong Zhong. The nickel foil was washed again in deionized water. Then dip the nickel foil in a volume containing 1% vol / vol

I > 1- [3- (triethoxysilyl) -propyl] -4,5-dihydroimidazole and 1% by volume / volume of tetraethoxysilane in an aqueous solution and allowed to dry. Although the present invention has been described in terms of its preferred embodiments, it should be understood that: those skilled in the art can understand various methods after reading this specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover their modifications within the scope of the appended claims. (Please read the precautions before filling this page): ¾¾. The Ministry of Rong 榡 榡 扃 扃 Only disappeared in the seal of Hezhu Society * ')? :: Paper I standard 36 public 7 29 * TJ · I-. 1-^ ---- T LT ·

Claims (1)

6. Scope of patent application i. A method for processing copper or nickel foil, which includes: I n Ϊ nn I 1 · II (Please read the precautions on the back before filling this page) Make the copper or nickel foil contact A first solution containing a copper or nickel foil oxidant and a hydroxide of less than or equal to 3 g / L, or water and at least 7 ppm dissolved oxygen, contacting the copper or nickel foil with a chromium-containing electrolyte Bath and electrolyze the bath, wherein the bath contains 0.1 to 12 g / L of chromium compound; and the copper or nickel foil is contacted with a second solution containing 0.1 to 10% vol / vol of silane compound ' However, the limitation is that the copper or nickel foil does not contact the reducing agent after contacting the first solution. The copper or nickel foil oxidant is selected from the group consisting of chlorite compounds, hypochlorite compounds, and persulfuric acid. At least one of the salt compounds, wherein the hydroxide is a hydroxide or ammonium hydroxide of an alkali metal or an alkaline earth metal, wherein the chromium compound is a chromium oxide, and wherein the copper or nickel foil oxidant is g / l 値The ratio of grams to liters of this hydroxide is at least 20 to 1 . 2. The method of claim 1 in which the first solution includes less than 3 g / L of hydroxide. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3. If the method of the first scope of the patent application, it further includes contacting the copper or nickel foil with an acidic solution before contacting the first solution, and washing the Copper or nickel foil. ^ The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1. If the method of the scope of the patent application is No. 3, where the acid solution package 2 1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 B8 406137 g8s_ 6. The scope of patent application includes at least one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. 5. As for the method of claim 1 in the scope of patent application, it is further restricted that the copper or nickel foil is characterized as not containing a zinc-containing metal layer. 6. A method for improving the adhesion between a copper foil and a dielectric substrate, which includes sequentially: contacting the copper foil with a first solution containing 20 to 180 g / L of alkali metal chlorite Or hypochlorite and an alkali metal hydroxide of less than or equal to 3 g / L; contacting the copper foil with a chromium-containing electrolytic bath and electrolyzing the bath, wherein the bath contains 0.5 to 4 g / L A chromium compound; and contacting the copper foil with a second solution containing 0.1 to 5% vol / vol silane compound, but the limitation is that the copper foil does not contact the reducing agent after contacting the first solution, wherein The chromium compound is a chromium oxide. 7. The method according to item 6 of the patent application, wherein the first solution comprises 50 to 160 g / L of alkali metal chlorite or hypochlorite. 8. The method of claim 6 in which the first solution includes less than 3 g / L of sodium hydroxide. 9. For the method of applying for item 6 of the patent scope, wherein the first solution pack 2 paper sizes are applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) nn · 1 n I. · ϋ n 1 n 1 I! ^-° 4 It n ϋ I-"-(Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs AS B8 eg έΜ1Z2__ VI. The scope of patent application includes less than 3 G / L of alkali metal hydroxide. 10. The method of claim 6 of the patent application scope further comprises contacting the copper foil with an acidic solution before contacting the first solution, and washing the copper box if necessary 11. The method as claimed in claim 6 of the patent scope further comprises washing the copper foil after the copper foil contacts the first solution. 12. The method as claimed in claim 6 wherein the alkali metal chloride The ratio of g / L of gadolinium or hypochlorite to g / L of alkali metal hydroxide is at least 50 to 1. 13. A method of improving the adhesion between the copper foil and the dielectric substrate A method comprising: sequentially contacting the copper foil with a metal foil oxidant solution, comprising: Water and 8 ppm to 20 ppm of dissolved oxygen to form an oxide layer on the copper foil; contact the copper foil with a chromium-containing electrolytic bath and electrolyze the bath to form a chromium-containing layer on the oxide layer Layer, wherein the bath contains 1 to 3 g / l of chromium compound; and contacting the copper foil with a silane solution containing 0.1 to 5% vol / vol of silane compound to form a chromium-containing layer on the chromium-containing layer Silane layer. 14. The method according to item 13 of the scope of patent application, in which the oxide layer has 3 ^ -------- ^ 5 ·? I · '---- line-*-· (Please read first Note on the back, please fill out this page again) This paper size is applicable to the national standard (CNS) A4 specification (210 X 297 mm) A8 A8 C8 D8-Shed 137 6. The thickness of the patent application range is 1 to 25A. 15. Such as The method of claim 13 in which the temperature of the metal foil oxidant solution is 15 ° C to 3 ° C, and the copper foil is in contact with the metal foil oxidant solution for 2 to 50 seconds. The method according to item 13, wherein the thickness of the oxide layer is less than 15 A. Π. The method according to item 13 in the scope of patent application, wherein the chromium The compound is chromium oxide. ΙΙΙΙΙΙΙΙΙΙΙΙΙ—, · 1111111 ίτI- I 1. IIII I. • V, (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economy China National Standard (CNS) A4 specification (210 X 297 mm) No. of case No ............. JSjl h-—T ^ r less Λ c Supplement A4 C4 Ministry of Economic Affairs ^. ^ 5: 4 QH: Industry ^ / 1% ¾ Printed by the cooperative 11 _Patent Specification Λ〇 Invention 1. Method Chinese name for processing copper or nickel box New English A Method of Treating Copper or Nickel Foil Name (1 > Thomas J. Aming, Stuart A. Li Lai_ Invention, — '· / \-Creative Nationality I Residence, Residence (1) USA 44060, Mando, Golanga No. 6818 Lin Plaza (2) 8307 Lutian Road, Palma, Ohio 44129, USA Name (Name) Nationality of the Gould Electronics Company III. Applicant's residence, residence (office) United States. Ohio 44095, East Lake Gettys Road 34929 Name of Representative Michael A. Sentney 1 This paper size applies to China Standard (CNS) A4 grid (210X297 mm)% 12, 10 amended A5 B5 IV. Abstract of Chinese invention (Name of the invention: -11 '--- 4061S7 method for processing copper or gun foil in one embodiment, The invention relates to a method for treating metal foil, which comprises sequentially contacting the metal foil with a first solution, which contains a metal box oxidant and less than about 5 g / L hydroxide, or water and at least About 7 ppm of dissolved oxygen; contacting the metal foil with a chromium-containing electrolytic bath and electrolyzing the bath, wherein the bath contains about 0.1 to about 5 g / liter of a chromium compound; and contacting the metal foil with The second solution of the silane compound is about 0.1 to about 10% vol / vol; however, the limitation is that the metal foil does not contact the reducing agent after contacting the first solution. (Please read the notes on the back, and then fill out the columns on this page) English Abstract of Invention (Name of the Invention: A Method of Treating Copper or Nickel Foil Ordered by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed in one embodiment, the present invention relates to a method of treating metal foil including sequentially contacting the metal foil with a first solution containing either a metal foil oxidizer and less than about 5 g / l of a hydroxide compound or water and at least about 7 ppm dissolved oxygen / contacting the metal foil with a chromium containing electrolytic bath and electrolyzing the bathf except the bath contains about 0.1 to about 5 g / l of a chromium compound, and contacting the metal foil with a second solution containing from about 0.1 to about 10% v / v of a silane compound, with the proviso that the metal foil is not contacted with a reducing agent after contact with the first solution- The size of the wire paper is applicable to China National Standard (CNS) A4 (210X297 mm) 6. Scope of patent application i. A method for processing copper or nickel foil, which includes: I n Ϊ nn I 1 · II (Please read the precautions on the back before filling this page) Make the copper or nickel foil contact A first solution containing a copper or nickel foil oxidant and a hydroxide of less than or equal to 3 g / L, or water and at least 7 ppm dissolved oxygen, contacting the copper or nickel foil with a chromium-containing electrolyte Bath and electrolyze the bath, wherein the bath contains 0.1 to 12 g / L of chromium compound; and the copper or nickel foil is contacted with a second solution containing 0.1 to 10% vol / vol of silane compound ' However, the limitation is that the copper or nickel foil does not contact the reducing agent after contacting the first solution. The copper or nickel foil oxidant is selected from the group consisting of chlorite compounds, hypochlorite compounds, and persulfuric acid. At least one of the salt compounds, wherein the hydroxide is a hydroxide or ammonium hydroxide of an alkali metal or an alkaline earth metal, wherein the chromium compound is a chromium oxide, and wherein the copper or nickel foil oxidant is g / l 値The ratio of grams to liters of this hydroxide is at least 20 to 1 . 2. The method of claim 1 in which the first solution includes less than 3 g / L of hydroxide. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3. If the method of the first scope of the patent application, it further includes contacting the copper or nickel foil with an acidic solution before contacting the first solution, and washing the Copper or nickel foil. ^ Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1. For the method in the scope of patent application No. 3, where the acid solution contains 2 1